Physical Methods (Russell S. Drago)

f
PRO ERTIES OF SELECTED NUCLEI

Sensitivity Magnetic
NMR ro;' Equal Numbers 01 Moment, Electric
Frequency in Nuclel in multiples ,Quadrupole Anisotropic
p"yiz.ata at al of'nuclear 1, Moment, Q Hyperfine
7.0463 T ,4bOl)dance ;::on tant constant 'magneton in multiples In multiples Coupling, B
Isotope Fleld % field Irequeny (e",4n me) 01 h/2n f10-
2
'cm
2
In MHz
b
.IH
300.000 1000 1.000 2.79270 1/2
.2H
46.051
...
9.64 x 10-
3
0.409 0.85738 1 2.77 x 10-
3
.6Li
44.146
,. 8.51 x 10- 3
0.392 0.82191 1 4.6 x 10-
4
.7Li
116.5
c
"'2.57
0.294
.1.94
3.2560 3/.2
,4.2x 10-
2
. 9Be
42.16( 100
1.39 x 10-
2
0.703 1.1774 3/2'.
l 2 X 10- 2
672
.
1O
B
32.239 18.83 1.99 x 10-
2
i:n
),8'006 '
3 0.111 17.8 -672
,IIB
96.251 81.17 0.165 1.60 2.6880 3/2
3.55 x 10-
2
53.1 2,020
,I3C
75X2 1.108
1.59 x 10-
2
0.251 0.70216 1/2 90.8 3,110
.
14
N
21.611 99:635 1.01 x 10-
3
0.193 0.40357 1 2 x 10-
2
47.8 1,540
.
15
N
30.398 0.365
1.04 x 10-
3
0.101 -0.28304 1/ 2 -67.1 -2,160
.
17
0
40.670 3.7 x 10-
2
2.91 X 10-
2
1.58 - 1.8930 5/2
-4x 10-
3
-144 -4.628
.
19
F
282.231 100 0.834 0.941 2.6273 1/2 1515 47,910
.
23
Na
79.353 100 9.27 x 10-
2
1.32 2.2161 3/2 0.1
.
25
Mg
18.358 10.05 2.68 x 10-
2
0.714 -0.85471 5/2
.27Al
78.172 . 100 0.207 3.04 3.6385 5/2 0.149 59 2,746
.
29
Si 59.595 4.70
7.85 x 10 -
2
0.199 -0.55477 1/2
-86.6 -3.381
.31p
12t:442 100 6.64 x 10-
2
0.405 1.1305 1/2 287 10,178
.33S
23.009 \ 0.74
2.26 x 10- 3
0.384 0.64274 3/2
-6.4 x 10-
2
78 2,715
35CI
29.395 75.4 4.71 x 10-
3
0.490 0.82089 3/2
-797 x 10-
2
137 4,664
.37C\
24.6
2.72 x 10-
3
0.408 0.68329 3/2
-6.21 x 10-
2
117 3.880
.,
.
39
K ,,24.467 t 93.08 5.08 x 10-
4
0.233 0.39094 3/2 23
.'
., . .
43
Ca .;W,184 0.13 6.39 x 10-
2
1.41 -1.3153 7/2
.
45
SC 72.882 100 0.301 5.10 4.7491 7/2
1,833
.47;fi
16.910 7.75
2.10 x 10-
3
0.659 -0.78712 5/2
-492
. 16.914 5.51
3.76 x 10,- 3
1.19 - 1.1023 7/2
-492
.5}y
78.864 100 0.383 5.53 5.1392 7/2 0.3 2,613
.
53
tr 16.956 9.54
1.0 x 10-
4
0.29 -0.4735 3/2
-630
.55-Mn
73.993 100 0.178 2.89 3.4610 5/2 0.5 3,063
57Fe
9.693 2.245 :::;;0.05 450
.
59
CO 70.842 100 0.281 4.83 4.6388 7/2 0.5 3,666

4.6
5 x 10-
2
4.3 3.0 5?
611'.i'
26.808 1.25 3.52 x 10-
3
<0.25 1,51
.
63
CU 79.515 69.09 9.38 x 10-
2
1.33 2.2206 3/2 -0.15 4,9
.
65
CU 85.183 30.91 0.116 1.42 2.3790 3/2
-0.14 5,305
.
67
Zn 18.762 4.12 2.86 x 10-
3
0.730 0.8735 5/2
1,251
.
69
Ga
72.009 60.2
6:93 x 10-
2
1.201 2.0108 3/2 0.2318
.
71
Ga 91.485 39.8 0."i4L- 1.525 2.5549 3/2 0.1461
"
.
73
Ge 10.465 7.61 1.40 x JO-
3
1.15 -0.8768 9/ 2
.
.
75
As" 51.380 100
2.51 x 10-
2
0.856 1.4349 3/2 0.3 255
. 77S
e
57.203 7.50 6.97 x 10-
3
0.191 0.5333 1/2 376
.
79
Br
75.160 50.57 7.86 x 10-
2
1.26 2.0990 3/2 0.33 646
.
81
Br 81.018 49.43 9.84 x 10-
2
2.2626 3/2
0.28 696
.
85
Rb 28.965 72.8 1.05 x 10-
2
1.3483
5/2
0.31
*Magnetic moment measured by nmr.
t Radioaclive.
.Experimental hyperfine couplings as measured using the atomic-beam technique [See P.'Kusch and H. Taub. Pbys Rev., 75, 1477 (1949).]
a The magnetogyric ratio can be obtained from YN =J.lNtl{-
b Anisotroplc hyperfine couplinggiven by
2
"
B=- h-
l
g,vPNgp(r -
3
)
' 5
where (r- 3) is computed for a valence p electron from self-consistent-field wave functions. The couplings are such that the principal values ofthe
tensor are respectively - i, -1,and +2times the' lumber quoted. . ., '
e Isotrpic hyperfine coupling given by
8n _1 2
AO =- h gNPNgPlofJ,(O)1
3
where jI,(O) is the value ofthe valence-shell, self-consistent-field Swave function al the nucleus ofthe neulral atom.
NMR Relative Sensitlvlty

,soment, /lN"
..... . Elettr.. . . , , .., . ., ....
Isotropic Frequency in lar Equal Numbers 01 in multlples .' . Quad'l!lpole' :.dI{6.Qrroprc . :', Isotropic ... :..
e
r 8
Hyperfine
Coupling, A"
in MHz
c
Isotope
MHz at a
7.0463 T
Field
Natural
Abundance
% ,..,
.,
Nuciei at
. constant
field
! 01 nuclear
.magneton
(e,,/4rr: mc)
"'Moment, Q ': Hypei'tine '1
in mll.ltlpllis:", multipls ,,0 Coupllng: p'
orh/2rr: ' 0110 -
2
"cm
2
, in MHZ'"
f'"
Hyperfine
Coupling, AG, .
in MHz
c
1.420
218
.
87
Rb
.
87
Sr
98.163
13.001
'27.2'
7.02
0.177
2.69 x 10- 3 "
2.7415
-1.0893
j !ifY
9/2
"

"',... ,
jf- .
3,417*
152* .
89
y 14,697 100 1.17 x'1O -
4
. -0.1368
lJ2 ..
402*
672
- 672
2,020
3,110
1,540
91Zr
.9'Nb
.
95
Mo
.
97
Mo
.99Ru
lOlRu
27.991
73,328
19.554
19,557
10.169
14.824
11.23
100 -'
15.78
9.60
12.81
16.98
9.4 x 10-
3
0.482
3.22, .x 10;- 3 .
3.42 X iO- 3 ,.
_
,
'. -1.3
" 6.1435
,
-0.9290
5/2
9/2
5/2.

)/2
- 0.4 0.3
-3,528
- 3,601
- 2,160
.103Rh 9.442
100
3.12 x 10 - 5 -0.0879 1/2 .
-4.628 105Pd 13.728 22.23 7.79 X 10-
4
-0.57 5/2
47,910
886*
. 107Ag
. 109Ag
12.139
13.956
51.35
48.65
6.69 x 10- 5
1.01 X 10-
4
-0.1130
-0.1299
1/2
1/ 2
."
-3,520
, -4,044
.lllCd 63.616 12.86 9.54 X 10-
3
- 0.5922 1/2
2,746
-3381
10,178
.113Cd
.
115
In
.
117
Sn
66.548
65.742
106,875
12.34
95.84
7.67
1.09 X 10-
2
0.348
4.53 x 10 -
2
- 0.6195
5.5072
-0.9949
1/2
9/2
1/2
1.161
2,715
4,664
3.880
.1 19Sn
,
121
Sb

123
Sb
111.817
71.791
38.878
8.68
57.25
42.75
5.18 X
0.160
. 4.57 x
10-
2
10-
2
-1.0409
3.3417
2.5334
1/2
5/2
7/2
-0.8
- 1.0
,
-.
.1.
231 ,.. .125Te

127
1
94,790
60.021
7.03
lOO
3.16 X
9.35 X
10-
2
10 -
2
-0.8824
2.7939
1/2
5/2 -0.75
(o . :
_lo _'-
,
f
.. .av.f:
I? t . -.
1,833 .
129
Xe 80.981 26.44 2.12 X 10-
2
1/2 } .
-492
-492
2,613
177Hf
l79Hf
l81Ta
9.361
5.609
35,910
18.39
13.78
100
6.38 X 10 -
4
2.16 X 10-
4
3.60 x 10-
3
2.1
7/2
9/2
7/2 6.5
" t
, fI.
- 630
3,063
450
3,666

183
W
.
185
Re
.
187
Re
. 1
89
0 S
12.48
67.541
68.233
23.276
14.28
37.07
62.93
16.1
7.20 X 10-
4
0.133
0.137
2.24 x 10-
3
0.115
3.1437
3.1760
0.6507
1/2
5/2
5/2
3/2
2.8
2.6
2.0
_t '''''_
..
1,512
191Ir
193Ir
5.156
5.614
38.5
61.5
3.5 X 10-5
4.2 X 10 - 5
0.16
0.17
3/2
3/2

1.0
"
-.
4,952 .
195
pt 64.447 33.7 9.94 X 10-
3
0.6004 1/2
5,305
197Au 5.138 100 2.14 X 10-5 0.136 3/2 0.56
1,251
,199Hg 53.481
16.86 5.72 X 10-
3
0.4993 1/2
201Hg 19.799 13.24
1.90 x 10- 3 -0.607 3/2 0.5
,203Ti
,z05Ti
171.448
173.124
29.52
'70.48
0.187
0.-192 .
1.5960
1.6114 ..
1/2
1/2
9,582
,207Pb 62.765
21.11 9.13 x 10-
3
.' . 0.5837 1/2
13,468
,209Bi 48.208
100 0.137 4.0389 9/2 -0.4
21,738 Free E1ectron 197.246 2.85 x 10
8
-1836 1/2
23,432 1= 2.00
1,012*
b
6lvvIG f\1J --le.':'
of the traceJes.
..
' ;0 " ,
,..
.J...f.t I
:J- . -:;.s 4lC\j
Physical
Methods lor
Chemists
SECON D ED T o N
RUSSELL S. DRAGO
University of Florida, Gainesville
Saunders College Publishing
Harcourt Brace Jovanovich College Publishers
Ft. Worth Phil adel phia San Diego New York Orlando Austin
San Antonio Toronto Montreal London Sydney Tokyo
Preface
The revIsion of my earlier textbook, "Physical Methods in Chemistry," was
motivated by a sense of gratitude to those who continued to use the book even
though several parts were out of date. Those parts of the last edition that remai n
current have not been changed. As in the earlier edition, topics have be n
subdivided into numbered paragraphs so sorne can be dropped, if desired,
permitting use of the text in either a theoretical or more applications-oriented
course.
The popularity of the earlier edition is based on the recogni tion that there
is more to the application of physicaJ methods in chemistry than memorizing
where functional groups appear. Core material in the area of spectroscopy is
presented that is of importance to both organic and inorganic chemists. This
text is designed to reftect this unity. A fundamental subdivision of chemistry
involves dividing it into systems that do and do not contai n unpaired d-eJeclrons.
The material in this book has been so subdivided. In using Ihis book, a chemist
with an interest in organic or organometallic sysnt hesis can omit Chapters 10,
11, 12, and 13.
This book contains more material than can be covered reasonably in a
one-semester course. Accordingly, several methods in less common usage (Moss-
bauer, NQR, surface techniques) are presented in a succinct, basic manner. in
this way, the reader is at least made aware of their existence.
The book continues in the philosophy of the earlier edtion, namely, that
chemists without an advanced mathematical background learn to use spectro-
scopic methods by reading about how problems ha ve been solved with them.
Thus, the text relies heavily on examples whi ch illustrate the kinds of information
that can be obtained by application of the methods. Whenever a choice exists
regarding the selection of an application, an example from my own research has
been chosen, for 1 am most famili ar with the details of this work. 1 recommend
that instructors supplement this material with examples reftecting their particular
interests. Hopefully, more widespread knowledge of the core material in this text
will upgrade or at least make the reader more critical of conclusions from
spectroscopic measurements. 1 feel Ihis is one of the important contributions of
the earlier text and the original motivation for writing this book.
This text has evolved from the author' s presentation of courses in physical
methods. He gratefully acknowledges tlle contri butions to the development
of this material by the faculty, teaching assistants, and students involvd, v
particularly those mentioned in earlier editions. 1 appreciate very much the fine
contributions to this edition by Ivano Bertini, Claudio Luchinat, Arnie Rhein-
gold, and Joe Ziller, who found the time to help a friendo Thanks go to Kitty
Williams for Figure 8-25, Dave Powell for suggestions on the mass spectroscopy
section, and to Roy King for many valuable comments and a very thorough
review of Chapters 7 and 8. Thanks go to Steve Showalter, Steve Petrosius, and
Mike Robbins for hours of proofreading. This revision would not have occurred
if it were not for the help of "super secretary" Maribel Lisk and her able assistant
April Kirch. 1 appreciate their dedication, the pride they take in a job well done,
and thei r tolerance of a hyper, "1 want it yesterday," professor. 1 also thank
Dyana D rago for help in preparing the manuscript, but most of all, for
collaborating with son Steve and giving us (Ruth and 1) granddaughters Stacie
and Olivia. John VondeJing's faith in the value ofthis effort is greatly appreciated,
with the fond hope that, for this edition, he wiJl provide a cov,er that does not
self-destruct in ayear. Finally, 1 would like to apologize to my wife, Ruth, for
the many hours of my time spent on chemistry instead of with her and thank
her for encouragement and unselfishness.
RUSSELL S. DRAGO
1
d Contents
ti
It
k
lr
le
d,
Dt
)r
lk
1
Symmetry and the Point Groups 1
Introduction
1-1 Definition ofSyrnrnetry 1
1- 2 Syrnrnetry Elernents 2
1- 3 Point Groups 8
1--4 Space Syrnrnetry 11
1-5 Sorne Definitions and Applications ofSymmetry
Considerations 12
References Cited 14
Additional Reading 14
Exercises 14
2
Group Theory and the Character Tables 18
2-1 Introduction 18
2- 2 Rules for Elernents that Constitute a Group 19
2- 3 Group Multiplication Tables 19
2--4 Sumrnary ofthe Properties ofVectors and Matrices 25
2-5 Representations; GeornetricTransformations 30
2- 6 Irreducible Representations 34
2- 7 CharacterTables 35
2- 8 Non-Diagonal Representations 36
2- 9 More on CharacterTables 41
2-10 Moreon Representations 43
2- 11 Simplified Procedures for Generating and FactoringTotal
Representations: The Decornposition Formula 44
2- 12 Direct Products 46
Additional Reading 47
Exercises 47 vii
3
Molecular Orbital Theory and lis Symmetry Aspects 52
Introduction 52
3-1 Operators 52
3-2 A Matrix Formulation ofMolecular Orbital Calculations 56
3- 3 Perturbation Theory 57
Symmetryin Quantum Mechanics 59
J--4 Wave Functions as a Basis for Irreducible Representations 59
3-5 Projecting Molecular Orbitals 60
MolecularOrbital Calculations 68
3-6 Hckel Procedure 68
3-7 Properties Derived from Wave Functions 72
3- 8 Extended Hckel Procedure 74
3- 9 SCF-INDO(Intermediate Neglect ofDifferential Overlap) 78
3-10 Some Predictions from M.O. Theory on Alternately Double
Bonded Hydrocarbons 83
3- 11 Moreon Product Ground State Wave Functions 84
References Cited 85
AdditionalReading 85
Compilations 86
Exercises 86
4
General Introductlon lo Spectroscopy 90
4-1 Nature ofRadiation 90
4-2 Energies Corresponding to Various Kinds ofRadiation 91
4-3 Atomic and MolecularTransitions 92
4-4 Selection Rules 95
4-5 Relaxation and Chemical Exchange Influences on Spectral
Li ne Width 95
GeneralApplications 98
4-6 Determination ofConcentration 99
4-7 Isosbestic Points 103
4-8 Job's Method ofIsomolar Solutions 106
4-9 "Fingerprinting"
References Cited
Exercises
5
,Electronic Absorptlon Spectroscopy
Introduction
5- 1
MolecuJe
106
107
107
109
109
Vibrational and Electronic Energy Levels in a Diatomic
109
Contents ix
5- 2 Relationship ofPotential Energy Curves to Electronic Spectra 111
5-3 Nomencl ature 113
AssignmentofTransitions 117
5--4 Spin-Orbit Coupling 117
5-5 COllflguration Interaction 117
5- 6 Criteria to Aid in Band Assignment 11 8
The Intensi ty of Electronic Transitions 120
5-7 Oscillator Strengths 120
5-8 Transition Moment Integral 120
5-9 Derivation ofSorne Selection Rules 123
5-10 Spectrum ofFormaldehyde 123
5- 11 Spin-Orbi t and Vi bronicCoupling Contributions to Intensity 124
5- 12 Mixing ofd andp Orbitals in Certain Symmetries 126
5-13 Magnetic Dpole and Electric Quad rupole Contributions to
Intensity 127
5- 14 Charge TransferTransitions 127
5- 15 Polarized Absorption Spectra 128
Applications 130
5-16 Fingerprint ing 130
5-17 Molecular Addition Compounds ofIodine 133
5- 18 Effect ofSolvent Polarity on Charge-Transfer Spectra 135
5- 19 Structures ofExcited States 137
Optical RotaryDispersion, CircularDichroism, and
MagnetocircularDichroism 137
5-20 Introduction 137
5-21 Selection Rules 139
5-22 Applications 140
5-23 MagnetocircularDichroism 141
References Cited 143
AdditionalReferences 144
Exercises 145
6
Vlbration and Rotallon Spectroscopy: Infrared, Raman, and Microwave 149
Introduction 149
6-1 Harmonic and Anharmonic Vibrations 149
6-2 Absorption ofRadiation by Molecul ar Vibrat ions-
Selection Rules 150
6-3 Force Constant 151
Vibrations in a Polyatomic Molecule 153
6--4 The 3N - 6(5) Rule 153
6-5 Effects Gi ving Rise to Absorption Bands 154
6--6 Normal Coordinate Analyses and Band Assignments 156
6--7 GroupVibrations and the Limitations ofThis Idea 160
Raman Spectroscopy ) 162
6--8 Introduction 162
6--9 Raman Selection Rules 164
6--10 Polarized and Depolarized Raman Lines 168
6--11 Resonance Raman Spectroscopy 170
172 SymmetryAspects ofMolecular Vibrations
6--12 Significance ofthe Nomenc1ature Used to Describe Various
Vibrations 172
6--13 Use ofSymmetry Considerations to Determine the Number
ofActive Infrared and Raman Lines 172
6--14 Symmetry Requirements for Coupling, Combination Bands,
and Fermi Resonance 176
6--15 Microwave Spectroscopy 177
6--16 Rotational Raman Spectra 179
Applications ofInfraredandRaman Spectroscopy 179
6--17 Procedures 179
6--18 Fingerprinting 184
6--19 Spectra ofGases 186
6--20 Application ofRaman and Infrared Selection Rules to the
Determination ofInorganic Structures 192
BondStrength-FrequencyShiftRelations 194
6--21 Changes in the Spectra ofDonor Molecules upon
Coordination 196
6--22 Changein Spectra Accompanying Change in Symmetry
upon Coordination 198
AdditionalReferences 205
Exercises 206
7
NuclearMagneticResonance Spectroscopy-ElementaryAspects 211
Introduction 211
Classical Description ofthe NMR Experiment-The Bloch
Equations 212
7- 1 Sorne Definitions 212
7-2 Behavior ofa Bar Magnet in a Magnetic Field 213
7-3 Rotating Axis Systems 214
7--4 Magnetization Vectors and Relaxation 215
7-5 The NMRTransition 217
7--6 The B10ch Equations 218
7-7 The NMR Experiment 220
3
The Quantum Mechanical Description of the NMR Experiment 224
7- 8 Properties of ...
224
7-9 Transition Probabilities 225
Relaxation Effects and Mechanisms 227
7-10 Measuring the Chernical Shift 229
7-11 Interpretation of the Chernical Shift 232
7-12 Interatornic Ring Currents 241
7-13 Exarnples of Chernical Shift Interpretation 241
Spin-Spin Splitting 243
7-14 Effect of Spin-Spin Splitting on the Spectrurn 243
7-15 Discovering Non-Equivalent Protons 246
7-16 Effect of the Nurnber and Nature of the Bonds on
Spin-Spin Coupling 247
7- 17 Scalar Spin-Spin Coupling Mechanisrns 249
7-18 Application of Spin-Spin Coupling to Structure
Deterrnination 252
Factors Influencing the Appearance of the NMR Spectrum 257
7-19 Effect of Fast Chernical Reactions on the Spectrurn 257
7-20 Quanturn Mechanical Description of Coupling 259
7-21 Effects ofthe Relative Magnitudes of J and,1 on the Spectrurn
of an AB Molecule 263
7-22 More Cornplicated Second-Order Systerns 265
7-23 Double Resonance and Spin-Tickling Experirnents 267
7- 24 Deterrnining Sign_s of Coupling Constants 268
7-25 Effects on the Spectrurn of Nuclei with Quadrupole Mornents 269
Compilations of Chemical Shifts 272
Exercises 273
8
Dynamic and Fourier Transform NMR 290
Introduction 290
Evaluation of Theormodynamic Data with NMR 290
NMR Kinetics 291
8-1 Rate Constants and Activation Enthalpies frorn NMR 291
8-2 Deterrnination of Reaction Orders by NMR 295
8- 3 Sorne Applcations of NMR Kinetic Studies 297
8-4 Intrarnolecular Rearrangernents Studied by NMR-
Fluxional Behavior 300
8-5 Spin Saturation Labeling 305
8-6 The Nuclear Overhauser Effect 306
Contents xi
Fourier Transform NMR 309
8-7 PrincipIes 309
8-8 Optimizi ng the FTNMR Experiment 314
8-9 The Measurement ofT by FTNMR 315
8-10 Use ofTI for Peak Assignments 31 7
8-11 NMR ofQuadrupolarNuclei 319
Applications and Strategies in FTNMR 319
8-12 l3C 319
8-l3 Other Nuclei 323
More on Relaxation Processes 326
8-14 Spectral Density 326
Mu/tipulse Methods 328
8- 15 Introduction 328
8- 16 Spi n Echoes 329
8-17 Sensi tivity-Enhancement Methods 331
8-18 Selecti ve Excitation and Suppre sien 332
8- 19 Two-Di mensionalNMR 334
NMR in Solids and Liquid Crystals 340
8-20 Direct DipolarCoupling 340
8-21 NMR Studies ofSolids 341
8-22 NMR Studies in Liquid Crystal Solvents 342
8-23 High Resolution NMRofSolids 347
Additional References 351
Exercises 352
9
Electron Paramagnetlc Resonance Spectroscopy 360
Introduction 360
9- 1 PrincipIes 360
Nucl ear Hyperfine Splitting 363
9- 2 The Hydrogen Atom 363
9- 3 Presentation ofthe Spectrum 368
~ Hyperfi ne Splitti ngs in lsotropic Systems Involving More
Than One Nucleus 370
9-5 Contributions to the Hyperfine Coupling Constant in
Isotropic SysleOms 374
Anisotropic Effects 380
9-6 Anisotropy in the g Value 380
9-7 Anisotropyin the Hyperfine Coupling 383
9-8 The EPR ofTriplet States 390
Contents xii i
9-9 Nuclear Quadrupole Interaction 392
9-10 Line Widths in EPR 394
9-11 The Spin Hamiltonian 396
9- 12 Miscellaneous Applications 397
Referenees Cited 400
AdditionalReferenees 401
Exereises 401
10
The Electronlc Structure and Spectra of Transition Metal lons 409
Introduetion 409
Free Ion Eleetronie States 409
10-1 Electron-Electron Interactions and Term Symbols 409
10-2 Spin-Orbit Coupling in Free10ns 413
CrystalFields 416
10-3 Effects ofLigands on the dOrbital Energies 416
10-4 Symmetry Aspects ofthe dOrbital Splitting by Ligands 419
10-5 Double Groups 427
10-6 The Jahn-Teller Effect 429
10-7 Magnetic Coupling in Metal Ton Clusters 430
Applieations 433
10-8 Survey ofthe Electronic Spectra ofOh Complexes 433
10-9 Calculation ofDq and f3 for Oh Ni(II) Complexes 437
10-10 Effect ofDistortions on the d Orbital Energy Levels 443
10-11 Structural Evidence from the Electronic Spectrum 447
Bonding Parameters from Speetra 450
10-12 (J and n Bonding Parameters from the Spectra of
Tetragonal Complexes 450
10-13 The Angular Overlap Model 452
Miseeflaneous Topies Involving Eleetronie Ttransitions 458
10-14 ElectronicSpectraofOxo-Bridged Dinuclear Iron Centers 458
10-15 Intervalence Electron Transfer Bands 459
10-16 Photoreactions 462
Referenees Cited 462
Exercises 463
11
Magnetism 469
11- 1 Introduction 469
11-2 Types ofMagnetic Behavior 471
11-3 Van Vleck's Equation 476
11-4 Applications ofSusceptibility Measurernents 483
11-5 Intrarnolecular Effects 486
11- 6 High Spin-Low Spin Equilibria 489
11- 7 Measurernent ofMagnetic Susceptibilities 490
11-8 Superpararnagnetisrn 491
Exercises 496
12
Nuclear Magnetic Resonance of ParamagneUc Substances in Solutlon 500
by Ivano Bertini and C. Luchinat
12-1 Jntroduction 500
501
503
507
508
510
512
514
12- 2 Properties ofPararnagnetic Cornpounds
12-3 Considerations Concerning Electron Spin
12-4 The Contact Shift
12-5 The Pseudocontact Shift
12-6 Lant hanides
12- 7 Factoring the Contact and Pseudocontact Shifts
12-8 The Contact Shift and Spin Density
12-9
12-10 Relaxornetry 524
527
530
531
534
543
12-11 Electronic Relaxation Times
12-12 Contrast Agents
12-13 Trends in the Developrnent ofPararnagnetic NMR
12-14 Sorne Applications
12-15 The Investgation ofBimetallic Systerns
Factors Affecting Nuclear Relaxation in Pararnagnetic
Systern 519
Exercises 556
13
Electron Paramagnetic Resonance Spectra 01 Transition Metal Ion
Complexes
559
13-2 Interpretation ofthe g-Values 564
13-3 Hyperfine Couplings and Zero Field Splittings 571
13-4 Ligand Hyperfine Couplings 576
13-5 SurveyoftheEPRSpectraofFirst-RowTransitionMetalIon
Cornplexes 578
13-6 The EPR ofMetal Clusters 591
13-7 Double Resonance and FourierTransforrn EPR Techniques 594
Exercises 597
14
476
483 Nuclear Quadrupole Resonance Spectroscopy, NQR
486 14-1
489 14-2
490 14-3
491 14-4
494
14-5
496
14-6
Introduction
ofthe QuadrupoleTransitions
Effect ofa Magnetic Field on the Spectra
Relationship Between Electric Field Gradientand
Molecular Structure
Applications
Double Resonance Techniques
References Cited
AdditionalReferences
Exercises
500
500 15
501
Mossbauer Spectroscopy
503
507
15-1
508
15-2
510
15-3
512 15-4
514
15-5
15-6
519
Introduction
Interpretation ofIsomer Shifts
QuadrupoleInteractions
Paramagnetic Mossbauer Spectra
Mossbauer Emission Spectroscopy
Applications
References Cited
524
Series
527
Exercises
530
531
534
16
543
lonization Methods: Mass Spectrometry, Ion Cyclotron Resonance,
552
Photoelectron Spectroscopy
556
Mass Spectrometry
16-1
16-2
559
16-3
559 16-4
564 16-5
571
576 16-6
578 16-7
591
594 16-8
Instrument Operation and Presentation ofSpectra
Processes That Can Occur When a Moleculeand a High
Energy Electron Combine
Fingerprint Application
Interpretation ofMass Spectra
Effect ofIsotopes on the Appearance ofa Mass
Spectrum
Molecular Weight Determinations; Field Ionization
Techniques
Evaluation ofHeats ofSublimation and Species in the
Vapor Over High Melting Solids
Appearance Potentials and Ionization Potentials
594 FTlCR/MS
596
16-9 TheFourierTransformIonCyclotronResonanceTechnique
597
Contents XV
604
604
607
611
612
616
620
622
623
624
626
626
630
631
633
635
635
646
646
647
650
650
650
655
657
659
660
662
663
664
665
665
Surface Science Techniques
16--10 Introduction
16--11 Photoelectron Spectroscopy
16-- 12 SIMS (Secondary Ion Mass Spectrometry)
16--13 LEED, AES, and HREELS Spectroscopy
16--14 STM(Scanning Tunneling Microscopy) and AFM
(Atomic Force Microscopy)
EXAFS and XANES
16--15 Introduction
16--16 Applications
References Cited
Exercises
17
X-Ray Crystallography
by Joseph W. Ziller and Arnold L. Rheingold
17-1 Introduction
PrincipIes
17-2 Diffraction ofX-Rays
17-3 Refiection and Reci procal Space
17-4 The Diffraction Pattern
17-5 X-Ray Scatteringby Atoms and Structures
Crystals
17-6 Crystal Growth
17- 7 Selection ofCrystals
17-8 MountingCrystals
Methodology
17-9 Diffraction Equipment
17-10 Diffractometer Data CoIlection
17-11 Computers
Some Future Developments
17-12 Area Detectors
17-13 X-Ray versus Neutron Diffraction
17-14 Synchrotron Radiation
Symmetry and Related Concerns
17-15 Crystal Classes
17-16 Space Groups
17- 17 Space-Group Determination
17-18 Avoiding CrystaIlographicMistakes
17- 19 Molecular versus Crystallographic Symmetry
17-20 Quality Assessment
17- 21 CrystaJl ographic Data
667
667
667
677
678
680
681
681
682
682
685
689
689
690
690
691
693
693
695
695
696
697
698
698
699
700
700
700
701
701
701
701
703
704
705
707
707
710
7
?
7
'8
;0
31
81
82
,82
85
"S9
689
690
690
691
693
693
695
695
696
697
698
698
699
700
700
700
701
701
701
70t
703
704
705
707
707
710
Contents xvii
References Cited
Exercises
711
711
Appendix A
Character Tables lor Chemically Important Symmetry Groups 713
Appendix S
Character Tables lor Some Double Groups 724
Appendix C
Normal Vibration Modes lor Common Structures 727
Appendix D
Tanabe and Sugano Diagrams lor Oh Fields 732
Appendix E
Calculation 01 (10Dq) and fJ lor Oh Ni" and T
d
CO" Complexes 735
Append ix F
Conversion 01 Chemical Shift Data 739
Appendix G
Solution 01 the Secular Determinant lor the NMR Coupling 01 the AS Spin
System 740
Index 745
Symmetry and the
Point Groups
1-1 DEFINITION OF SVMMETRV
Symmetry considerations are fundamental to many areas of chemical reactivity,
electronic structure, and spectroscopy. It is customary to describe the structures
of molecules in terms of the symmetry that the molecules possess. Spectroscopists
have described molecular vibrations in terms of symmetry for many years. Modern
applications of spectroscopic methods to the problem of structure determination
require a knowledge of symmetry properties. We shall be concerned mainly with
the description of the symmetry of an isolated molecule, the so-called point
symmetry. Point symmetry refers to the set of operations transforming a system
about a common point, which usually turns out to be the center of gravit y of a
molecule.
Ir a molecule has two or more orientations in space that are indistinguishable,
the molecule possesses symmetry. Two possible orientations for the hydrogen
molecule can be illustrated in Fig. 1-1 only by labeling the two equivalent
hydrogen atoms in this figure with prime and double prime marks. Actually, the
two hydrogens are indistinguishable, the two orientations are equivalent, and the
molecule has symmetry. The two orientations in Fig. 1- 1 can be obtained by
rotation of the molecule through 180
0
about an axis through the center of and
perpendicular to the hydrogen-hydrogen bond axis. This rotation is referred to
as a symmetry operation, and the rotation axis is called a symmetry elemento The
terms symmetry element and symmetry operation should not be confused or used
interchangeably. The symmetry element is the line, point, or plane about which
the symmetry operation is carried out. The operation can be defined only with
respect to the element, and the existence of the element can be shown only by
carrying out the operation.
A simple test can be performed to verify the presence of symmetry. Ir you
were to glance at a structure, turn your back and have someone perform a
symmetry operation, on once again examining the molecule, you would not be
able to determine .that a change had been made. The symmetry operations of a
molecule form a group and, as a result , are amenable to group theoretical
procedures. Mastery of the material in this chapter is essential to the understand-
ing of most of the material in this book.
Introduction
H
Figure 1-1 Equivalent
orientations for H
2
.
1
2 Chapter 1 Symmetry and the Point Groups
lO ...--A
2-
\ -
~
-; \
Inversion 0'1
8
center -
FIGURE 1-2 The center 01
symmetry in the hyponitrite
ion .
C\ /H
Sr/
C=C
""CI
el
FIGURE 1-3 Absence al a
center al symmetry in CCI.
and HCCI=CBrCI .
1- 2 SYMMETRY ELEMENTS
Five types of symmetry elements wilI be considered for point symmetry: (1) the
center of symmetry (inversion center), (2) the identity, (3) the rotation axis, (4)
the mirror plane, and (5) the rotation-reflection axis. The symmetry operations
corresponding to these elements wilI be defined in the course of a further discussion
of each element.
The Center 01 Symmelry, or Inversion Center
A molecule is said to possess a center of symmetry or inversion center when
every atom in the molecule, if moved in a straight line through this center and
an equal distance on the other side of the center, encounters a like atom. If oxygen
atom A of the hyponitrite ion (F ig. 1-2) is moved through the inversion center,
it comes into coincidence with another oxygen atom, B. T he same arguments
must apply to atom B and aIso to both nitrogen atoms if the molecuIe is to
possess a center of symmetry. This operation corresponds to placing this center
at the center of a coordinate system, and taking every atom with coordinates
(x, y, z) and changing its coordinates to ( - x, - y, - z). At masl one atom can .
be at the center, and alI other atorns in the molecule must exist in pairs. Nei ther
of the two structures indicated in Fig. 1-3 nor any other tetrahedral molecule
possesses an inversion cent r. Ot her molecules or ions that should be examined
for the presence of an inversion center are 1,4-dioxane, tetracyanonickelate(ll),
trans-dichloroethylene, and trans-dichlorotet raammine cobalt(III). The molecuIe
RCCl=CHBr (c is or tran s) does not possess a center of symmetry beca use the
symmetry operation on bromine does not resul t in coincidence. Al! points in the
molecule must be inverted in this operation, if the molecule as a whole is to
possess this symmetry element. The symbol used to indicate an inversion center
(center of symmetry ) is i.
\
The Idenlity
In the identity operation, no change is made in the molecule. Obviousl y, the
result of this 'Operation is not only to produce an equivalent orientation but an
identical one; i.e., even if similar atoms were labeled with prime or double prime
marks, or any other notati on, no change would be d tected. AlI molecules possess
this symmetry elernent, and it is indicated by the symbol E. This operation
probably seems t rivi al at present, but, as will be seen in Chapter 2, this operation
is required so that symmetry elements can be treated by group theory.
The Rotation Axis
Ir an imaginary axis can be constructed in a molecuIe, around which the molecule
can be rotated to produce an equivalent (i.e ., indistinguisha ble from the original)
orientation, this molecule is said to possess a rotati on axis. T he symmet ry element
previously discussed for the hydrogen molecule iS"a rotation axis. This eIemen t
is usuaIly referred to as a proper rotation axis. It may be possible to carry out
several symmetry operations around a single rotation axi s. lf the moIecule can
occupy n different equivalent positions a bout the axis, the axis is said to be of
order n. For example, consider the axis through the center of the boron atom in
3
11
,f
11
BCl
3
perpendicularto the plane ofthe molecule. Rotation, which by convention
is in a c10ckwise direction, about this axis two times through an angle of 120
eachtimeproducestwoequivalentorientations.Takenwiththeinitialorientation,
we have the three different equivalent orientations, illustrated in Fig. 1--4. The
order, n, of this axis is three, for three rotations are needed to return to the
original position. The molecule is said to possess a threefold rotation axis,
indicated by the symbol C3' Rotation of the molecule through 2n/n (i.e., 120
when n = 3) produces equivalent orientations, and n operations produce the
starting configuration referred to as the identity. The symbol C/ is employed
2
to indicate a rotation of240 around a C
3
axis. The C3 operation is identical
to a counterc1ockwise rotation of 120, which is indicated as C
3
-. Itsbould be
c1ear thatanaxis throughthecenterand perpendicularto the planeofa benzene
ring is a sixfold axis, C6 Since n = 6, rotation by 60 (=360/6) six times
produces the six equivalent orientations. F urther examination of the BCl
3
molecule indicates thelackofa centerofsymmetryand the presence ofthe three
additional twofold rotation axes, C
2
, illustrated in Fig. 1-5. One twofold axis,
arbitrarilyselected,is labeled C
2
; theothertwoarelabeled C
2
' and C
2
". Ifn = 1,
the molecule must be rotated 360 to produce an equivalent (and in this case
identical) orientation. A molecule is said to possess no symmetry if no elements
other than the identity are present.
el

C Rotation el"
el'
2 -------'>
axis
FIGURE 1-5 The results of
rotations aboutthe three twofold
rotation axes in BCI
2
. The 180
0
rotation on the left produces the
result on the right.
Arotationaxisofordern generatesn operations:Cn' C
n
2, C
n
3
, . .., cnn - l, Cn"'
2
Furthermore, the operation C/ is equivalent to C
2
, the operation C
6
is
equivalentto C
3
, and cnn is the identity. The rotation axis is re[erred
to as the principal axis in a molecule. Ifall ofthe C
n
axes areequivalent, any one
may be chosen as the principal axis.
In Fig.1- 6,arotationaxisis illustratedfortheH
2
molecule,forwhichn = oo.
The C
2
rotation axes are not illustrated but are perpendicular to the bond axis
and centered between the two hydrogen atoms. There are an infinite number of
these twofold axes. ltshould also be obvious that benzene possesses six twofold
axes t hat he in the plane ofthe molecule.Three pass through pairs ofopposite
carbon atoms,and the other three pa% through the centers ofC- bonds.
ThemoleculeClF3 is illustratedin : :ig.1-7.Thegeometryis basicallya trigonal
bipyramid,with two lone pairs ofelectrons in theequatorial planeand with two
fiuorines bent down toward the equatorial fiuorine. Thi s molecule has only one
rotationaxis, the C2 axisshown in Fig. 1-7.The readershould verify theabsence
ofsymmetry along the axes indicated by dashed lines.
1-2 Symmetry Elements
el" el el
"B....... 3
e2 I
3 el'
l
,
1
3
e
3
3 el' el"
....... .......
B
I
el
FIGURE 1-4 The results of
clockwise rotations about the
threefoldrotationaxisofBCI
3
.
- H-H-B-
Rolation
axis
FIGURE 1-6 The e% axis in
H
2
i/
F
C2 Rotation
:
el-F-
"; ,/ '\
" : F
FIGURE 1- 7 The symmetry
axis in CIF
3
.
For many purposes, it is convenient to locate a molecule and its symmetry
elements in a eartesian coordinate system. A right-handed coordinate system
will be used. Movement of y to x is a po si ti ve rotation. The center of gravity of
the molecule is located at the center of the coordinate system. If there is only
one symmetry axis in the molecule, it is selected as the z-axis. If there is more
than one symmetry axis, the principal rotation axis in the molecule is selected
as the z-axis. If there is more than one highest-fold axis, the one connecting the
most atoms is selected. If the molecule is planar and if the z-axis lies in this plane
(as in the water molecule), the x-axis is chosen perpendicular to this planeo If the
molecule is planar and the z-axis is perpendicular to this plane, e.g., in
el" / H
~ = e , the x-axis is chosen to pass through the largest number of atoms.
H ""'el
In trans-dichloroethylene the x-axis pass es through the two carbons.
The Mirror Plane or Plane of Symmetry
If aplane exists in a molecule that separates the molecule into two halves that
are mirror images of each other, the molecule possesses the symmetry element
of a mirrar planeo This plane cannot Iie outside the molecule but must pass
through il. Another way of describing this operation involves selecting aplane,
dropping a perpendicular from every atom in the molecule to (he plane, and
placing the atom at the end of the line an equal distance to the opposite side of
the planeo If an equivalent configuration is obtained after this is done to al! the
atoms, the plane selected is a mirror planeo Refiection through the mirror plane
is indicated by Fig. 1-8. A linear molecule possesses an infinite number of mirror
planes.
reflect
FIGURE 1-8 Operation 01 a
",
"'O
o ~
mirror plane (CT) reflection on
H' H' H H
H
2
0.
Mirror plane
Often rotation axes lie in a mirror plane (see Fig. 1-9, for example), but
there are examples in which this is not the case. The tetrahedral molecule PO Br2el,
illustrated in Fig. 1-10, is an example of a molecule that contains no rotation
axis but does contain a mirror planeo The atoms P, el, and O lie in the mirror
pl aneo In general, the presence of a mirror plane is denoted by the symbol (J. In
those molecules that contain more than one mirror plane (e.g., BeI
3
), the
horizontal plane (Jh is taken as the one perpendicular to the principal (highest-fold
rotation) axis. In Fig. 1-9, the plane of the paper is (Jh and there are then three
vertical planes (Jv (two others, similar to the one illustrated, each containing the
b o ~ o n atom and one chlorine atom) perpendicular to (Jh'
- --
5
ry
m
of
y
e
e
in
1-2 Symmetry Elements
When a molecule is located in a coordinate system, the z-axis always lies in
the vertical plane(s).
Sorne molecules have mirror planes containing the principal axis but none
of the perpendicular e
2
axes. These planes bisect the angle between two of the
e2 axes (in the xy-plane) ; they are referred to as dihedral planes and are abbrevia ted
I
as a
d
. Two a
d
planes are illustrated in Fig. 1-14, vide infra* Jn sorne molecules
el....... I ./CI
there is more than one set of mirror planes containing the highest-fold axes; e.y., ' S/
in PtCl
4
2
-, one set consists of the xz- and yz-planes (z being the fourfold axis,
and the CI-Pt-CI bond axes being x and y), and the other set bisects the angle
I
el
between the x- and y-axes. The former set, including the chlorine atoms, is called
a by convention, and the latter set is called a
d
. The diagonal plane is always
v
1
taken as one that bisects x, y, z, or twofold axes in the molecule.
The Rotation-Reflection Axis: Improper Rotations
This operation involves rotation about an axis followed by reflection through a
FIGURE 1-9 A mirror plane
mirror plane that is perpendicular to the rota tion axis, or vice versa (i.e.,
in BCI
3
.
rotation-reflection is equivalent to reflection-rotation). When the result of the
two operations produces an equivalent structure, the molecule is said to possess
a rotation-reflection axis. This operation is referred to as an improper rotation,
and the rotation-reflection axis is often called an alternating axis. The symbol S
o
is used to indicate this symmetry element. The subscript n in Sn indicates rotation
(c1ockwise by our convention) through 2n/n.
I
Obviously, if an axis en exists and there is a aperpendicular to it, en will
p-- --- 8r
also be an Sn' Now, we shall consider a case in which Sn exists when neither C
n Sr / / / \
or the mirror pl a ne perpendicular to it exists separately. In the staggered form
el
of ethane, Fig. 1-11,the C-C bond defines a e
3
axis, but there is no perpendicular
mirror plane. However, if we rotate the molecule 60 and then reflect it through
a plane perpendicular to the C-C bQnd, we have an equivalent configuration.
Consequently, an S6 axis exists and, c1early, there is no C
6
.
FIGURE 1-10 The mir ror
The dotted line in Fig. 1-12 indicates the S2 element in the molecule
plane in POBr2CI.
trans-dichloroethylene. The subscript two indicates c10ckwise rotation through
180. S2 is equivalent to i and, by convention, is usually called i.
H
1 6
H
3 '

H--C
H H
"'H
3 ~ 2
v
5 ~
H,
, 6 1
3
H
'C--H
6'V'
C
S
2
o
y
H
H
H/
,
5 ~ 4
5 2
FIGURE 1-11 Improper rotation axis in the slaggered lorm 01 ethane.
A par ti cular orientation of the moJecule methane is illustrated in Fig. 1-13.
Open circles or squares represent hydrogen atoms in aplane parallel to but aboye
the plane of the paper, and the solid squares or circJes are those below the plane
We will use this term to indicate that a statement will be treated more fully later in the text.
6 Chapler 1 Symmetry and the Point Groups
H el
\ /
- - -e= e--s
/ \ 2
el H
FIGURE 1- 12 Rotation-
rellection axis 01 symmetry.
of the papeL The plane of the paper is the reftection plane, and it contains the
carbon atom. The C
4
operation is straightforward. The operation of reflecti on,
(J, moves the hydrogens below the plane to aboye the plane and vice versa. This
is indicated by changing the solid squares to open squares and lhe open circles
to solid circles. However since al! four hydrogens are identical, the initial and
final orientations are equivalent. Tbe molecule contains a fourfold rotation-
reflection axis, abbreviated S4' This operation can be repeated three more times,
or four times in aH. These four operations are indicated by the symbols S4 1, S4
2
,
S4
3
, and S44. The reader should convince himself or herself that S4
2
is equi valent
to a C
2
operation on this axis. It should also be mentioned that the molecule
possesses two other rotation-reflection axes, and these symmetry elements are
abbreviated by the symbols S' and S". The operation S4
3
is equivalent to a
counterclockwise rotation of 90 followed by reflection. This is often indicated
as S4 -.
FIGURE 1- 13 Ellect 01 the
C. G
h
operations C. and (J
perpendicular to C. on the
hyd rogens 01 CH . (Open
o C

o - - - Q ~ - - ~ .~ . - - - Q - - - ~ o ~ o
symbols aboye the page; o

solid symbols below.)
Next we shall consider sorne differences in improper rotation axes of even
and odd order. With neven, Sll
m
generates the set S/ , S/ , Sil 3, ... , S,,"' T his is
equivalent to C n1(Jl, C/(J2, C
n
3
(J3 , ... , Cn"(J"' (Note: In carrying out C,,"(J", one
reflects first and then rotates, while in carrying out (J" C/, one rotates and then
reflects. ) We have the relation (Jn! = (J when m is odd, and (Jm = E when mis even.
The latter leads to the identities S,," = C,,"E = E and S" m = C
n
m
Notice that the existence of an S" axis of even order always requires a C
n
/
2
,
since Sn
2
= C/(J2 = C
n
/
2
.
Consider the set S6' S6
2
, S6
3
, S6
4
, S6
5
, S66 by carrying out the operations
described below on the staggered ethane example.
S6 cannot be written any other way.
S6
2 2
= C
6
(J 2 = C
3
S6
3
=S2 =i (An S2 axis always equals i.)
S6
4
= C/
S6 5 cannot be written any other way.
The complete set would normal!y be written:
When n is odd, Snn! generates the set Sil ' Sn
2
, Sn
3
, S,,4, . .. , S,/ n. An odd-order
S" requires that C
n
and a (J perpendicular to it exist. Note that the operation S,,"
when n is odd is equivalent to c nn(J" = C,,"(J = (J. (Compare this with S/ when
n is even.)
7 1-2 Symmetry Elements
o
Forexample,considerS3. Firstonewould reflect, producingaconfiguration
that is equivalent to the starting configuration (because of the existence of(J in
the molecule).Then onerotates by e
J
to givetheconfigurationcorrespondingto
S/ .SinceSJl is a symmetry operationfor the moJecule, the configuration after
the e rotation must be equivalent to the starting one, and therefore e
3
exists.
3
In general,for anySil (withn odd),e
ll
is also a symmetryoperation. Forpractice,
consider the Ssni operations:
Ss= C
s
and then o-
SS2 = e/
S
S
3 =C
S
3
aod then a
4
S5
4
=e
s
Sss = (J
SS6= e s
S 5
7
=C
S
2
and then o-
3
ss8 =e
s
4
s/ = C
s
and then o-
SS10 = E
SSl1= Ss , etc.
The boldface indicates Ss operations that cannot be written as a single
operation. Thus, Sn with n odd generates 2n operations. Table 1- 1 summarizes
the key aspects ofourdiscussion ofsymmetry operations and elements.
TABLE 1-1. A Summary of Symmetry Elements and Symmetry Operations
Symmetry Operation Symmetry Element Symbol Examples
identity E all molecules
(J reflection plane H
2
0 , BF3 (planar)
inversion point (center of
symmetry)
proper rotation axis e" (n-order) H
3
, H
2
impropera rotation axis and plane S" (n-order) ethane, ferrocene
(rotation by 2n/ n followed (staggered structures)
by reflection in pl ane
perpendicular to axis)
'Ferrocene is staggered and possesses an SI oimproper rotation axis.
1-3 POINT GROUPS
A point group is a coHection of aH the symmetry operations that can be carried
out on a molecule belonging to this group. It is possible to classify any given
molecule into one of the point groups. We shall first examine molecules belonging
to sorne of the very common, simple point groups for the symmetry elements
they possess. This will be followed by a general set of rules for assigning molecules
to the appropriate point groups.
A molecule in the point group en has only one symmetry element, an n-fold
rotation axis. (Of course, all molecules possess the element E, so this will be
assumed in subsequent discussion.) A molecule such as trans-dichloroethylene,
which has a horizontal mirror plane perpendicular to its en rotation axis, belongs
to the point group e
nh
. The point group e
nv
ineludes molecules like water and
sulfuryl chloride, which have n vertical mirror planes containing the rotation
axis, but no horizontal mirror plane (the horizontal plane by definition must be
perpendicular to the highest-fold rotation axis). The e
2 v
molecules, H
2
0 and
S02CI2' contain only one rotation axis and two (Ju planes. The molecule is
assigned to the point group that contains aH of the symmetry elements in the
molecule. For example, H
2
0, which has a e
2
axis and two vertical planes, is
assigned to the higher-order (more symmetry elements) point group e
2u
rather
than to e
2
.
The symbol Dn is used for point groups that have, in addition to a en axis,
n e
2
axes perpendicular to it. Therefore, the D" point group has greater symmetry
(i.e., more symmetry operations) than the en group. A D" molecule that also has
a horizontal mirror plane perpendicular to the en axis belongs to the point group
DnlP and as a consequence wiH also have n vertical mirror planes. The addition
of a horizontal mirror plane to the point group e
nv
necessarily implies the presence
of n 'e
2
axes in the horizontal plane, and the result is the point group D"h' BCI
3
is an example of a molecule belonging to the D3h point group. In the Dnh point
groups, the (Jh planes are perpendicular to the principal axis and contain aH the
axes. Each (Ju plane contains the principal axis and one of the e
2
axes. e
2
e"
2
e'

FIGURE 1-14 The C
2
-axes and two Ud planes in aliene.
9 1-3 Poin! Groups
TABLE 1-2. Symmetry Elements in Some Common Point Groups
d
n
g
'S
ti
LS
3
lt
le
.'
' 2
Poin! Group Symmetry Elements' Examples
eI no symmetry SiBrCIFI
one n-fold axis and a horizontal plane (Jh
which must be perpendicular to the n-fold axis
one e
2
axis and two (J v planes
one e
3
axis and three (Jv planes
three e
2
axes all .1, two (Jv planes, one (Jh plane,
and a center of symmetry
N
2
0
4
(planar)
one e
3
, three e
2
axes .1 to e), three (Jv
planes, and one (Jh
Bel)
three e
2
axes, two (Jd planes, and one 54
(coincident with one e
2
)
H
2
C=C=CH
2
three e2 axes .1 to each other, four e) , six (J,
and three 54 containing e
2
AIi point groups possess he identit y element, E.
Dn molecules may also have (Jd planes that contain the principal (e,J axis
but none of the perpendicular e
2
axes. As mentioned previously, these dihedral
planes, (Jd' bisect the angle between two of the e
2
axes. The notation for a D"
molecule containing this symmetry element is D"d' Such a molecule wiU contain
an n-fold axis, n twofold axes perpendicular to e" , and in addition n (vertical)
planes of symmetry bisecting the angles between two twofold axes and con taining
the n-fold axis. Aliene, H
2
C=C=CH
2
, is an example of a molecule belonging
to the D2d point group. Sorne of its symmetry elements are iUustrated in Fig.
1-14. The two hydrogens on one carbon are in a (Jd plane perpendicular to the
(Jd plane containing the two hydrogens on the other carbono The e
2
axes (the
principal axis being labeled e
2
, the others e
2
' and ez") and the dihedral planes
containing the principal axis are indicated. The two other e
2
axes, e
2
' and e/,
which are perpendicular to the principal e
2
axis, form 45 angles with the two
dihedral planes. (Study the figure carefully to see this. Constructing a model may
help.)
Table 1-2 contains the symmetry elements and examples of sorne of the
more common point groups. The reader should examine the examples for the
presence of the symmetry elements required for each point group and the absence
of others. Remember that the symbol e indicates that the molecule has only one
rotation axis. The symbol Dn indicates n e
2
axes in addition to the n-fold axis;
e.g., the point group D4 contains a e
4
axis and four e
2
axes.
H O-H
\ /
0-8
b
l
FIGURE 1-15 A structure
with C
3h
symmetry.
A more exhaustive compilation of the important point groups is contained
in Herzberg.(l) In addition to the point groups listed in Table 1-2, the 0" point
group which ineludes molecules whose structures are perfect octahedra
(SF6' PCl
6
-) is very common.
It is important to realize that although CHCl
3
has a tetrahedral geometry,
it does not ha ve tetrahedral symmetry, so it belongs to the point group e
3 u
and
not T,. A tetragonal complex, trans-dichlorotetraammine cobalt(rrr) ion, belongs
to the point group D
4/
, (ignoring the hydrogens) and not 0 . Phosphorus
"
pentachloride belongs to the point group D
3
" , and not to e
3/
" for it has three
e
2
axes perpendicular to the axis. The structure of monomeric boric acid e
3
(assumed to be rigid), illustrated in Fig. 1-15, is an example of e
3
" symmetry. It
has a threefold axis and a (J" plane but does not have the three e
2
axes or (Ju
planes necessary for the D3" point group.
It is helpful but not always possible to elassify additional structures by
memorizing the aboye examples and using analogy as the basis for elassification
instead of searching for all the possible symmetry elements. T he following sequence
of steps has been proposed(2) for elassifying molecules into point groups and is
a more reliable procedure than analogy.
1. Determine whether or not the molecule belongs te one of the special
point groups, e"" u' D""", 1", 0", or T
d
. The group 1" contains the regular
dodecahedron and regular icosahedron. O nly linear molecules belong to e""u or
D ooh
2. If the molecule does not belong to any of the special groups, look for a
proper rotation axis. If any are found, proceed to step (3); if no L, look for a center
of symmetry, i , or a mirror plane, (J. If the element i is present, the molecule
belongs to the point group e; if a mirror is present, the molecule belongs to the
point group es.lf no symmetry other than E is present, the molecule belongs to el.
3. Locate the principal axis, en. See if a rotation-reflection axis S2" exists
that is coincident with the principal axis. If this element exists and there are no
other elements except possibly i, the molecule belongs to one of the S" point
groups (where n is even). If other elements are present or if the S2" element is
absent, proceed to step (4).
4. Look for a set of n twofold axes lying in the plane perpendicular to e ".
If this set is found, the molecule belongs to one of the groups D", D
n
", or D nd.
Proceed to step (5). lf not, the molecule must belong to either en' C
n
", or e
nu
.
Proceed to step (6) and skip (5).
5. By virtue of having arrived at this step, the molecule must be assigned
to D" , D
nh
, or D"d. If the molecule contains the symmetry element 0" , it belongs
to D ". If this element is not present, look for a set of n (Jd ' S, the presence of
n
which enables assignment of the molecule to D"d. lf (Jd and (J" are both absent,
the molecule belongs to D".
6. By virtue of having arrived at this step, the molecule must be assigned to
e", e"", or e"v. lf the molecule contains (Jh, the point group is e"". 1f (J" is absent,
loo k for a set of n (Ju's, which places the molecule in e"v. Ir nei ther (Ju nor (Jh is
present, the molecule belongs to the point group C".
The following flow chart provides a systematic way to approach the
classification of molecules by point groups:
1-4 Space Symmetry 11
No
No Yes
Oh
S2" or S2" and i only,
co/linear with unique or
No Yes
highest arder en
es
No Yes
el e; ne;Sl.. lo e"
s"
No Yes
Oh Oh
No Yes No Yes
nov's no/s
D nh
Yes
e"h
No No Yes
en e
nv
Dn D nd
1-4 SPACE SYMMETRV
In describing the symmetry of an arrangement of atoms in a crystal (essential to
x-ray crystallography), two additional symmetry elements are required: (1) the
glide plane and (2) the screw axis, corresponding to mixtures of point group
operations and translation. A space group is a collection of symmetry operatons
referrng to three-dimensonal space. A glide plane is illustrated in Fig. 1-16. The
unit (represented by a comma) is translated a fraction (in this case 1/
2
) of a unit
ceH dimension and is reflected. (A unit cell is the smallest repeating unit of the
crysta1.) The comma must lie in a plane perpendicular to the plane of the paper
and all of the comma tails must point nto the paper. A screw axis is illustrated
in Fig. 1-17. Each postion, as one proceeds from top to bottom of the axis,
represents rotaton by 120
0
along with translaton parallel to the axis. This is a
threefold screw axis. Rotations by 90
0
, 60
0
, and other angles are found in other
structures. There are 230 possible space groups. These are of importance in x-ray
crystallography, 'and will be cavered in more detail in that chapter.
Unit
cell t
FIGURE 1-16 A glide plane.
(The tails 01 these commas
point into the page.)

x
o

FIGURE 1- 11 A screw axis.
I
~ J e ~
--CI-- Pt--CI--c'
I ~ ,
CI e;'
I
e,
FIGURE 1-18 Equivalenl
symmelry elemenls and
alomsinIhemoleculePICI/-.
1-5 SOME OEFINITIONS ANO APPLlCATIONS OF SYMMETRY
CONSIOERATIONS
Products or Combinations 01 Symmelry Operalions
The product of any two symmetry operations, defined as their consecutive
application, must be a syrnrnetry operation. Hence, the product of the e
2
and
(JI!' operations on a molecule with e
2v
symmetry (e.g., H
2
0) is (Jv. (Recall that
the e2 axis is the z-axis, the plane of the molecule is yz, and (Jv' is the yz-plane.)
This can be written as :
Instead of the terrn product, the term combinatan is a better description of the
above operations. The order in which the operations are written (i.e., from left
to right) is the reverse of the order in which they are applied. For the aboye
exam pie, the (Jv' operation is carried out first and is followed by e2 to produce
the same result as (Jv. The final result often depends on the order in which t he
operations are carried out, but, in sorne cases, it does no!. When the result is
independent of the order (e.g., e
2
(Jv' = (J v' e
2
) , the two symmetry elements e
2
and
(J v' are said to commute. In a D311 molecule (see, e.g., Fig. 1-4),the two operations
and (Jv do not commute; i.e., e
3
Equivalent Symmetry Elemenls and Equivalenl Atoms
Ifa symmetry elernent A can be moved into the elernent B by an operatan
corresponding to the element X, then A and B are said to be equvalent. Ifwe
define X - 1 as the reverse operation of X (e.g., a counterclockwise rotation instead
of a clockwise one), then X-
1
will take B back into A. Furthermore, if A can be
carried into e, then there must be a symmetry operation (or a sequence of
symmetry operations) that carries B into e,since B can be carried into A. The
elements A, B, and e are said to form an equivalent seto
Any set of symmetry elements chosen so that any member can be transformed
into each and every other member of the set by application of sorne symrnetry
operation is said to be a set of equivalent symmetry elements. This collection of
elements is said to constitute a class. To make this discussion clearer, consider
the planar molecule ptC1
4
2
- illustrated in Fig. 1-18. The e
2
' and e
2
axes forrn
an equivalent set, as do the e/ and e/'. However, e
2
' is not equivalent to e
2
" ,
because the molecule possesses no symmetry operation that takes one into the
other.
Equivalent atorns in a molecule are defined as those that rnay be interchanged
with one another by a symmetry operation that the molecule possesses.
Accordingly, all of the chlorines in PtCI
4
2
- (Fig. 1- 18) and all of the hydrogens
in methane, benzene, cyclopropane, or ethane are equivalen!. The fluorines in
gaseous PFs (trigonal bipyramidal structure) are not all equivalent, but form two
sets of equivalent atoms, one containing the three equatorial fluorines and one
containing the two axial ftuorine atoms. These considerations are very important
1-5 Some Delinitions and Applications 01 Symmetry Considerations 13
when the topic of nuclear magnetic resonance is discussed, for , under favorable
conditions, non-equivalent atoms give rise to separate peaks in the spectrum.
Oplical Aclivily
If the mirror image of a molecule cannot be superimposed on the original, the
molecule is opticaJly active; if it can be superimposed, the molecule is optically
inactive. In using this criterion, the mirror is understood to be externa! to the
whole molecule, and reflection through the mirror gives an image of the whole
molecule. With complicated molecules, the visualization of superimposability is
difficult. Accordingly, it is to our advantage to have a symmetry basis for
establishing the existence of optically active isomers. Any molecule that has no
improper rotation axis is said to be dissymmetric, and opticaLly active molecules
must be dissymmetric. One often hears the incomplete statement that in order for
optical isomerism to exist, the molecule must lack aplane or center of symmetry.
Since SI = (J (S1 is a rotation by 360
0
followed by a reflection) and S2 = i, if the
molecule lacks an improper rotation axis, both i and (J must be lacking. To show
the incompleteness of the earlier statement, we need to find a molecule that has
neither (J nor i, but does contain an Sil axis and is not optically active. Such a
molecule is 1,3,5,7-tetramethylcyclooctatetraene, shown in Fig. 1-19. This mol-
eH
3
ecule does not have aplane or center of symmetry. However, since it has an S4 FIGURE 1-19 Strueture 01
axis, it is not optically active.
1,3,5,7-tetramethyleyelo-
oetatetraene.
A dissymmetric molecule differs from an asymmetric one,for the latter type is
completely lacking in symmetry. The molecule trans-1 ,2-dichlorocyclopropane,
shown in Fig. 1-20, is dissymmetric (there is no Sil axis) and hence optically
active, but it is not asymmetric, for it possesses a C
2
axis.
Many molecules can exist in sorne conformation that is optically active.
I H
However, if rotation of the molecule about a bond produces a conformation with
H" ,- : /
an improper axis, the molecule will not be optically active. If the conformation
is frozen in a form that does not possess an improper axis, optical activity could
result.
H el /i\
" I //
, I /
In summary, then, we can state that if a molecule possesses only C , it is
Il e I e
dissymmetric and optically active. If n = 1, the molecule is asymmetric as well
as dissymmetric; and if n > 1, the molecule is dissymmetric. If a molecule possesses el : H
/ i "
Sil with any n, it cannot be optically active. e
2
FIGURE 1-20
Trans-1 ,2-
Dipole Momenls
deh loroeyelopropane.
Molecules possess a center of gravity of positive charge, which is determined by
the nuclear positions. When the center of gravity of the negative charge from the
electrons is at sorne other point, the molecule has a dipole moment, which is
related to the magnitude of the charge times the distance between the centers.
The dipole moment is a vector property; that is, it has botb a magnitude and a
direction. For a fixed geometry (i.e., a non-vibrating molecule) the dipole moment
is a non-fluctuating property of the molecule ; as a result it, like the total energy,
must remain unchanged by the operation of every symmetry element of the
molecule. In order for this to occur, the dipole moment vector must be coincident
with each of the symmetry elements.
There are several obvious consequences of these principies. Molecules that
have a center ofsymmetry cannot possess a dipole moment,because the vector
cannot be a point, and any vector wouJd be changed by inversion through the
center. Molecules with morethan one e"axiscannot have a dipole moment, for
a dipole momentvectorcould not be coincidentwith more than one axis.Thus,
only the following types ofmoleculesmay have dipole moments: those with one
en (n > 1), those with one (J and no en, those with a en and symmetry planes
thatineludeen, andthosethathavenosymmetry.Inallcases,wherethemolecule
has symmetry, the direction ofthe dipole vector is determined; for it must lie in
all ofthe symmetry e\ements that the molecule possesses.
REFERENCES 1. G. Herzberg, "Infrared and Raman Speetra," p. 11, Van Nostrand, New York, 1945.
2. F. A. Cotton, "Chemieal Applieations of Group Theory," p. 54, Wi ley-Interseienee,
CITED
New York, 3rd ed., 1990.
ADDITIONAL
READING
M.Tinkham,"GroupTheoryandQuantum Meehanies," McGraw-HilJ,New York, 1964.
F. A. Cotton, "Chemieal Applieations of Group Theory," 3rd ed., Wily-I nterseienee,
New York, 1990.
M. Orehin and H. H. Jalf, 1. Chem. Educ., 47, 246, 372, 510 (1970).
M.Orchin and H. H.Jalf, "Symmetry, Orbitals, and Speetra," Wiley-Interscience, 1971.
C. D. H. Chisholm, "GroupTheoretical Techniques in Quantum Chemistry," Academic
Press, New York, 1976.
A. Vincent, "Molecular Symmetry and Group Theory," Wiley, New York, 1977.
Forspacegroups,see: 1. D.DonaldsonandS. D. Ross,"SymmetryandStereochemistry,"
Wiley, 1972.
1. Classi fy the folJowing molecules in the appropriate pointgroups and, ror (e) through
EXERCISES
(k), indicate all symmetry elements except E.
a. CoC1
4
2
-
b. Ni(CN)4
2
-
C. cis-CoCl
4
(N H
3
)2 - (ignore the hydrogen atoms)
c. Si(CH3h AB (with A and B trans in a trigonal bipyramid)
b. Cl-I-Cl-
i. planar cis-PdCl
2
8
2
(B = base)
Exercises 15
j. planar trans-PdCl
2
B
2
(B = base)
k. staggered configuration for C
2
H
6
1. ferrocene (staggered)
2. a. How does a Du complex for formula MCl,.2- differ from a T', complex(.e., which
symmetry elements differ)?
b. What importantsymmetry element is absent in the PF3 molecule that is present
in the D3h point group?
C. lfeach Ni-CN bond in planar Ni(CN)/- was not linear but was bent
C ~
(Ni ~ N), to whatpointgroupwould thision belong?Whatessentialsymmetry
element present in D
4h
is missing in e
4h
?
d. lndicate which operation is equivalent to the following products for the T', point
group
(1) S4 x S4 = ?
(2) x = ? e
3
e
2
(3) <7d x e2 = ?
3. Does POCl
2
Br possessa rotation-reftectionaxiscoincidentwith the P-Obond axis?
4. a. Rotate the molecule in Fig. 1-14, 180
0
around the S4 axis, and draw the resulting
structure.
b. Locate the mirror planeofthe S4 operationand indicateon thestructure resulting
from part(a) where all the atoms are located after reflection through the planeo
Use script letters to indicate the final location ofeach atom.
C. Is S2 a symmetry operation for the molecule?
5. To which pojnt group does the molecule triethylenediamine (also called 1,4-di-
azabicyclo[2.2.2]octane, or dabco) belong?
6. Assign PtCI/- to a point group and locate one symmetry element in each c1ass of
this point group.
7. Give the point group for each ofthe following and indicate whetber the entity could
have a dipole moment:
a. three-bladed propeller
16 Chapler 1 Symmetry and the Point Groups
b. hexahelicene
Above
c. 2,2-cyc!ophane
d. hexadentate ligand on Fe
2
+
o = Co
=0
Exercises 17
8. Is the following compound opt ically act ive?
~ H
H-----t'-'--
9. er(en)/+(whereen = ethylenediamine) belongs to the D) point group. Is it opt ically
acti ve? Why ?
10. Determine the point groups of lhe following molecules, and find the requested
equivalent atoms within these molecules.
a. Cl el Which protons,ifany, are equivalent ?
?,
el
b. el Which protons are equivalent?
H 8 ~ H 5
H7 H6
Fe
H ~ H 2
H4 H
Cl
Which protons are equivalent?
Which chlorides are equivalen t ?
11. Locate the a
d
planes in e 6H6' Are these equivalent to a
u
? Why?
'Group Theory and
the Character
Tables
2- 1 INTRODUCTION
Grouptheoryisa topicin abstractalgebrathatcan be applied tocertainsystems
ifthey meetspecific requirements.Therearemanysystemsofinteres t tochemists
that can be treatcd by these techniques, and by the end ofthis chapter you wil!
only have begun to gain an appreciation for the powerofthis method. We shaIl
usetheseconceptsfrequently throughouttherestofthebook.Wcshallbeinvolved
in sorne abstract and seemingly irrelevant concepts in the course of our
developmentofthis topic. Thereader is encouraged to persevere,for the rewards
are many.
There are two common major types ofapplications ofgroup theory.
a. It can be used in the generaton 01 symmetry combinations. Ir you are
given sornebasisset, thatis, asetoforbitalsormathematicalfunctions pertaining
to a molecule, you can use group theory to construct linear combinations of the
things in the basis set that refiect the symmetry ofthe molecule. Forexample, if
you aregiven a set ofatomic orbitals for a molecule, you can use group theory
to assist you in mapping out the shape of the molecular orbitals for the given
molecule. There are many areas where such an application can be made, and a
list ofa few inelude our ability to:
1. determine hybrid OI'bitals used in bonding the atoms in the molecule.
2. determine which atomic orbitals can contributeto the various molecular
orbitals in a molecule
3. determine the number and symmetries ofmolecular vibrations
4. predict how the degeneracies 01 che d-orbitals are removed by crystal
.fields ofvarious symmetries
5. predict and generate the spin lunctions to be used in the Hamiltoni a n
for epr, nqr, and Mossbauer spectroscopy
6. construct symmetry adapted combinations of nuelear spin functions to
work out nmr equations.
b. It can be used toascertain which quantum mechanical integrals are zero;
i. e., is SI/t* op I/t dr equal to zero? Such integrals are important to:
1. determine the allowedness ofeledronic transitions
2. determine the activity ofinfrared and Raman vibrations
3. determine the alIowedness ofany given transition in nmr, esr, etc.
e
if
Y
n
a
/1'
ni
ln
o
o;
2-3
2-2 RULES FOR ELEMENTS THAT CONSTITUTE A GROUP
The symmetry operations can be treated with group theory, and we shaJI use
them to illustrate the principIes. In order for any set of elements to form a
mathematical group the following conditions must be satisfied.
1. T he combination (Chapter 1; often referred to as the "product") of any
two elements, and the square of each element, must produce an element of the
group.
This combination is not the same thing as a product in arithmetic. We are
referring to the consecutive operation of elements. It is a simple matter to square
and take all possible combinations of the elements of the e
2
" point group to
ill us trate the point that another element is obtained. The reader is encouraged
to do so, using H
2
0 as an example. Unlike multiplication in ordinary arithmetic,
we must worry about the order of the combination, i. e., e
2
x 0"" or O"v X e
2
.
2. One operaton of the group must commute with a// others and leaue them
unchanged. 7his is the identity elemento
3. The associative law of multiplication must hold, i.e. ,
(XY)Z = X( YZ)
The result of combini.ng three elements must be the same if the first element
is combined with the product of the second two (i.e., O"v(e
2
0"v') or if the produc
t
of the first two is combined with the last element (i.e., (O" ve2)O'v').
4. Every element must have a reciprocal that is also an elemc..lt of [he
group. This requires that for every symmetry operation there be another operation
that will undo what the first operation did. For any mirror plane, the inverse is
the identical mirror plane, e.g., O' x O' = E. For a proper rotation e
n
m
, the inverse
is e
n
n
-
m
; en'" x e/-m = E. If A has the reciprocal element B, then AB = BA = E.
If Bis the reciprocal of A, then A is the reciprocal of B. In general, the reciprocal
of A can be written as A - l.
e3 has the reci procal element e3
2
:
We shall illustrate these rules in an abstract way in the next section.
2-3 GROUP MULTIPLlCATION TABLES
Properties 01 Ihe Multiplicalion Tables
If we have a complete and non-redundant list of all the elements in a finite grou p,
and we know al! the products, then the group is complete!y and uniquely defined.
This information can be summarized with a group multiplicaton tableo This tabIe
is simply an array in which each column and row is headed by an element. The
matrix format is employed here because it is a convenient way to insure that we
have taken alJ possible permutations of products of the elements. T he number
Group Multiplication Tables 19
20 Chapter 2 Group Theory and the Character Tables
of elements in the group is referred to as the arder of the group, h. The group
multiplication table will consist of h rows and h columns. Certain groups have
an infinite number of elements, e.g., H
2
belongs to D", h '
In order to illustrate simply the rules of group theory discussed earlier, we
will consider a group of order three containing the abstract elements A and B
as well as the identity E. We shal! determine what requirements these elements
must satisfy (i .e. , how their combinations must be defined) in order for these
elements to constitute a group. Each matrix element is the result of the product
of the column element times the row element:
E A B
E
A
B
Since multiplication is gene rally not commutative, we must adhere to a consistent
arder for multiplication. The convention is to carry out the operations in the
order, column element times row element ; i.e., when we write a product RC, where
C is column and R is row, we take the column element first , followed by the row.
Each of the original h elements in the group must appear once and only
once in each row and each column of the group multiplication table, and no two
rows or columns may be alike. The fol!owing argument proves this. For a group
of h different elements E, Al' ... An' ... A
h
-
l
, the elements of the nth row (A
n
)
are A"E, AnAl' '" AnAh-l ' If any two products AnA and A"Aj were the same,
left multiplication by the inverse of An would give A" - 1A"A = A and
A,, - IAnA
j
= Aj respectively, and thus require A and Aj to be the same. This
conc1usion is contrary to our original assumption that all e1ements of the group
were different. Thus, al! the products and all the h elements of the row must be
different. Each of the original h elements in the group must thus appear once
and only once in the row. A similar argument can be used for the columns. We
can illustrate the requirements for the general, unspecified set of elements E, A,
and B described aboye to constitute a group, and show how these rules define
the multiplication table.
Since E is the identity, it is a simple matter to indicate the matrix elements
for
mul
products involving
tiplication):
E and write (REMEMBER column first , then row
E A B
E
A
B
E
A
B
A B
There are only two ways to complete this table; these involve defining either
AA = E or AA = B. If AA = E, then according to rule 4, A is its own reciprocal,
so BB = E. (A cannot be reciprocal to both B and A unless A = B, so B must
be the reciprocal of B.) Then, if BA = A or B, we would not be able to complete
the table without repeating an element in a row or column; i.e. , BA = A makes
2-3 Group Multiplication Tables 21
J
p
:e
'e
4,
A repeat in a column, while BA = B repeats B in the row. However, if we define
AA = B, the foJlowing table results:
E A B
E E A B
A A B E
B B E A
If AA = B, we know that A must have a reciprocal , so AB = BA = E.
We can consider this entire group to be generated by taking an element and
aH its powers, e.g., A, A 2( = B), and A 3( = E). Such a group is a cyclic group. For
such a group, aH multiplications must commute.
Thus, by adhering to the conditions specified for a collection of elements to
constitute a group, we have been able to define our elements so as to construct
a group multiplication table that specifies the result of all possible combinations
of elements.
The very same procedures and rules can be used to construct group
multiplication tables of higher order. When atable of order four is made, two
possibilities result, which we shall label G 4
1
and G/:
G
l
4
E A B e
G 2
4
E A B e
E
A
B
e
E
A
B
e
A
B
e
E
B
e
E
A
e
E
A
B
and
E
A
B
e
E
A
B
e
A
E
e
B
B
e
E
A
e
B
A
E
The superscripts arbitrarily number the two possibilities.
We can make these procedures more specific by considering a system in
which the elements are symmetry operations. In so doing, our definition of the
products will not seem so arbitrary, for we know physically what the results of
the products of the symmetry operations are. We shall proceed by considering
the e
3v
ammonia molecule, whose point group contains the symmetry operations
E, 2e
3
, and 3(Jv ' The three (Jv planes are labeled as in Fig. 2-1, and the group
muItiplication table is given as Table 2-1. The reader is encouraged to carry out
TABLE 2-1. Group Multiplication Table for the C
3v
Point
Group
C 2
E C, , (f : (fu
"
~
C 2
,
E E C
3 3
(fu (f u (fu"
C 2
E
"
C
3
C
3 3
(f u (f u (f :
C 2 C 2
3 3
E C
3
(f u (fu
"
(fu
C 2
(fu (f u (f : (J u" E C
3 3
C 2
(fu (f u a,/' (f u
3
E C
3
{Jv " (f
u
" (f u (f u C
3
C
3
2
E
H
,
,
,
,
a v
FIGURE 2-1 The (f v planes
(..l lo pagel in Ihe e
3v
ammonia molecule.
and verify the combinations given in this table. AH of the points made in
conjunction with the discussion of the group A, B, E should al so be verified.
The group multiplication table (Table 2-1) contains sub-groups, which are
smaller groups of elements in the point group that satisfy aH of the requirements
for constituting a group. E is such a sub-group, as is the collection of operations
E, e
3
, e/. The order of any sub-group must be an integral divisor of the order,
h, of the full group.
Similarity Transforms
A second way in which the symmetry operations of a group may be subdivided
into smaller sets is by application of similarity transforms. If A and X are two
operations of a group, then X -1 AX will be equal to sorne operation of the group,
say B:
The operalion Bis said Co be the similarity transform of A by X. In the general
definition of a similarity tranform, X does not necessarily represent an operation
of the group. However, when taking the similarity transform of A in order for
the result B to be sorne other operation of the group, X must be an operation of
the group. We chen say lhat A and B are conjugate. There are three important
properties of conjugate operations :
1. Every operation is conjugate with itself. If we select one operation, say
A, it must be possible to find at least one operation X such that A = X -1 AX.
Proo!:
Left multiply by A - 1:
(The reciprocaJ of the product of two or more operations is equaJ to the product
of the reciprocals in reverse order; see Cottonpl " ehemical Applications of Group
Theory," if you desire to see the proof.) By definition, E must also equal
(AX) -1(AX).
Both equations can be true only if A and X commute. Thus, the operation
X may always be E, but it may also be any other operation that commutes with
the selected operation A.
2. If A is conjugate with B, then B is conjugate with A ; i.e. , if A = X-
1
BX,
then there must be sorne operation in the group, y, such that B = Y- 1A Y Note
that X equals Y - 1 and vice versa.
3. If A is conjugate with both B and e, then B and e are conjugate with
each other.
The use and meaning of the similarity transform will be made more concrete
as we employ it in subsequent discussion in this chapter. For the moment, it may
help to point out that a similarity transform can be used to change the coordinate
2-3 Group Multiplication Tables 23
ti
n
Ir
Jet
up

on
ith
IX ,
l
ote
ith
rete
nay
ate
system seleeted to describe a problem. A right-handed eoordinate system is given
by:
Z

or any rotatioo of these axes. A left-handed coordinate system is given by:
Z
lt'y
The two eoordinate systems are seen to be related to ea eh other by a mirror
plane (J, that eontains the Z-axis and bisects the X - and Y-axes.
Now, eonsider a C
4
1
rotation about the Z-axis. A point with eoordinates
(a, b) (the X coordinate is always given first) in a right-handed system goes to
(b, - a) upon a 90 clockwise rotation, but to (- b, a) with a 270 rotation.
In a left-handed system C
4
1
takes (a,b) to (-b,a), while C
4
3
yields (b, -a).
(Construet a figure if needed.) Thus, the roles of C
4
and C
4
3
are interehanged
by changing the coordinate system. We can say that there is a similarity transform
of C
4
3
to C
4
by (J d; i.e., .
A A

B3 B
2
B4 B
L I ____________________
Classes 01 Elements
A A

B3 B4 B
2
Bl

A complete set of elements that are eonjugate to one another is called a class of
the group. The order of each class must be an integral divisor of the order of the
group. To determine the classes, begin with one element, say A, and work out
all of its similarity transforms with all the elements of the group, including itself.
Then find an element that is not one of those conjugate with A, and determine
all of its transforms. Repeat this procedure until all of the elements in the group
have been divided into elasses. E will a/ways constitute a class by itself of order
l, E-lEE = E.
We shall demonstrate this procedure by working out aH of the c1asses of
elements in the group:
G
I
6
E
A
B
C
D
F
E A B C D F
E A B C D F
A E D F B C
B F E D C A
C D F E A B
D C A B F E
F B C A E D
First of aH, E is a c1ass by itself. Next , work out aH of the similarity transforms
of A. These would be EAE, A - IAA, B-IAB, C-IAC, D-IAD, and F-IAF. We
already know that EAE = A. To carry out the combination A -1 AA, we first note
from our table that AA = E. Thus, A - 1AA = A -1 E, so we have 10 find out what
element is equal to A - l. We know that A -1 A = E; accordingly, we go to the A
column and determine which element, when combined with A, produces the result
(matrix element) E. This element is A, and therefore A - 1 = A. As a result,
A -1 AA = A-1 E = AE = A. In a similar fashion, we can show that B-
I
= B. To
determine B- 1 AB, we see that AB = D and B- 1D = BD = C. Proceeding in a
similar fashion, aH of the similarity transforms of A can be determined:
E-IAE=A
A -1 AA = A
B-IAB = C
C-IAC = B
D-IAD=C
F-IAF=B
Thus, we have determined that A, B, and C are all conjugate andmembers of
the same cJass. We now know that aH transforms of B and C are al so A, B, or
C (see rule 3, p. 19), so these do not have to be worked out.
Next, we find an element that is not conjugate with A and determine its
transforms. Such an element is D, and its transforms are:
E-IDE=D
A-IDA=F
B- IDB=F
C-IDC=F
D-IDD = D
F-IDF=D
AII transforms of D are either F or D, so these two elements constitute a cJass.
Note that we have now placed every element in a class.
ns
Ve
)te
lat
A
ult
Jlt,
To
a
of
,or
its
2--4 Summary 01 the properties 01 Vectors and Matrices 25
Wecan again make this procedureless abstract by working out the classes
for the symmetry group of the ammonia molecule from Table 2-1. (You might
try closing the book, working this out yourself, and then using the ensuing
discussion to check your result.)
EEE =E
C/EC
3
= E (note: C
3
-1 = c/)
The first result is,ofcourse, that E is always in a class by itself. Next, it can be
shown that C
3
and C/form a class ofthe group.
EC
3
E = C
3
=
C
3
C
3
C/= C
3
C
3
2
C
3
C
3
C
3
(JvC3(Jv = C/
2
(J v' C
3
(J v' = C
3
(J v" C3(J v" = C3
2
Similarly, (J v, (Jv', and (Jv" form a class ofthe group:
C/(JV C 3 = (J v"
C
3
(Jv C / = (J v'
Ingeneral,equivalentsymmetryoperationsbelongtothesameclass.(Recall
thatequivalentelementsareonesthatcanbetakenintooneanotherbysymmetry
operations ofthe group.) Forexample, in the planar ion PtCl/- (D
4h
), shown
in Fig. 2-2, (J v and (Jv' can never be taken into (Jd and (J/ Therefore, (J v and (Jv'
form one class ofthe group, while (Jd and (Jd' form another.
2-4 SUMMARY OF THE PROPERTIES OF VECTORS
ANO MATRICES
Vectors
A vector in three-dimensional space has a magnitude and a direction that can
be specified by the lengths ofits projections on the three orthogonal axes ofa
Cartesian coordinate system. Vector properties may be more than three-
FIGURE 2-2 The (J v and
(Jd planes in the D
4h
PtcV-
~
A
(A)
y
~ ~ ~
(8)
FIGURE 2-3 a. Two vectors,
A and B. separated by an
angle (J. b. The vectors
placed in a two-dimensional
xy-coordinate system.
square of a vector is given by
A
2
I
dimensional, so the aboye statement can be extended to p-dimensional space and
p orthogonal axes in p-space.
It is often necessary to take the product of vectors. One type of product that
produces a number (i.e., a scalar) is called the scalar or dot product. This is given
by:
~ ~
A B = AB cos f} (2-1)
Here the boldface A and B refer to the two vectors, and the dot refers to
their dot product. On the right-hand side of the equation, A and B refer to the
lengths of the Aand Bvectors, and eis the angle between them as shown in Fig.
2-3a. Accordingly, if the angle ebetween vectors is 90 , the dot product is zero
(cos 90 = O) and the vectors are orthogonal.
It is necessary to reference our vectors to a coordinate system. This is done
for a two-dimensional example (Le. , the xy-plane) in Fig. 2-3b. The angle f} is
now seen to be 8 - <p, so the dot product becomes
x
A . B = A B cos (e - <p) (2-2)
Simple trigonometry now gives us the projections of the Aand Bvectors on the
x and y axes as:
A, = A cos (p (2-3)
Ay = A sin <p (2-4)
Bx = B cos e (2-5)
By = B sin e (2-6)
Using a trigonometric identity, equation (2-2) can be rewritten as
A . B = AB(cos <p cos 8 + sin <p sin e)
= A cos <p B cos e + A sin <p B sin e (2-7)
Substituting equations (2-3) through (2-6) into (2-7) produces
Thus, the dot product of two vectors in two-dimensional space is the product of
the components with all cross terms (AxBy and so forth) absent. In p-space, the
result obtained is
p
A B = AB;
i;::: 1
where i ranges over the p orthogonal axes in p-space. Accordingly, the scalar
e
i)
S)
7)
of
he
2-4 Summary 01 the properties 01 Vectors and Matrices 27
Matrices
A matrix is a rectangular array of numbers or symbols that has the following
general form:
The square brackets indicate that this is a matrix, as opposed to a determinant.
The entire matrix can be abbreviated with a script letter or by the symbol [aJ.
The symbol a
ij
refers to the matrix element in the ith row and jth column. When
the number of rows equals the number of columns, the matrix is called a square
matrix. The elements aj of a square matrix for which i = j (i. e., a 11 ' a
22
, a
33
, etc.)
are called the diagonal elements, and the other elemen ts are off-diagonal.
When all of the off-diagonal elements of a matrix are zero, the matrix is said to
be diagonali zed or to be a diagonal matrix. When each of the diagonal elements
of a square matrix equals 1 and all off-diagonal elements are zero, the matrix is
called a unit matrix. The unit matrix is often abbreviated by the Kronecker delta, (j.
Unless i = j , the matrix element ij of a diagonal matrix has a value of zero.
The trace or character of a square matrix, an important property (vide in{ra), is
simply the sum of the diagonal elements. A one-row matrix can be conveniently
written on a single lineo In order to write a one-column matrix on a single hne,
it is enclosed in braces, { }.
A vector is conveniently represented by a one-column matrix. In a three-
dimensional orthogonal coordinate system, a vector initiating at the origin of
the coordinate system is completely specified by the x, y, and z coordinates of
the other end. Thus, the matrix {x, y, z} is a one-column matrix that represents
the vector. In p-space, a p by 1 column vector is needed. In both instan ces, the
elements of the matrix give the projections of the vector on the orthogonal
coordinates.
Matrices may be added, subtracted, multiplied, or divided by using the
appropriate rules of matrix algebra. In order to add or subtract two matrices Ql
to give a matrix (f, the matrices must all be of the same dimension; i.e. ,
contain the same number of rows and columns. The elements of the
(f matrix are given by:
A matrix can be multiplied by a scalar (a single number). When multiplying by
a scalar, each matrix element is multiplied by this scalar
The ijth matrix element of a product matrix is obtained by multiplying the ith
row of the first matrix by the jth column of the second matrix, i.e., row by
column to produce the product matrix. That is, the matrix elements of (f. ,
the product of l2r and lB, are given by
"
Cik = L a ij b j k
j = 1
where n is the number of elements in the ith row and in the jth column. This
ma trix multiplication is equivalent to taking the dot product of two vectors.
lt should be clear that , in order to multiply a matrix by another matrix, the
two matrices must be conformable; i.e. , if we wish to multiply l2r by lB to give
(f., the number of columns in l2r must equal the number of rows in lB. If the
dimensionality of matrix l2r is i by j and that of ~ is j by k, then (f. will have a
dimensionality of i by k. This can be seen by carrying out the following matrix
multiplication:
3 by 2 2 by 3 3 by 3
The number of columns (two) in 121 equals the number of rows (two) in lB. The
matrix elements of (f. are obtained by a row by column multiplication; i. e. ,
C
ll
C2
C
13
C
21
C
2 2
C
23
C
31
C
3 2
C
33
= ab1 + a
12
b
2

= a
11
b 2 + a
1 2
b
22
= ab
13
+ a
12
b
2 3
= a
21
b1 + a
22
b
2 1
= a
2
b
12
+ a
2 2
b
2 2
= a
2 1
b
13
+ a
2 2
b
23
= a
3
b
11
+ a
3 2
b
21
= a
31
b
i2
+ a
32
b
2 2
= a
3 1
b
13
+ a
32
b
23
Matrix multiplication always obeys the associative law, but is not necessarily
commutative. Conformable matrices in the order IllIB may not be conformable
in the order 1B1ll.
Division of matrices is based on the fact that 121 divided by lB equals l l ~ -1 ,
where lB - is defined as that matrix such that lB lB - = bij' Thus, the only new
problem associated with division is the finding of an inverse. Only squa re matrices
can have in verses. The procedure for obtaining the inverse is described in matrix
algebra books, which should be consulted should the need arise.
Conjugate matrices deserve special ment ion. If two matrices 121 and lB are
x
2-4 Summary 01 the properties 01 Vectors and Matrices 29
a
1- 1
,
are
conjugate, they are related by a similarity transform just as conjugate elements
of a group are; i.e., there is a matrix such that
(2-8a)
One advantage of matrices that will be of significance to us is that they can
be used in describing the transformations of points, vectors, functions, and other
entities in space. The transformation of points will be discussed in the next section,
where we deal with a very important concept in group theory : how symmetry
operations (elements) can be represented by matrices and what advantages are
thus obtained.
We can use matrices and vectors to gain a further appreciation of similarity
three distinct fixed points O, and P2 in three-dimensional
space. Let X be the vector from O to PI' and let Y be the vector from O to P2'
A set of three-dimensional Cartesian coordinates centered at the point O will be
referred to as frame 1. Suppose that an operator A, also thought of as being
associated with frame J, transforms the vector Xin frame I into the vector Yin
frame I according to the equation
y =AX
Next rotate frame I into a new position, keeping the origin of the coordinates
fixed at O and leaving the points PJ and P2 fixedjn Frame I in its new
position is called frame JI. Notice that the vectors X and Y have been unaffected
by this procedure, since the three C!:., PI ' and P
2
have remained fixed in
space. However, the projections of X and Y on the coordinate axes of frame JI
wiU give numerical values different from those obtained when the vectors were
the coordinate axes of frame 1. Thus, in frame JI we write the vectors
as X' and Y . We now to find an operator A' with frame 11 that
transforms the vector X' in frame II into the vector Y in frame II according to

Y' =A' X'
The operator A frame JI is said to be simila!.., to the operator A in frame 1.
Thus, A' sends X' (expressed in frame JI) into Y (also expressed in frame JI),
while A does the same thing in frame 1. In order to evaluateJ he A', we
need to know the relationship between the components of X and Y in frame I
and the components of X' and Y' in frame JI. This information is given in the
form of a transformation of coordinates expressed by a matrix S. Thus,
X =SX'
Y = SY
so that
Y=AX
beco mes
SY = ASX'
y
P'(1,1,1)
z
FIGURE 2-4 A point in the
Cartesian coordinate system.
Since I SI 1= O, we know that S-l exists, and
Thus,
Y' =A' X'
if
(2-8b)
ThesimilarmatricesA' and A areconnected by equation(2-8b),which is known
as a similarit y transformation. The trace of a matrix is invariant under a similarity
transformation.
2-5 REPRESENTATIONS; GEOMETRIC
TRANSFORMATIONS
As discussed previously, E, (J, i, en, and S" describe the symmetry of objects.
Each of these operations can be described by a matrix. Consider the point P in
Fig. 2-4 with x, y, and z coordinates of 1, 1, and 1 corresponding to the
projections of the point on these axes. The identity operation on this point
corresponds to giving rise to a new set ofcoordinates that are the same as the
old ones. The following matrix does this.
Matrix multiplication yields:
X=X'
y = Y'
Z=Z'
This unit matrix is said to be a representation ofthe identity operation.
A reflection in the xy-plane, (J xy' changes the sign of the z-coordinate, but
leaves x and y unchanged.The following matrix does this.
Matrix multiplication gives X = X', Y= Y', and Z = -Z', which is the
resultofreflectionin thexy-planeonthexyz-coordinatesofthepointP. Similarly,
n
ty
ts.
In
he
et
he
the
rly,
2-5 Representations; Geometric Transformations 31
the result of the operation a
y z
is given by
and axz is represen ted by .
The inversion operation is given by
y
Call the z-axis the rotation axis; we shall derive the matrix for a clockwise
p (x"y,)
(as viewed down the positive z-axis) rotation of the point by an angle ({J . This
rotation is illustrated in Fig. 2-5. The point (x , y) defines a vector r that
connects it to the origin, and rotation leads to the vector r
2
. For any rotation
of r about the z-axis by ({J, the z component is unchanged, leading to: - - - - - - - - ~ ~ - - - - - - x
FIGURE 2-5 Clockwise
In Fig. 2- 6, the rotation of r to r
2
is shown. The problem is to determine the
rotation 01 the point (x" y,)
new coordinates for r
2
. The dots show rotation of the y coordinate of r by ({J, by the angle C{J .
y
x component
r, (Xl' YI)
~ ~ - - - - - - - - - - L ~ - - - - - x
FIGURE 2--6 Rotation 01 the
vector r, and its y-coordinate
through the angle C{J.
y component
producing the vector y'. The vector y' now has both x- and y-components, which
are given by:
y' = y sin qJ + y cos qJ
This result is obtained by the following trigonometric arguments : y' still has
a length of y. Using trigonometry on the triangle defined by qJ, y' , and the y-
component of y', we see that
y component
cos qJ = ----'----
y'
y component
y
or y component = y cos qJ. Similarly, since sin qJ = x component/y, we have
x component = y sin qJ. The vector y' then has components given by:
y' = x component + y component = y sin qJ + Yi cos qJ
Figure 2-7 illustrates the rotation of the x-coordinate of the vector f ,
producing a new vector x' with both x- and y-components. As befo re, we can
show that the y-component is -x, sin qJ and the x-component is x cos qJ. This
leads to:
x' = X cos qJ - X sin qJ
x component
r, original
vector
FIGURE 2-7 Rotation 01 the
x-coordinate 01 the vector r, by the angle
<p .
,
y component
X'
The x
z
- and yz-components of the rotated vector f
z
must equal the sums of the
x- and y-components of x' and y', so:
X
z
= Xl COS qJ + y 1 sin qJ
Yz = -Xl sin qJ + y cos qJ
Writing these equations in matrix form, we obtain for the clockwise rotation of
a point in a fixed axis system:
[
cos qJ sin qJ J[xJ = [x
2
J
-Sin qJ COS qJ y Yz
15
l'-
l'
In
liS
mI
he
of
2-5 Representations; Geometric Transformations 33
For the reverse transformation (i.e., countercJockwise rotation ofa point in a
fixed axis system) the transformation matrix is given by*:
cos cp
- sin cp ]
[slO cp cos cp
The total transformation matrix for a cJockwise proper rotation is:
SIO cp 001]
cos cp

Fora C
2
rotation we substitute cp = - 180 into the cJockwise proper rotation
matrix. A negative angle corresponds to a cJockwise rotation according to the
trigonometricconvention.

AC
3
rotationmatrixcan be written bysubstituting cp = -120in the cJockwise
proper rotation matrix.
For an improper rotation around the z-axis, we rotate in the xy- plane and
then reflect through it, leading to the matrix representation
SIO cp
cos cp

The multiplication of these matrix representations of the symmetry oper-
ations produces the same result as the product ofthe symmetry operations, as
they must ifthey are indeed the correct representations.
(Ixz X (Ixz = E
-!
Al! matrices that describe the tranformations of a set of orthogonal
coordinates* by the symmetry operations of a group are orthogonal matrices.
Theirinverses can be obtained by transposing rows and columns. Forexample,
*Thi s isequivalent lo a clockwise rotation orthe axis system, which would be written as:
cos rp -sin
[ SIO rp cos rp Y Y
* Orthogonal coordinates are those whose dot product is zero.
the inverse of the matrix that corresponds to
[cos (- 30) = 13/2J
13
O
2 2
1
-
13
O
2 2
O O
IS
a 30 rotation about the z-axis
13
O
-
2 2
13
O
2 2
O O
2-6 IRREDUCIBLE REPRESENTATIONS
The total represent a tion describing the effect ofall ofthe symmetry operations
in the e
2 v
point group on the point with coordinates x, y, and z is
E (Jyz
[1 J-I -1 Jr-1J[-1 J
Notice each of these matrices is block diagonalized; Le., the total matrix can be
brokenupinto blocksofsmaller matrices with no off-diagonalelements between
the blocks. The fact that it is block diagonalized indicates that the total
representation mustconsistofa setofso-called one-dimensional representations.
We can see this as follows. Ir we were to be concerned only with operations on
a point that had only an x-coordinate (i. e. , the column matrix
{x, O, O}), then only the first row of (he total representation would be required
(i.e., 1, -1, 1, -1). This is an irreducible representation, which in this case is a
set ofone-dimensional matrices describing the symmetry properties ofthe one-
dimensional x-vector in the specified point group. The symbol B 1 will be used
to symbolize this irreducible representation. Do not concern yourself with the
meaningofthe B and 1for now, butjust think ofthis as alabe!'The irreducible
representation for y is:
1 -1 -1
which is labeled B
2
; and that for z is:
1
which is labeled Al.
The total representation-thefour 3 x 3 matrices- is a reducible represen-
tation. It is reducible,as discussed above,into three sets of1 by 1 matrices,each
set a representation by itself. The trace or character of each of the total
representation matrices is the sum of the characters ofeach of the component
irreducible representations ; in order, these are 3, -1, 1, and l.
We will show shortly that the block diagonalized 3 x 3 matrices for the
effect ofsymmetryoperationsonourpoint resulted becausetheX-, y- , and z-axes
IS
be
en
tal
ns.
on
nx
red
s a
nc-
sed
he
I e
2-7 Character Tables 35
of our coordinate sys tem were selected as the basis set 01vector:s for the symmetry
operations, i.e., z ror rotation, xy for reflection. We shall subsequently consider
a representation that is not block diagonalized. Z
There is one additional irreducible representation in the e
2v
point group.
We can illustrate it by carrying out the operations of the group on a rotation
Rz described by the sketch on the right. The identity and e
2
rotation do not
change the direction in which the arrow points, but reftection by (Jxz and (Jyx do.
None of the irreducible representations we now have, nor any combination of
these irreducible representations, describes the effect of the e
2v
symmetry
operations on this curved arrow representing rotation around the z-axis. The
result is another irreducible representation:
-1 -1
which is labeled A
2
.
2-7 CHARACTER TABLES
We now have empirically derived all of the irreducible representations of the e
2v
point group, but we cannot be sure we have all of them with the procedures
employed. There are rigorous procedures ror deriving all of the irreducible
representations of the various poi n t groups, which are covered in many treatments
of group theory. These procedures will not be covered here, for we will be more
concerned with using the irreducible representations and will not have to generate
them; they are readily available. The results of the preceding discussion for e
2v
symmetry are summarized by the character table of the e
zv
point group shown
in Table 2-2.
TAB LE 2-2. Character Table for the e
2v
Point Group
E e, (J xz (Jyz
Al +1 +1 +1 +1 z
A
2
B
+1 +1 -1 -1 R,
1
+1 -1 +1 -1 x, Ry
B
2
+1 -1 -1 +1 y, Rx
Each entry in the character table is the character of the matrix ror that
operation in that representation. For 1 x 1 matrices, the character and the matrix
are the same. There is a row for each irreducible representation.
The la beis have the following general meaning:
1. The symbol A indicates a singly degenerate state (i.e. , it consists of only
one representation) that is symmetric about the principal axis: i.e., the character
table contains values of +1 under the column for the principal axis for all A
species.
2. The symbol B indicates a singly degenerate state that is antisymmetric
about the principal axis; i.e., the value -1 a ppears under the column for the
principal axis for al! B species.
X
z
FIGURE 2-8 A basis set for
geometric transformations on
p that are not coincident with
the Cartesian coordinates. (P
has positive x, y, z
coordinates.)
3. The subscripts 1 and 2 indicate symmetry or antisymmetry relative to
a rotation axis other than the principal axis. If there is no second axis, the
subscripts refer to the symmetry about a (Ju plane (e.g., in the C
2u
group, subscript
1 is symmetric about the xz-plane and 2 is antisymmetric).
AII properties of a molecule with symmetry can be expressed in C
2u
mathematical terms that will, for a basis set, form a general representation that
consists of one (or a combination of more than one) of these irreducible
representations. As we shall see, appropriate combinations of the irreducible
representations summarize the results of our matrices operating on anything
belonging to the C
2
!! point group. Character tables are available for all of the
point group symmetries, and are Iisted in Appendix A.
2-8 NON-DIAGONAL REPRESENTATIONS
If, instead of selecting the C
2
and (J elements to be coincident with the axes of
our coordinate system, we selected as our basis the C
2
axis shown in Fig. 2-8
(and the other elements appropriately), then our matrix representation would not
be block diagonalized. For example, the C
2
rotation would not simply change
the sign of the x-coordinate as we saw before, but instead would have to keep
the sign the same and change the magnitude of the coordinates. Instead of
o
-1
O
the new x-coordinate would be dependent on what the y- and z-coordinates of
the original point were; Le., there would be off-diagonal matrix elements. We
shall not work this all out, for it is not worth the effort. However, the point
should be made that the trace of the matrices for ail of the symmetry operations
would be the same for any Cartesian basis set, Le. , 3, -1, 1, 1. The matrix
representation for the axis selection we have made here can be converted into a
block diagonal matrix by using an appropriate matrix, Q, for the similarity
transform ; Le.,
In this case, the similarity transform is a rotation to the new basis set (for the
symmetry operation with the rotation matrix) from the basis set of the original
X, Y, Z axis system. The basis set is rotated, not the points or the molecule. In
practice, when off-diagonal elements result, we realize that a poor selection of a
coordinate system was made. We choose a new orthogonal coordinate system,
each basis vector of which transforms as one of the irreducible representations,
so that a block diagonal representation will result. This will be made clear by
picking a simpler example that we can work through completely. Such a
representation, which is not block diagonalized, can be obtained by considering
the operations of the C
2u
point group on two vectors a and b, using these vectors
as the basis set to describe the representation. The problem is illustrated in Fig.
e
If
8
1I
of
'l/e
101
ms
IX
~ a
Iy
the
nal
. In
m,
i1 a
ring
wrs
Fig.
2 ~ Non-Diagonal Representations 37
z
- a
\
\
\
\
\
-b \
\
\
b
(1 / O. --, 1 / O.
\
\
\
~ ~ y
O) a (1 / 0.1 / 0. o)
X
FIGURE 2-9 Geometric transformations in the a,b basis.
2- 9. The coordinates were selected as 1/J2 to produce normalized (i.e., unit)
vectors:
The angle between a and bis 90 . We are going to set up our matrices to operate
on the a, b basis set, so these matrices will not work for the x, y, z basis set of
the X, y, Z-coordinate system. They will tell us what a and b are changed to, in
terms of a and b. Since we wish to illustrate with this example the dependence
of our matrices on the location of our basis set in the coordinate system, we shaIl
carry oul all of the symmetry operations about axes and planes in the X- , Y-,
Z-coordinate system. In terms of the a, b basis, we have
Ea = a
Eb = b
Now, the e2 operation changes a to - a and b lo - b
[
-1 0J
O -1
Reflection in the xz-plane moves a into b and b into a:
Furthermore,
O'yz a = -b
[
O-lJ
O' yz b = -a -1 O
)
Nate that these reftections have moved a into b and b into a with off-diagonal
elements, and that the trace is zero. Further note that the trace of their
representation matrices is the same as Ihose for the x, y parts of the matrices
generated earlier in the x, y basis for the C
2v
point group. The off-diagonal
elements immediately tell us that we made a bad choice ofaxes for this basis set.
We know from earlier discussion that x and y form the basis of irreducible
representations in C
2v
; thus, if we loca te our vectors along x and y, and use
matrices that work on the x- and y-coordinates of the point defined by the vector
(i.e., an x, y basis set), then diagonal matrices will result. We can do this with a
similarity transformo
For our first example of this procedure, we shall consider the operation O"yz.
The similarity transform is Q - IO"yzQ, where Q is a clockwise rotation matrix of
the xy-axis system by 45 (this operation makes x and y coincide with a and b).
[cos qJ
SID qJ
-SID qJ J
COS qJ
= Q when qJ = 45
so
~ [ ~
1 1
~ l
- )2
and
Q-l =
)2
1 1
)2
- )2
1 1
[-:
-:1
1 1
~ [-: : 1
Q- (ab) Q =
)2j2 j2
- j2
O" yz
1 1 1 1
- j2 j2
j2 j2
Note that the trace of the resulting matrix is the same as that of the starting one.
The trace of a matrix is always invariant under a similarity transformo When we
operate on al! ofthe matrices for the various operations in C
2v
with this similarity
transform, we will have
E
(Jvxz O" vyz
[
1 0J[-l 0J[l 0J[-l 0J
1 -1 -1 1
corresponding to the B 1 (upper left) and B
2
(lower right) representations ror x
and y, respectively; i.e., our reducible representation in the a, b basis is decomposed
into Bl and B
2
.
Oegenerate Representstions
For further practice, consider the ammonia molecule, represented in Fig. 2-10
with an x, y, z-coordinate axis basis set. The symmetry operations are E, 2e
3
,
:s
1\
t.
;e
)[
a
"
)1'
l
lOe.
we
Iy
HX
)sed
2-8 Non-Diagonal Representat ions 39
a" y a'
( -1 12, V3/;;'1< ,/
FIGURE 2-10 The ammonia molecule in
\ ,/ a
-----N ---H-__L X
a Cartesian coordinate system. (N is
above the xy-plane, and the projection 01
/ (1, O)
the N-H bond on the x-axis is taken as 1.)
( -1 / 2, -
and 3(Tv' Consider the x-, y-, and z-axes all together:
1
--
13
O
2 2
13
O
E= 1 C
3
=
2 2
O
O
O O
The C
3
rotation matrix is obtained by substituting qJ = 2n/ 3 (= 120) into the
general proper rotation matri x defined earlier (p. 33).
In order to determine the matrices for (Tv, we must work out the reflection
matrix for each planeo The matrix for (Tv is qui te simple :
-1

O
O
We see that reflection in (T v just changes the sign of y. The following matrices
give the new x- and y-coordinates after reflection by (T v' and (Tv" :
_13
O
13
O
2 2 2 2
(J ' = (J "==
1 v v _13
- O
13
-
1
O
2 2 2 2
O O O O
To employ these matrices, substitute the x, y, z-coordinates of one of the hydrogens
for X, y, and Z to get the new coordinates x', y', and z' after the operati on.*
For example, to determine the etfect of (1,' on (- 1/2, j3/2), we see that the z-coordinate will
not change, and x and y are given by
y
x'
FIGURE 2-11 A rotation 01
the x-axis by 120
0
about a
z-axisrepresentedbythedol.
Note that (Jv' does not change (-1/ 2, -}3/ 2) but does interchange the other
two hydrogens. For this symmetry we have off-diagonal elements that
simultaneously change the old X-coordinate into a new one with x- and y-
components.
Next, we shall work out the irreducible representations for the x, y, and
z axes in the C
3v
point group. The z-axis, which is the rotation axis, transforms
unchanged andcan be thoughtofas beingdescribed by the three 1 x 1matrices
[1].
E 2C
3
3(Jv
[lJ [lJ [lJ
A 120
0
rotation ofa vector on the x-axis produces a vector with both x- and
y-components(Fig. 2-11). The same thing occurs for rotation ofy. Substituting
({J = -120
0
intotherotationmatrix andmultiplying by {x,y}gives x'and y' as:
x'= -G)-ef)
y' = +(xf)- ~ )
As we have just shown, the two vectors, x and y, are related and cannot be
transformedindependently.Thex- andy-vectorsarerepresented in thecharacter
table by the symbol E, used to indicate double degeneracy. The trace of the
matrix(obtained by summingthediagonalelements,and which has been shown
to be independent ofthe basis selected)is the characterreported in thecharacter
tableo Thecharacteris invariant under any similarity transformation carried out
on the matrix. The significance of this will be made c1earer when we consider
more complicated transformations,
In summary, the characters ofall non-degenerate point groups (.e., those
having a C
2
as the highest-fold rotation axis) are 1 x 1matriceswith characters
of +1 or -1, which indicate symmetric or antisymmetric behavior of an
appropriate basis function under the symmetry operation. A degenerate point
group contains a character that is the trace of the transformation matrix and
that summarizes how the degenerate basis set transforms together.
Generally speaking, then, we shall end up with an n x n matrix for our
representation(wherenis thesizeofourbasisset) foreachoperationin the point
group; e.g.,in C
2v
E (Jyz
[
J[ J[ J[
J
If each oftheseis block diagonal,they correspond to irreducible representations.
Ifnot, we want a similarity transform to block diagonalize them.
le
er
~
vn
er
ut
ter
)se
'rs
an
mt
nd
[ur
int
2-9
2-9 MORE ON CHARACTER TABLES
We earlier defined a class as a complete set of elements that are conjugate to
each other. We also mentioned that conjugate matrices have identical characters.
(You can confirm this by checking the trace of the (1u, (Ju' , and (Ju
n
matrices just
given for the degenerate x and y vectors.) Thus, cIasses are grouped into one
entry in the character tables; see, for example, 3(J u of the C
3u
character tableo
The different irreducible representations may be thought of as a series of
orthonormal vectors in k-dimensional space, where k is the number of classes in
the point group. Since vectors that form the basis for two different irreducible
representations, Xi and Xj , are orthogonal, we have
I 9X *(R)XJ{R) = O when i i= j (2-9)
R
The sum is taken over all h symmetry operations (each denoted by R) in the point
group, and 9 represents the number of elements in the cIass. The suro of the
squares of the characters of any irreducible representation equals h, the order of
the point group.
I g[XJR)]2 = h (2-10)
R
where R is a sum over all operations, so 3(J u is counted as three times (J u in this
summation for 9 = 3.
A character table (Table 2-3) is divided into four main areas, as explained
in the following paragraphs.
TABLE 2-3. Character Table for the e
3v
Point Group
C
3u
E 2C
3
30"u
Al 1 1 1 Z X2 + y2, Z2
A
2
E
1
2
1
-1
-1
O
Rz
(x, y) RxRy (x
2
_ y2 , xy)(xz, yz)
1 II III IV
Area I: The meanings of A, B, E, and the 1 and 2 subscripts have been
discussed. Other symbols are encountered in the character tables; see Appendix
A for examples. The symbols E and T represent doubly and tril?ly degenerate
states, respectively. (F is often employed instead of T). If the molecule has a
center of symmetry (see the C
2h
, D
2h
, D
4h
, and Oh character tables in Appendix
A), the subscript 9 is used to indicate symmetry (+ 1) with respect to this center,
while u indicates antisymmetry ( - 1). Prime and double prime marks are employed
to indicate symmetry and antisymmetry, respectively, relative to a (Jh plane of
symmetry.
More on Character Tables 41
Examples of the application of these rules can be obtained by referring to
the character tables in Appendix A. Al! A species in the D 3h group have values
of + 1 in the column for the principal axis, 2C
3
. The species A are symmetric
(i. e. , have + 1 values) to 3C
2
, and A
2
species are antisymmetric (-1) to these C
2
axes. In D
4h
, al! A species are symmetric with respect to the perpendicul ar C
2
axes. The prime species are symmetric ( + ) to the horizontal plane (Jh ' while the
double prime speci.es are antisymmetric (-) to this planeo The ti species are
antisymmetric ( - ) to the center of symmetry, while the g species are symmetric
(+ ).
Area II : This has already been discussed, but there are a few additional
points to be made. Sorne character tables contain imaginary or complex
characters. Whenever complex characters occur, they occur in pairs such that
one is the complex conjugate of tbe othcr. While they are mat hematically di st inct
irreducible representations, in all physical problems no difference is observed and
the res ults are as if they had been a doubly degenerate irreducible representation.
In the T, point group, two tri ply degenera te species exist, TI and T
2
For T
2
, x,
y, and z form a basis ; for TI ' all three of the rotations aboullhese axes form a basis.
Area IIJ: This area li sts the transformation properties of vectors along the
x, y, and z axes and rotations Rx R
y
, and Rz (represented as curved arrow )
about the x, y, and z axes.
Area IV : Tbis area indicates the transformation properties of lhe squares
and binary products of the coordinates. Al though there are six po sible square
and binary products (x
2
, y2, Z2 , xy, xz, and yz), only fi ve are ever indicated beca use
X2 + y2 + Z2 = r
2
and, as a resuJt, one of the li near combinations is redundant
(r
2
is the square of the radius of the X2 + y2 + Z2 sphere). The direct product of
two vectors is obtained by multi plying the species for each, e.g.,
XY = B X = A
2
. To perform this multiplication, the fol!owing procedure is B
2
used:
or
(1)(1) (-1)(-1) (1)( - 1) ( -1)(1)
giving the result
+ 1 +1 -1 -1
The result +1, +1, -1, -1 is identical to the irreducible representation A
2
;
hence, B x B
2
= A
2
. In subsequent chapters we shall have occasion to take the
direct product ofirreducible representations, and this procedure wil! be employed.
Many of the combinations in this area have symmetry properties identical to
those of the d-orbitals (e.g. , xy and d
xy
are identical). Thus, these products can
be used to indicate which orbitals wil! remain degenerate in transition metal ion
complexes of various symmetries. The pair X2 - y2 and xy are degenerate in a
molecule as are xz and yz, but xz and yz belong to a different c1ass than do C
3v
X2 - y2 and xy. The different c1asses can have different energies in complexes
wi th different symmetries.
The wave functions of a molecule are an example of a basis for a
representation; that is, they can serve as the basis set for the representation
matrices of a group. These wave functions must possess the same transrormation
properties under the operations of the group as the irreducible representations.
11
e
le
'e
le
al
~ x
el
Id
n.
x,
IS.
he
14
2
;
lhe
led.
1 10
can
ion
in a
I do
~ x e s
2-10 More on Representatons 43
Thus, each molecular orbital in a molecule will have a symmet ry given by one
of the irreducible representations in the point group of the molecule.
2- 10 MORE ON REPRESENTATIONS
If, instead of vectors, we choose to obtain a representation using a set of atom
coordinates, the resulting matrix could have dimensions of 3N x 3N associated
with the three Cartesian coordinates for each of the N atoms in the molecule
(Fig. 2- 12).
FIGURE 2- 12 The 3N coordinates f or
H
2
0 in a Cartesian coordinate system.
t ti xa
~ Y a
z
For the E matrix, we have a 9 x 9 representation
1 X
o
X
o
,
Yo
Yo'
,
Zo Zo
Xa' 1 Xa
Yo'
Ya
,
Zo Za
X'
X
b b
Yb Yb
,
Zb Zb
Any 1 x 1 diagonal matrix element in this large matrix corresponds to a
non-degenerate irreducible representati n in the final block diagonalized matrix.
Accordingly, we shall need nine irreducible representations to describe this system.
For the e
2
symmetry operation\9fl our nine dimensional basis set, we have
-1 X
o
X
0
1
-1
Yo Yo
Zo
zo'
O O O -1 O O xa xa
,
O O O O -1 O
Ya
y;
O O O O O 1 Za
za'
-1 O O O O O x
b
X'
b
O -1 O O O O
Yb
Yb'
O O O O O Zb
zb'
Similar matrices can be constructed for (Jo ((JJ and (Jo ((Jo')
xz yz
FIGURE 2-13 Form 01 a
matrix alter diagonal ization.
These larger representations can be broken up, i.e., are reducible into the
sum of many of the smaller irred uci ble ones given earlier for the e2v poin t gro u p.
We could proceed by looking for a similarity transform Qthat block diagonalizes
the 9 x 9 E, e
2
, (Ju' and (Ju' matrices. Then the blocks in the diagonalized matrix
would correspond to the irreducible representations for this molecule and in this
basis set. Although this would not occur in the e
2u
point group (or any point
group with a lower than threefold axis), matrices that cannot be reduced to a
1 x 1 matrix would correspond to degenerate representations. After diagonali-
zation, the matrix would have the form shown in Fig. 2-13, and each block can
be treated separately as a representation, provided that the reducible represen-
tations of the other symmetry operations are similarly block diagonalized. There
is an easier way to solve this problem, and we shall describe it next.
2-11 SIMPLlFIEOPROCEOURES FOR GENERATING ANO
FACTORING TOTAL REPRESENTATIONS;THE
OECOMPOSITION FORMULA
The trace of the matrices for E, e
2
, (Ju' and (Ju' operations for the problem
described above is
E
XT = 9
In actual practice, similarity transforms are not used to find the irreducible
representations that constitute this representation. E ven the total representation
is found by simpler procedures, and this is then factored into the individual
irreducible representations by using the decomposition formula, vide infra.
With a little reflection, it can be seen that the following rules summarize
what we have already said about generating the character of the total represen-
tation.
1. Any vector (or part of the basis set) that is unchanged by a symmetry
operation is assigned +1. (This diagonal matrix element left the coordinates
unchanged in our earlier discussion.)
2. Any vector or part of the basis set that is changed into the opposite
direction is assigned -1. (The diagonal matrix element reflects this: in the e
2u
example discussed earlier, all changes were either symmetric (+ 1) or unsymmetric
( -1)).
3. A vector or part of the basis set that is moved onto another vector by
a symmetry operation is counted as zero. Recall that in our discussion of the a
and b vectors, the vectors were interchanged in our earlier example of H
2
0 with
off-diagonal e1ements, and the trace of the mitrix dealing with Ha and Hb is zero.
These rules give us directly the value of the trace of the matrices we generated
in our earlier discussion of the nine coordinates (3N) of the water molecule.
Applying these rules to these nine coordinates, we see that E gives a trace
for the total representation, XT, of 9. The e
2
operation moves all Ha coordinates
into Hb and vice versa for a result of zero; while for oxygen, x goes to -x (-1),
Y goes to - y ( -1), and z remains unchanged (+ 1). Accordingly, XT for the e
2
operation is -1. With x perpendicular to the plane of the atoms, reflection in
IP
es
'IX
liS
:re
em
ible
ion
[\lal
2-11
the xz-plane moves all Ha and Hb vectors for a result of zero. The x and z vectors
remain unchanged, while y goes to - y for a net result of +1. Refiection in the
yz-plane does not change any of the six y or z vectors (+ 6), while the three
x vectors go to -x (-3) for a total (+6 - 3) of +3. Thus, XT = 9, -1, 1, 3
as described before.
When an operation does not interchange atoms but moves them into a new
position that is sorne combination of the old coordinates (e.g., C3 on x), the trace
of the matrix must be determined by working out the matrix for the geometrir.
transformation as was done earJier. For rotations, the rotation matrix can be
employed.
Next, we shall describe how to determine all of the different irreducible
representations that make up the total representation. The following formula
shows how to do this; books on group theory should be consulted by those
interested in the derivation. The formula summarizing how to factor a total
representation, the so-called decomposition formula, is:
(2-11)
Bere a is the number of contributions from the ith irreducible representation,
R refers to a particular symmetry operation (or, if there is more than one element
in the class, to the whole class); h, the order of the group, is given by the total
number of symmetry operations in the point group (in determining this, be sure
to count 30"v's as three); 9 is the number of elements in the class ; X(R) is the
character of the irreducible representation; and XT(R) is the character for the
analogous operation (R) in the total representation. The use of this formula is
best demonstrated by decomposing the total character for the 3N coordinates
of water,
XT=9 -1 3
using the C
2v
character tableo The value of h is 4, and 9 = 1 for all symmetry
operations. We sum over the R (in this case, 4) symmetry operations as follows:
a
A
= [gXAJE)XT(E) + gX4C2)XT(C
2
) + gX40"v)XT(O"v) + gXA(O" v' )xT(O"V')]
= "4
1
[1 x 1 x 9 + 1 x 1 x (-1) + 1 x 1 x 1 + 1 x 1 x 3] = 3
1
a = "4 [1 x 1 x 9 + 1 x 1 x (- 1) + 1 x (-1) x 1 + 1 x (-1) x 3] = 1
A2
1
= - [1 x 1 x 9 + 1 x (-1) x (-1) + 1 x 1 x 1 + 1 ?< (-1) x 3] = 2 a
B
4
1
= - [1 x 1 x 9 + 1 x (-1) x (- 1) + 1 x (-1) x 1 + 1 x 1 x 3] = 3 a
B
2 4
Thus, we find that the total representation consists of the sum of the irreducible
representations 3A, lA
2
, 2B , and 3B
2
. The total representation aboye describes
The Decomposition Formula 45
;/0,,\
H H
FIGURE 2-14 Vectors
representing the two bonds
in H
2
0.
all of the degrees of freedom of the molecule. In infrared spectroscopy, we are
concerned with all of the possible vibrations that a molecule can undergo. If one
subtracts the irreducible representations for the three basic translational modes
and three rotational modes from the total representation, the remaining irreduc-
ible representations describe the vibrations.
A physical view of the decomposition formul a can be had by considering
the irreducible representations as vectors in a given point group. The general
representation is also taken as a vector. The dot product of the general
representation vector with an irreducible representation vector that does not
contribute will be zero. The group order is used as a normalization factor to
insure that the dot product of a contributing irreducible representation vector
will give the number of contributions from the vector.
Another basis set, used to give a more transparent view of certain molecular
vibrations, employs the bonds to be stretched during a vibration as vectors.
Consider the two vectors for stretching the OH bonds of water, illustrated in
Fig. 2-14. The matrices using these bond vectors (SI a nd S2) asthe basis set are:
av(xz)
E=G

=

' [0
e2 av(yz) = 1
=

The total representation XT is given by:
E e
2 a v(Xz)
XT = 2
2

Factoring the total representa tion for these bond stretches leads to the
symmetry of the two stretching modes as A l and B
2
, which correspond to the
symmetric and asymmetric stretch, respectively.
2-12 DIRECT PRODUCTS
We have already mentioned that the characters of the representation of a direct
product are obtained by taking the products of the characters of the individual
sets of functions. In e
lv
'
That is, B1 X B1 = Al ' When dea ling with degenerate irreducible representations,
remember that the degenera te bases are t ransformed in pairs, with the character
corresponding to the trace of the transformation mat rix for both. This can be
g
II
II
)t
a
)r
H
S.
In
'e:
the
the
reet
(lual
ians,
r
be
iJlustrated by the product ofE x E in the C
4v
point group. In terms of the x, y
basis for C
4v
, we have
-
C4 =
C
2
E= [ ~ ~ J
G
~ J
_[-1 0J
O -1
x = E E ~
~ J x [ ~ ~ J =
1 O
1 O
O O
~
O O
~ ]
By analogy to taking the cross product, the identitygives a total representation
offour because the cross product oftwo matrices increases the dimensionality
ofthe matrix. The formula for taking the cross productoftwo matrices involves
taking the a element (where a is the left matrix and b is the right) times the b
matrix to give the upper left 2 x 2 part ofthe resulting 4 x 4 c matrix; that is,
ab =c,ab2 =c
12
,ab
2
= c
2p
anda
ll
b
22
= c
22
.Thea2 elementtimes
the b matrixgives the upper right quarter ofthe c matrix, thea
2
element times
the b matrix gives thelower left quarter,and the a
22
element times the b matri,x
gives the lower right quarter. The character ofthe direct product matrix is the
productofthe charactersofthe original matrices. In general,thedirect products
ofirreducible representation matrices may be reducible.
M. Tinkham,"GroupTheoryand Quantum Mechanics," McGraw-Hill,New York, 1964.
F. A. Cotton, "ChemicaJ Applieations of Group Theory," 3rd ed., Wiley-Interscience,
New York, 1990.
M. Orchin and H. H. Jaff, 1. Chem. Educ., 47, 246, 372, 510 (1970).
M. Orchin and H. H. Jaff,"Symmetry, Orbitals, and Spectra," Wiley-Interscience, 1971.
C. D. H. Chisholm, "GroupTheoretical Techniques inQuantum Chemistry," Academic
A. Vincent, "MolecularSymmetry and GroupTheory," WiJey, New York, 1977.
Forspacegroups, see: 1. D. Donaldsonand S. D. Rass,"SymmetryandStereochemistry,"
Wiley, 1972.
1. Work out all the classes (of symmetry operations) in a two-dimensional equiJatera1
triangle. (Only x and y dimensions apply, so there is only a threefold rotation axis
and 30" v planes.)
2. Work out the group multiplication table for NH
3
. Determine all classes.
1 2 1
3. Identify the subgroups in G
4
, G
4
, and G
6
(The groups were given in this chapter.)
4. Demonstrate that the Eg and B
2g
irreducible representations ofthe D
4h
point group
are orthogonaJ.
Exercises 47
ADDITIONAL
READING
EXERCISES
48 Chapler 2 Group Theory and the Character Tables
S. In the C
4 U
point group, indicate the operations that comprise
2 3 4
a. the2C
4
givenin thecharactertable;thatis, whichofC
4
t, C
4
, C
4
, orC
4
comprise
2C4
b. the 20"u'
c. the 20"d'
d. Construct a group multiplication table for the symmetry operations in C
4u
.
e. Can a molecule with C
4 u
symmetry have a dipole moment ? Ir it can, where is it
located?
6. In addition to vectors and coordinates of a point, the orbitals of an atom can be
assigned to irreducible representations. Using the character table for the D
4h
point
group, indicate the representations for the p-orbitals and d-orbitals. Takethe center
ofthe orbitals as the point about which al] operations are carried out. Why do the
p-orbital representations have a u subscript?
7. Forwhich irreduciblerepresentationdothefollowingvibrationalmodesform a basis ?

CI/ ""CIJ
(c)
8. RecalltheproblemofapointintheCartesiancoordinatesystemwithanx,y, zbasisset.
a. Write the matrix for an inversion operation.
b. Perform the matrix multiplication that shows
c. Complete the multiplication table for the C21, point group.
9. Consider the C
2 u
point group in thexy plane. Using unit vectors along the x- and
y-axes as the basis, one finds the following representation :
E C
2
O" xz O" y.

where C
2
is along the z-axis.
(b)
Exercises 49
it
be
nI
ter
he
s?
el.
and
Consider the axes x' and y', which are at an angleofIX = 30 counterclockwise with
respect to the x- and y-axes and in the same plane. Keeping e
2
along the z-axis and
the (J planes in the xz- and yz-planes, give the representation for which unit vectors
aJong x' and y' serve as a basis se!. Show that the traces are the same in the new
representation for each operation as those in the representation aboye.
10. Generate the matrices describing how the sets offunctions (x, y, z), (xy, xz, yz), and
(2z
2
- X2 - y2, X2 - y2) are transformed by the various operations of the group O.
Show how the trace transforms as irreducible matrix representations designated TI '
T
2
, and E, respectively.
11. Write the matrices describing the effect on a point (x, y, z) of reftections in vertical
planes that lie halfway between the xz- and yz-planes. By matrix methods,determine
what operation results when each ofthese reftections is followed by reftection in the
xy-plane.
12. ConsiderAuC1i with D
4h
symmetry. Usethex, y, and zCartesiancoordinatevectors
at eaeh atom as a basis set to form a total representation. Determine the irreducible
representations.
13. In thegroupsspecified, determinethedirect productrepresentationsand reduce them
when possible.
b. E x E in e
4U
'
c. E x E in e
3u
'
14. Consider the two complex ions cis-[CoF4Cl2]3- and trans-[CoF 4ClzJ3-. For each
ofthese ions, find the symmetry designations ofthe d orbitals.
15. In problem 10, we worked to find out that in the Opoint group the sets offunctions
(x, y, z), (xy, yz, xy), and (x
2
- y2, 2z
2
- X2 - y2) transformed as TI ' T
2
, and E,
respectivel y.Thecharactertablecontainsthisinformation,butis truncatedaftergiving
information on product functions (xy, xz, etc.) and does not show how the triple
product functions (e.g., the xyz) transformo The triple products correspond to the
f-orbital functions(x
3
, y3, Z3, xyz, X(y2 - Z2), Y(Z2 - X2), z(x
2
- y2)). Takeall ofthese
combinations to ascertain how the seven f-orbitals transform in the e
2
" poiritgroup.
16. Use this square in the following problems. You are to assume that the square is like
atable;i.e. , it cannot beturned upsidedownandstill be thesame.Thetwocoordinate
systems sharea common z-axis perpendicular to the plane ofthe figure.
~ /x'
~
x
Consider a reftection, (J xz. (Since the z-coordinate is always constant, work the
following problemsas two-dimensional cases.)
a. Derive the matrix corresponding to this reftection in the x, y-axis system.
b. Derive the matrix corresponding to this reflection in the x', y'-axis system.
c. Showthat(J x: in thenew axissystemisrelated to(Jx: by asimilaritytransformation
ofthe type
DerivetheT matrix and verify this equation.Thebold symbolsrepresentmatrices.
17. a. Wediscussed theproblem ofusing theOHbondsin watertoform a basisfor 2 x 2
representation matrices in C
Zv
symmetry. Consider the HzS molecule and assume
a 90bondangle. Writethefour matricesfor thesymmetryoperationsin C
z
" using
the S-Hbonds as a basis set.
b. ActualIy, thesameinformation is obtained from a set ofaxeszand yset up at the
S nucleus as shown, with '1. along the Cz-axis and y in the molecular planeo Write
out the matrices using this basis of'land y.
c. Suppose thatR is the matrix for sorneoperationin the z, y frame and thatR' is the
corresponding matrix in the S-H bond frame. Then a 135 countercJockwise
rotationofthepointsintheplanewillconvertR toR'byasimilaritytransformation,
i.e.,
Write out the matrix n.
18. ThefolIowingisexcerptedfromStrommenandLippincottJ. Chem. Ed., 49,341 (J972):
Ina recentissueitwaspointedoutby SchiiferandCyvinthatthewelI-knowngroup
theoretical equation
(1)
fails to work when applied to linear groups. Equation (1) is used to determine the
number of times, n(y), that a given symmetry species y will occur in the reducible
representation ofa particular molecule. XR is the characterofthe reducible represen-
tation r;XR
1Y
) is the character of the irreducible representation; and R is the index
used to denote each ofthe symmetry operationsofthe group.
Outlioe ofMethod
1. Assume a lower molecule symmetry which corresponds to a subgroup G of the
molecular group GO
2. Placeasetof cartesiancoordinatevectorsoneachatom.(Thez-axismust be placed
along the maximum symmetry axis of the parent group.)
3. Using standard methods obtain the characters ofr,educ;bl e'
on
:es.
x: 2
,me
ing
the
Vrite
wise
[tion,
972) :
~ r u p
(1)
Icible
rcsen-
index
01' the
laced
Exercises 51
4. Ca1culate the values ofeach n(y) by application ofequation (1).
S. Finallycomparethe basis vectors ofthe irreducible representations under GO with
those obtained for the molecule assuming G.
(By "basis vectors," rule 5 means the functions x, y, Z, X2 - y2, etc., found in the
right-hand columns of the character table.)
a. To what symmetry group does the molecule acetylene (C
2
H 2) belong?
b. Why does equation (1) fail to work for groups to which linear molecules belong?
c. Use the method outlined (with G= D
2h
) to obtain the irreducible representations
(in the group to which C
2
H
2
belongs) for a basis set consisting of x, y, and
zvectors located ateach atom.
Molecular Orbital
Theory and Its
Symmetry Aspects
Introduction 3-1 OPERATORS
As is true for many of the topics in this text, whole books have been written on
the subject of this chapter. This chapter will be a very brief presentation of those
fundamentals of molecular orbital theory that should be a part of the background
of any modern chemist. We shall concentrate on those aspects that will be needed
for our considerations of spectroscopy. One can well appreciate that a complete
understanding of the spectroscopy, reactivity, and physical properties of substan-
ces will not be possible until we can interpret these phenomena in terms of the
electron distribution in the molecule.
In principIe, al! the information about the properties of a system of N partic\es
is contained in a wave function, 1/1, which is a function of only the coordinates
of the N particles and time. If time is inc\uded explicitly, 1/1 is called a time
dependent wave function; if not, the system is said to be in a stationary state.
The quantity 1/1*1/1 (where 1/1* is the complex conjugate of 1/1) is proportional to
the probability of finding the electron at a particular point.
For every observable property of a system, there exists a linear Hermitian
operator, a, and the observable can be inferred from the mathematicaJ properties
of its associated operator. A Hermitian operation is defined by
We shall abbreviate the aboye integrals by the so-called bra <Iand ket 1> notation
as:
To construct an operator, a, for a given observable, one first writes the c\assical
expression for the observable of interest in terms of coordinates, q, momenta and
time. Then the time and coordinates are left as they are and for Cartesian
coordinates the momenta, Pq, are replaced by the differentiaJ operator, i.e.,
where q is the coordinate that is conjugate to Pq' For example, the quantum
mechanical operator for kinetic energy, f, can be constructed by first wrlting the 52
3-1 Operators 53

.les
tes
re
ate.
.to
jan
"ties
tion
sical
.and
esian
the
classical expression for the kinetic energy:
1 1 1
T = 2mv
x
2 + 2muy 2 + 2mvz 2
Momenta = mv = p, so,
1
T = 2m (p/ + p/ + p/)
where
If an operator fX corresponds to an observable, and if 1/15' the wave function
fo,. the state, is an eigenfunction of the operator ti, then ti l/l
s
= asl/l
s
where as is a
number. An experimentalist making a series of measurements of the quantity
corresponding to ti will a/ways get as' The wave functions are eigenfunctions of
the Hamiltonian operator which yields energies as eigenvalues, i.e., numbers ;
iN" = EI/I"
(3- 1)
Theoperatorfor angularmomentum about the Z-axis is also suchan operator:
[zl/l" = mhl/l"
(3- 2)
where m, the azimuthal quantum number, has values of +/...O... -1.
Some properties ofa system are not characterized by an eigenfunction for
the appropriate operator which descr ibes that property. Then a series of
measurements of this property will not give the same result, but instead a
distribution ofresults.The average va/ue orexpectation value, <as)' is given by:
(3-3)
1/1 is generally not an eigenfunction of the operatorti, but using equation (3-3),
one can obtain the average value.
Inthecourseofthisbook,weshallhaveoccasiontoconsidermanyoperators.
We shall discuss them as the need arises. Our immediate concern will be with
the Hamiltonian operator and the Schrodinger equation:
fIl/I = EI/I
Thisequation cannot be solved directly for the energy, E, on molecularsystems
because one cannot find a function 1/1 such that HI/IN is a constant and not a
54 Chapler 3 Molecular Orbital Theory and Its Symmetry Aspects
variable function of the position of the electron. Consequently, we average H!/I
over al! space by multiplying by !/I* and integrating over al! space:
f!/I*H!/I dr = f!/I*E!/I dr = E f!/I*!/I dr
so
(3-4)
The Hamiltonian operator for most systems is easily written as
where V is the potential energy of the system. Other operators are just as easily
written by writing the classical expression for the property of interest and replacing
the momentum by -ih%
x
' Thus, ifwe had accurate wave functions and could
sol ve the resulting integrals, we could calculate all of the properties of a molecule.
Unfortunately, such calculations are rarely practical.
In the LCAO-MO method (linear combination of atomic orbitals-molecular
obital) of solving this problem, the wave functions, !/Ij' of the resultingj molecular
orbitals are approximated as linear combinations of atomic orbitals:
(3-5)
where C
jy
is the coefficient describing the contribution of ([Jy to the jth molecular
orbital. The total electronic ground state wave function \f is a product of the
individual molecular orbital wave functions. As we shall show shortly, the !/l/s
form the basis for irreducible representations of the molecular point group.
Therefore, the symmetry of the total electronic ground state wave function is
obtained by taking the direct product of the irreducible representations of the
occupied !/l/s.
The various ways of carrying out molecular orbital calculations correspond
to different approximations that are used in the solution of the problem. One
such approximation ignores the correlation of the motion of the electrons in the
molecule. If there are two electrons in a molecule, we know that at any instant
one of the electrons wil! tend to avoid the region occupied by the other. Over a
longer time period, the motion of one electron will be correlated with the motion
ofthe second electron. When this correlation is ignored, the resulting !/l/s describe
the system in terms of the coordinates of a single electron. Such wave functions
are labeled one electron molecular orbitals. In describing the molecule, two
electrons are added to each of the one electro n m.o.'s.
For clarity, we can proceed with the problem of determining our wave
functions by using a two-term basis set ([J 1 and ([J2 (i.e., two atomic orbitals on
two different atoms) without any loss of generality, i.e., equation (3-5) for our
wave function is
3-1 Operators 55
Ir
le
's
a
m
be
ns
1' 0
ve
on
Substituting this equation for !/J into equation (3-4) produces
E = J(CC'p + C
2
C'p2)fI(cC'p + C
2
C'p2) d,
J(CC'p + C
2
C'p2)(CC'p + C
2
C'p2) d,
J(cC'pfIcC'p + CC'pfIC
2
C'p2 + C2C'p2fIcC'p + C2C'p2fIcZC'p2] d,
J[CC'pCC'p + C
2
C'p
Z
CC'p + CC'pC
2
C'pz + C2C'p2C2C'pZ] d,
Since C and C
2
are constants, they can be taken out of the integrals. We can
abbreviate JC'pfIC'pjd, as Hu and JC'piC'pjd, as Sij' Furthermore, H
2
= H2 and
SlZ = SZ' leading to equation (3-6).
(3-6)
The various types of integrals are given different names:
H integrals are referred to as Coulomb integrals;
Hij as resonance integrals; and
Su as over/ap integra/s. The value of Si; = 1 for normalized a.o.'s.
The variationa/ principie is employed to find the set of coefficien ts C and C2
that minimizes the energy, Le., gives the most stable system. The energy we get,
called the variation energy, will depend upon how good our wave function is.
E var > EO(ground , lale energy)
(3-7)
This minimization (i.e., the variation procedure) is carried out by setting the
partia] derivative of E with respect to each of the coefficients (C's) equal to zero.
Taking the partial derivative of equation (3- 6) with respect to each of the
coefficients, setting oE/ oC and oE/ oC
2
both equal to zero, and collecting terms,
we get
C(H
ll
- ES) + C
z
(H2 - ES2) = O
(3-8)
C(H
21
- ES
2
) + C
2
(H
z2
- ES
22
)= O
This gives us two homogeneous linear equations in two unknowns. The trivial
solution is C = = O, but this would require!/J = O(where!/J = C C'p + C
z
C'pz) C
2
Other solutions exist only for certain values of E, and these values of E can be
found by solving the secular determinant:
H - ESl
(3-9)
HZl - ESZ
I
The determinant is solved by standard mathematical procedures. Essentially, we
are solving two linear, homogeneous equations in two unknowns. An n x n
determinant gives an nth-order polynomial equation in energy with nroots. Since
the size of the determinant, n, equals the number of atomic orbitals, we get n
56 Chapter3 Molecular Orbital Theory and Its Symmetry Aspects
energies or n molecular orbitals from n atomic orbitals. In the case where the
two atoms are the same, we get
(with SIl and S22 = 1). The two roots for this equation are:
_HII+HI2
E1 - and (3- 10)
1 +SI2
Solving or approximating the integrals enables one to solve for the energies.
The energies so obtained can be substituted one at a time back into equation
(3-8), and the coefficients are then obtained by using a third equation:
e/ +e/ = 1. The t'-Yo equations that result are not independent (the deter-
minant equals O), so we need the third equation.
The evaluation of the S 12 integrals is straightforward when the structure of
the molecule is known. The integrals H11 and H12 cannot be determined
accurately for complex molecules.
For the hydrogen molecule, the Hamiltonian operator is
L(-h
2
/8n
2
m)Vi.2 - e
2
/r
A
.
l
- e
2
/r
8
, 1 - / r
A
.
2
- e
2
/ r8.2 +e
2
/ r
A
.
8
+e
2
/ r
I2
)
1.2
The two hydrogen nucIei are labeled A and B and the two electrons 1 and 2.
The charge on the electro n is e, the distance from nucIeus A to electro n 1 is rA , l '
and so forth. We solve the integrals by using the various individual terms in the
Hamiltonian separately. Accordingly, for one Jep/lepj dr , there are many integrals
to be evaluated. The electro n-electro n repulsion integrals <epi I e
2
/r121 ep) are
particularly difficult. You can well imagine how complicated the Hamiltonian is
and how many integrals would be needed even for PCl
s
' Ab initio calculations
do all the integrals and thus are practical only for small molecules or wealthy
chemists.
The various ways to "guesstimate" values for these integrals correspond to
various ways to do molecular orbital calculations. We shall return toa more
detailed description of sorne of these procedures subsequently.
3-2 A MATRIX FORMULATION OF MOLECULAR
ORBITAL CALCULATIONS
Modern approaches to the solution of eigenvalue problems employ a matrix
formulation. Since the quantum mechanical description of many of the spectro-
scopic methods treated in this text is discussed in matrix terms, the previous
section will be reformulated in matrix terms to introduce the general approach.
The solutions ofthe secular equations are eigenvalues ofthe Hamiltonian operator
H, so HIj = EIj can be written in the LCAO approximation in matrix form as
[Hu][e] = [S] [e][E] (3-11 )
3-3 Perturbation Hleory 57
,:
)f
d
2.
.1'
he
lis
lre
1 is
ms
.hy
lo
Jre
tri x
.tro-
ious
lach.
~ t r
~ as
11)
where [e] is the coefficient matrix, [Hij] is the energy matrix of elements
{Ji IHI({J), [S] is the overlap matrix, and [E] is the diagonal matrix of orbital
energies, one for each m.O. The [E] and [e] matrices are to be determined.
Dividing both sides by [e], we obtain
(3-12)
The coefficient matrix is, in effect, a similarity transform that diagonalizes the
[Hu] matrix to produce a unit [S] matrix. The energies result directly from the
diagonalized [H] matrix, as do the LCAO coefficients of the corresponding
molecular orbital.
3-3 PERTURBATION THEORY
Perturbation theory is a useful technique in quantum mechanics when one is
trying to ascertain the effect of a small perturbation on a system that has been
solved in the absence of this perturbation. Basically, we have the solution to
We wish to determine the effect of sorne perturbation on this ith molecular orbital,
i.e.,
(3-13)
where
(3- 14)
and the term H' is a small perturbation on the system. lt can be shown that the
first-order correction to the energy is given by:
(3- 15)
The correction to the old wave function, t/!/, can be written as a linear combination
of the k unperturbed wave functions of the original system:
t/!/ = I aikt/!ko
(3-16)
k .. i
By mixing the appropriate empty excited-state wave function into the ground
state, it is possible to polarize or distort the ground state molecule in any way
we desire. The contributions that the various t/!k functions make in our perturbed
system are given by lhe coefficients a
ik
, where
(k =1 i) (3-17)
58 Chapter 3 Molecular Orbital Theory and lIs Symmelry Aspecls
Thus, our final expressions for the energy and wave function of the perturbed
orbital, E and 1/1 , correct to first order, are
(3-18)
and
(3-19)
Note that the zero-order wave function gives us the first-order energy.
The formula for the second-order correction to the energy is given by
(3-20)
It is informative to examine what we have done in the context of a rigorous
solution of a 2 x 2 secular determinant. A 2 x 2 problem is selected because its
secular determinant can be solved easily. We shall again use our original wave
functions and the new Hamiltonian R. We write <1/I1 IRIl/l l) as H
11
and
<1/I2I RI1/I2) as H
22
, leading to
which in turn leads to
with roots
E = H
11
+ H22 JH11
2
+ H 2 / - 2H11 H22 + 4H 12
2
2
Ignoring H 12' we obtain the solutions
Using the perturbationequations given above, we write directly
and
We now see that first-order perturbation theory is permissible only when
the off-diagonal eJements can be ignored, compared with the diagonal ones.
len
3-4 Wave Functions as a Basis lor Irreducible Representations 59
/'
The second-order correction to the energy gives us:
which is an even closer approximation to the exact solution.
3-4 WAVE FUNCTIONS AS A BASIS FOR
IRREDUCI BLE REPRESENTATIONS
Since the energy of a molecule is time invariant and independent of the position
of the molecule, the Hamiltonian must be unchanged by carrying out a symmetry
operation on the system. (Recall that the symmetry operation produces an
equivalent configuration that is physically indistinguishable from the original.)
Thus, any symmetry operation must commute with the Hamiltonian; i.e.,
H R = RH. Like the irreducible representations, the eigenfunctions are constructed
to be orthonormal:
i.e., (j = O when i f= j and (j = 1 when i = j. It is a simple matter to show that the
wave functions form a basis for irreducible representations.
If we take the wa ve equation:
and multiply each side by the symmetry operation R, we get (for non-degenerate
eigenvalues):
where RHtf = HRtf , and E commutes with R beca use E is a constant.
Consequently, Rtf is an eigenfunction. Since tf is normalized, Rtf must also be,
for we do not change the length of a vector by a symmetry operation; therefore,
We have just shown that by applying each operation of the point group to tf (non-
degenerate), we generate a representation of the group with all characters equal
to 1, that is, a one-dimensional and therefore irreducible representation. Thus,
the eigenfunctions (non-degenera te) for a molecule are a basis for irreducible
representations. It can also be shown that this is true for degenerate eigenfunctions.
Symmetry in
Quantum
Mechanics
60 Chapter 3 Molecular Orbital Theory and Its Symmetry Aspects
Any integrals involving products of molecular orbitals that belong to two
different irreducible representations must be zero. To show this, let t/Ja and t/J bbe
such molecular orbitals that are eigenfunctions of k with eigenvalues a and b.
Thus, <t/JaIHklt/Jb) = b<t/JaI HI t/J b) Since Hk = kH, we have
k (Iike other operators with physical significance) is Hermitian, so
We have just shown that
a<t/Ja I HIt/Jb ) = b<t/Ja IHIt/Jb); since a "# b, the integral <t/Ja I HIt/Jb ) must be zero.
3-5 PROJECTING MOLECULAR ORBIT ALS
In quantum mechanical calculations, we begin with LCAO's that themselves
form a basis for an irreducible representation. Although this is not necessary, it
is c1early often convenient to do so. We shall show next how symmetry
considerations alone provide much information about the atomic orbitals that
contribute to the various molecular orbitals in a molecule. In the last chapter,
it was shown that any mathematical function (e.g., points, 3N Cartesian vectors,
or bond vectors) could be used as a basis set for a reducible representation. lt
is a simple malter to extrapolate to the case in which the va:lence atomic orbitals
for a given molecule are used as a basis set for a reducible representation. As a
simple example, we shall work out the traces of the reducible representation for
the three a.o. 's comprising the n-orbitals of the nitrite ion, shown in a coordinate
system in Fig. 3-1.
Recall that earlier, when we carried out symmetry operations on the two
vectors a and b, many symmetry operations transformed one vector into the
other and the trace of the representation matrix was thus zero, the only non-zero
elements being off-diagonal. Accordingly, referring to Fig. 3-1 , 0
1
is moved into
O) with e
z
and (Jv, so contributions to the total character from the oxygen
orbitals are zero. This is true whenever atoms are interchanged. The e
z
and (Jxz
operations on the nitrogen pz orbitallead to -1 and +1, respectively. Refiection
in the yz-plane changes the sign of the p orbitals, making a contribution of -1
for each of the three p orbitals. The total representation is (e
zv
point group;
recall that x is perpendicular to the plane).
e
zv
E e
z
(J v(x z) (Jv'(yz)
3 -1 +1 -3
Factoring the total representation gives Az and 2B1; i.e. , the symmetries of the
three m.o.'s (from three a.o.'s, we must get three m.o.'s) that result from these
a.o.'s must be A
z
, B
1
, and B
1
.
We can now use a technique involving projection operators, P, to give us
more information about the wave functions. The projection operators work on
the basis set (in this example, the three p orbitals) and annihilate (convert to zero)
x
.t
Y
tt
Ir,
's,
,t
Is
a
or
.te
wo
Ihe
~ r
Ita
;en
up;
the
nese
~ liS
: on
lero)
3--5
any element in the basis set that does not contribute to a given irreducible
representation. In using the projection operators, we generally work on one
atomic orbital (or a linear combination of them) (e.g., <PI the p orbital of atom
1 of Fig. 3-1) at a time with the operator
(3-21)
where Ris the symmetry operation, XR is the character of that operation in the
appropriate point group, 1is the dimension of the irreducible representation, and
h is the order of the group. The sum is taken ayer all symmetry operations in
the point group. Accordingly, if we operate on <P I of the nitrite ion with the
projection operator of the A
2
irreducible representation, we get:
The numbers in parentheses are characters of the A
2
irreducible representation.
Next, we carry out the specified operations on <PI' and indicate the result in terms
of what the orbital <P is changed into. The result is
.P(A
2
)<p = [(l)(1)<p +(1)( -1)<p3 +( - 1)(1)<p3 +(-1)( -1)<p J
4
= N[<p - <P3J
The result is the molecular orbital corresponding to the A
2
irreducible represen-
tation. We shall ignore the factor / 4' for we will want to obtain the absolute
values for the nonnalized wave function, and not the relative values resulting
from the operators.
Ifwe had selected the orbital <P 2 to operate on, we would have obtained
This result could mean that there is no A
2
, but we know better, from having
factored the trace of the reducible representation. In this case, a node exists at
atom 2 in the m.o. with A
2
symmetry.
In order to normalize the wave function that we have just obtained, we
realize that
RecalJ that <P 1 and CfJ 3 have the same coefficient. Using an orthonormal basis set,
f<p2 dr = 1; fCfJCfJ3 dr = O; and fCfJ/ dr = 1.
Projecting Molecular Orbitals 61
y
FIGURE 3-1 A.O. basis set
larIhe n-orbital s 01 the nilrite
ion. (x is perpendicular lo
the N0
2
plane.)
62 Chapter 3 Molecular Orbital Theory and lis Symmetry Aspects
These substitutions convert the normalization equation to
1
or = - C
1
j2
The normalized function is
From factoring the total representation, we know that there is no Al symmetry
m.o. We shall use 1>(A 1) to show that a consistent result is obtained. First, consider:
_ 1
P(A
1
)<)) = 4" [(1)(1)<))1 + (1)( -1)<))3 + (1)(1)<))3 + (1)( -1)<))IJ = O
Try the other p orbitals, and you wiU see that there is no Al symmetry m.o. Next
try P(B
2
) on <))1:
We know that there are two m.o.'s with B1 symmetry. Accordingly,
~ 1
P(B
1
)<))1 = 4" [(1)(1)<))1 + (-1)( -1)<))3 + 1 ) 1 ) < ) ) 3 + (-1)( -1)<))IJ
= N[<))1 + <))3J
When we use 1>(B 1) on <))2' the following result is obtained:
_ 1
P(B
1
)<))2 = 4" [(1)(1)<))2 + (-1)( -1)<))2 + (1)(1)<))2 + (-1)( -1)<))2J = <))2
Thus, the projection operators produce two m.o. 's of B1 symmetry,
1/1 = N[<)) + <))3J and 1/1 = <))2 The A
2
and two B
1
molecular orbital wave
functions that we have generated are referred to as symmetry adapted linear
combinations of atomic orbitals. Since the B 1 m.o.'s have similar symmetries, they
can mix so that any linear combination of these two m.o. 's also has the appropriate
symmetry to be one of the two B1 m.o. 's; i.e., the two m.o.'s can be:
1/1 1 = a<))1 + b<))2 + a<))3
1/12 = a'<)) - b'<))2 + d<))3
The magnitudes of a and b will depend on the energies of the <))1 and <))2 atomic
orbitals and their overlap integrals. Thus, we cannot go any further in determining
the wave function without a molecular orbital calculation. We shall indicate
approximate ways of doing ths in the next sections. We can at this point make
one further generalizaton. Since there is no symmetry operaton that interchanges
l ~
~ y
te
~ I C
ng
lte
lke
ges
FIGURE 3-2 Shapes 01 Ihe
n-molecular orbilals 01 Ihe
nilrile ion.
Bl Bl
the nitrogen orbital with oxygen, the nitrogen must form a separate irreducible
representation.
Wearenow in a positiontodraw pictures ofthem.o.'swe haveconstructed.
They are shown in Fig. 3-2.
If onecarries out the operationsofthe C
2v
pointgroupon the m.o.'s shown
in Fig.3-2,it will befoundthattheseshapestransformaccordingto thesymmetry
labels.
Weshall work through the C
3v
ammoniamolecule as ournext example, for
it has more than oneelement in sorne classes and also has a doubly degenerate
irreducible representation. The coordinate system is given in Fig. 3-3. Our
procedure is as follows:
1. First work out the total representation and factor it:
OrbitalShapes E
z
3 0*
y
3 O
Total 7 3
z
t

- ---N----x
' :"
1 : - "
/ ~ j ... . ~
H ~ . H
/ H \
7 \ 5
6
FIGURE 3-3 The localion 01
NH
3
in a coordinale syslem.
The xz-plane passes Ihrough
H5 and N.
I
- -
+-
J3
O x x
c,
2 2
_J3
O
Y Y
2 2
O O
(trace is O)
Factoring the total representation, we obtain:
1
= - [1 x 1 x 7 + 2 x 1 x 1 + 3 x 1 x 3J = 3 a
A
6
a
A2
= 6
1
[1 x 1 x 7 + 2 x 1 x 1 + 3 x (-1) x 3J = O
a
E
= 6
1
[1 x 2 x 7 + 2 x (-1) x 1 + OJ = 2
No symmetry operation can take a hydrogen atom into a nitrogen atom, so we
can factor the total reducible representation formed from the hydrogen orbitals
(3, O, 1) and find an A and E. In this way we can work on the nitrogen atom
and hydrogen atoms separately.
2. Next, work with projection operators PA and PE' There is no need to
work with PA , for factoring the total representafion told us that there are no
molecular with this symmetry. For this purpose, we label our atomic
orbitals as folJows :
({J = N2s
({J = N2px
({J3 = N2py
1
({J4 = N2pz
6
({Js = Hsls (O"v contains H
s
)
({J6 = H
6
1s (O" v' contains H
6
)
For
For
PA operating on ({J6 and ({J 7 will, of course, gjve the same wave function, so there
is do need to carry these out. We need linear combjnations that are not identical ;
i.e. , they must not be re1ated to one another by multiplication by - 1 or by
interchange of the la beis of equivalent atoms.
For
P
A
, on q>4' None of the operations take ({J4 into anything else, so it is not
necessary to use the projection operator on ({J4' Jt is a basis set by itself and must
ere
cal;
by
not
nust
belong to the irreducible representation A 1> for it is not changed by any of the
symmetry operations. Ir we use the projection operator, we obtain:
"A I on <P I' We recognize by inspection that qJl is also a basis set by itself
and must belong to the irreducible representation A l '
"A,on <P2 ' We know by inspection that qJ2 and (P 3 form a doubly degenerate
basis set that must belong to an E irreducible representation. Thus, it is not
necessary to carry out this operation. We shall do so here to show that we get
the right answer with the operator and to demonstrate how the symmetry
operations work on a doubly degenerate basis set.
6
1
[IEqJ 2 + IC
3
qJ2 + lC/qJ2 + 10"vqJ 2 + IO"v' qJ2 + 1O"v"qJ 2]
,-A-.,,-A-., ,-A-.,,-A-.,
= ~ [qJ 2 - ~ q J f qJ3 - ~ q J + f - ~ qJ 2 + f - ~ q J - f - qJ3 + qJ 2 qJ 3 qJ3 ]
=0
For C
3
, we use
2
For a clockwise C
3
rotation, qJ = -120; for C
3
, we have qJ = -240.
x' =xcos qJ + y sin qJ
y' = - x sin qJ + y cos qJ
For the mirror planes, we use the matrices developed in Chapter 2 and the
coordinate system shown in Fig. 3-4.
Likewise, the result of PA on qJ 3 is O.
FIGURE 3-4 Effect 01
reflections through (J v on C{>2
and the ammonia hydrogen.
1
Now we apply the projection operator for the degenera te irreducible repre-
sentation E.
SI
O
ol
= - [ - - f J-[ - + f J} =

- 1 2
PE on =:3 - - 1e
3

Our resulting orbitals from and are not orthogonal, and we know that
there are only two wave functions in E. Appropriate linear combinations must be
taken to get an orthonormal basis. There are various ways to do this. One that
works for this system involves working with the matrix elements, instead of with .
the trace as we did aboye. The diagonal elements are:
ase
e 2
E
3
(J,/'
1 o -- o -- o 1 o -- o -- o
1 ][ 1 ][ ][ 1 ][ 1 ]
[ ][
o 1 o :
where a
l1
corresponds to PE and a
22
to PE .
a b
(This
PE on gives :
a
the e
1 1 2 1 , 1 " J
by i:
I/la = N
[
- 2 - 2e3 + - 2<Tv - 2<T
v

= - -
lal
be
al
llh
3-5
There is a node in t/tb al ({Js ,. The resull ofsimilar operations with PE on ({J 6 leads
to the other wave function: b
One additional way to get wave functions for degenerate irreducible repre-
sentations involves working with the character table for the rotation group involving
only the principal axis, i.e., en.
For ammonia, we would use e
3
. In e
3
, the E representations are given terms
of the imaginaries ; e.g., for e
3
,
e 2
3
where e = exp (2ni/ 3). Thus,
P
a
({J 6 = lE({J6 + ee
3
<P6 + e*e/({J6 = ({J 6 + ;({J7 + e*({Js = t/to'
P
b
({J6 = lE({J 6 + e*e
3
({J6 + ee/({J6 = ({J6 + ;*({J7 + ; ({Js = t/tb'
If we add the two together, we get one wave function ; when we subtract the two
and divide by i, we get the second wave function. Upon addition, we get
where e = exp (2ni/h) and h is the order of the rotation group. Abbreviating these
as 1', = exp (i<l and e* = exp ( - i<l and using the tligonometric identities
exp (i<l = cos <1> + i sin <1>
exp ( - i<l = cos <1> - i sin <1>
we see that 1', + 1',* = 2 cos <1>.
In the e
3
group, the rotation axis is 120, so 2cos (-120) = 2( - 1/
2
) = -l.
Accordingly, we have
(This is equivalent to our previous result, tIta = 2({J 5 - ({J6- ({J 7, obtained by using
the e
3
" point group.)
To get the other degenerate wave function, we subtract t/to' from t/t b' and divide
by i:
Substituting the trigonometric functions for e and e* produces
(e - e*) = "!!. sin <1>
(e* - 1',) 2i.
and - -- = - - SIn <1>
i i i i
Projecting Molecular Orbitals 67
Since sin (-120) = -}3/2, we obtain
Molecular
Orbital
Calculations
The final wave functions should be normalized to complete the problem. Upon
normalization of l/Jb' we obtain:
The two E functions from <P s, <P6' and <P7 can be obtained in yet another
way. First, one projects PE on <Ps to obtain 2<ps - <P 6 - <P7 ' Now, if one can
judiciously select for projection another function involving <P6 and <P7 (or sometimes
<Ps, <P 6' and 7) that is orthogonal to the one just obtained, the desired function
will result. First, we try <P6 and <P7 and realize that <P 6 - <P7 will be orthogonal to
2<p s - <P 6 - <P7'
With these two examples, we see that the symmetry of the molecule determines
many aspects of our resulting wave functions. Next, we shall consider sorne
approximate molecul'ar orbital calculations that complete the problem (but not
always necessarily correctly).
~ HCKELPROCEDURE
The various ways to guesstimate values for the integrals presented in the
introduction correspond to various ways to do m.o. calculations. First, we shaIl
consider sorne very crude approximations, the so-called Hckel m.O. ca1culations,
which give a fair account of the properties of many hydrocarbons and which wiIl
make the solution of the quantum mechanical problem in the introduction more
specific while the math remains simple. General/y, only the n orbitals ofhydrocarbon
systems are trealed. The secular equations are written directly by generalizing
our earlier result for a two-atomic-orbital system as :
C(H - ES
ll
) + ... Cn(Hn - ESn) = O
. .
The following Hckel approximations are then introduced :
1. When two atoms i and j are not directly bonded, we take Hu = O.
2. When all atoms are alike and if aH bond distances are equal (e.g., the
carbon 2pz orbitals in benzene), aH neighboring atom Hi j values are taken as
equal and symbolized by f3 (Le., H l2 = HZ3 = (3) .
3. If all atoms are alike, the H
i
integrals are symbolized by
a (J<PJf<P de = J<P zH<p z de = a).
\\
ti
Zc
bo
Thi
pro
The
le
111
IS,
di
re
011
ng
he
as
by
4. Since we use normalized atomic orbitals in the basis set, S = 1.
5. AII Si) 's are set equal to zero.
The secular equations become
Cn,,(a - E) = O
The secular determinant now becomes
=0 (3- 22)
/3"l ..... . .. . a - E
where all but directly bonded /3's are zero. As a specific example, we shall consider
the n-system of the allyl radical in Fig. 3-5. (AH sigma bonds are ignored.)
The 3 x 3 secular determinant can be directly written from equation (3-22) as:
a-E /3 O
/3 a-E
/3
=0
O
/3
a-E
Zeroes arise for the /3l3 matrix element, for the carbon atoms 1 and 3 are not
bonded. Dividing by /3 and letting (a - E)//3 = X, we obtain the determinant:
X O
1 X = O
O X
This determinant can be solved by expanding by the method of cofactors. The
procedure involves an expansion as shown for the general case:
The expansion can be done by row or column. In expanding by row, we take
each element separately and multiply it by the determinant that results when the
row and column containing the element are eliminated. Labeling the row i and
the column j, the sign is positive whenever i x j is odd and negative when i x j
is even.
For the allyl radical determinant, we expand to get:
FIGURE 3-5 The n-system 01
the allyl radical.
l
Solving these determinants gives X
3
- 2X = with solutions X = 0, )2, i.e.,
a-E M M
-(3- = O, y2, - y2.
These three roots produce the three energies :
El = a +)2(3
For the allyl radical, the secular equations are easily written by taking the
general set of secular equations and writing explicit ones for the three-atom allyl
n system or by multiplying the column matrix {el' e
z
, e
3
} by the 3 x 3 secular
determinant :
(3-23)
(3-24)
(3-25)
where X = (a - E) j (3.
For tf; l' the bonding molecular orbital, X = -)2, so substituting this into
(3- 23) and (3-25) gives
and
Rearranging, we get :
and
Using the normalization criterion:
or
2e/ = 1 and
Now
Sil
Th,
nun
timl
wa\!
sym!
cale
e
11
.r
3)
A)
~ 5
~ t o
and since
we obtain
With the coefficients defined, we can write
111
t/l1 = 2: ({JI + Ji ({J2 + 2: ({J3
(Bonding)
For t/l2
and x =0
1
or el = -
Ji
Accordingly, we can write
(Non-bonding)
Similarly
(Antibonding)
Theradical,cation,andanionorallylareall described by addingtheappropriate
number orelectrons to these molecular orbitals.
Picturesorthese orbitalscan be drawn by realizing that a node exists every
time the wave runction changes signo In general, as the number ornodes in the
wave runctioo increases,its energy increases. Furthermore, we see that all orthe
symmetry inrormation about the molecuJe is built into the molecular orbital
ca\culation. Using projection operators on the allyl radical, one can show that :
and
and
l
The two Bl m.o.'s have the same symmetry and can mix. Projection operators
cannot teH us the extent of mixing. Using a and b to describe the mixing, we can
write from symmetry the two wave functions:
and
The Hckel caIculation gives the a's and b's, and also gives the same form for
the wave functions as the projection operator because aH of the symmetry is
automaticaHy incIuded in the Hckel Hamiltonian.
The symmetry considerations for the nitrite ion are the same as for aIlyl ,
but the molecular orbital coefficients are different. Hckel caIculations have been
carried out on systems containing heteroatoms, X. These are treated by using
and
Pc- x = k'Pc-c
Tables of values to use for the quantities k and k' are listed in books on Hckel
m.o. caIculations but wiH not be presented he re because the general agreement
between fact and prediction deteriorates rapidly when Hckel caIculations are
employed on molecules containing carbon bound to other kinds of atoms.
3-7 PROPERTIES DERIVED FROM WAVE FUNCTIONS
There are many quantities of chemical interest that can be caIculated from the
wa ve functions. A few are Iisted and defined :
1. ELECTRON DENSITY AT AN ATOM r, qr
The electron density qr at an atom r in a molecule is given by :
(3-26)
where n
j
is the number of electrons in the jth m.o. The summation is carried out
over aH of the j occupied m.o.'s and e
jr
is the coefficient of the atomic orbital r
in the jth m.o.
Using the Hckel wave functions for the filIed molecular orbitals of the aIlyl
anion (two electrons in each I/Jl and 1/J2):
111
I/J 1 = 2: ({> 1 + .Ji ({>2 + 2: ({>3
1 1
1/J2 = .Ji ({>1 - .Ji ({>3
T
IS
ca
bo
on
"fr
del
be!
Th
ch
i.e.,
the
alIy
welI
Thel
Hc
tha!
the (
s
1,
n
el
nt
re
:he
26)
out
.al r
allyl
3-7 Properlies Derived from Wave Funclions 73
We sum (with n = 2) over the bonding and non-bondi'ng m.o. 's and obtain for
the electron density on carbon 1:
(
1)2 (1)2 1
q = -2 2: - 2)2 = -1 2:
At carbon 2 we find:
q2 = -2(fiY -2(0) = -1
The sum of aH the q's equals the total number of electrons in the system.
2. FORMAL CHARGE, 5
The electron density at an atom in the molecule minus that on a free atom
is referred to as the formal charge on the atom in the molecule. Considering
carbon, we place one electron in each of the orbitals of the atom to form four
bonds. In Hckel theory, where we worry only about the n system, we consider
only the pz orbital on a carbono Since it contains one e1ectron, the charge on the
"rree atom" is -1. If the charge on this atom in a molecule (i.e. , the electron
density at an atom r) is -lA, o, the rormal charge, is - OA, that is, the difference
between the charge on this atom in the molecule and that on the neutral atom.
The sum of al! the rormal charges equals the total charge on the molecule.
For the allyl anion we obtain, using the charge density calculated aboye, a
charge of -0.5 at carbon 1 and a charge or zero at carbon 2.
3. BOND ORDER, PAR
The bond order between two adjacent atoms A and Bis given by:
(3-27)
i.e., just take the product of the coefficients or atoms A and B in each m.o. times
the number or electrons in the m.o. and sum over all of the m.o. 's.
Using this rormula, the pi-bond order between carbon atoms 1 and 2 of the
allyl anion is given by
_(1)( 1) (1) _)2 _
p 12 - 2 2: )2 + 2)2 (O) - 2 - 0.
7
Hckel theory contains many crude approximations which can be justified(l)
well for hydrocarbon molecules. With more polar molecules, they are very crude.
There have been many attempts to improve on these calculations. Extended
Hckel, CNDO, INDO, and others constitute various semi-empirical procedures
that have been used to approximate various integrals. In all of these procedures,
the overlap integral is evaluated and not set equal to zero. To go through the
74 Chapter 3 Molecular Orbital Theory and lis Symmetry Aspects
various procedures in detail would take more time than we ca n allot to this topic
in this tex!. We will provide only a very rough overview of the calculations, and
will concern ourselves more with what can be done with the outpu!.
3-8 EXTENDED HCKEL PROCEDURE
In the extended Hckel method, the Hij's are approximated by valence state
ionization potentials. The Hij ' s, given by the Wolfsberg-Helmholz formula, are :
(3-28)
where k is a constant usually taken to be 1.8. All overlaps are explicitly evaluated.
Slater or CIernenti atomic orbitals are gene rally used.
We shall briefly describe the criteria used to describe the eiectron density in
a molecule when S t= Ofor i t= j. With a LCAO wave function
we see that the total electron density, 1/1 / , is given by
J1/1/ dT = C/ f<fJ/ dT + 2CCz f<fJ <fJz dT + C/ J<fJ/ dT
= C/ + 2CC
z
SZ + C/
Using normalized a.o.'s <fJ / = 1, we also see that J<fJ <fJz dT is the overlap integral
S 2. We shall now define sorne quantities that are important results of calculations
in which S t= O.
e
1. NET ATOMIC POPULATION
o
The quantity ni c/ is referred to as the net atomic population (ni equals the
a
number of electrons in the m.o.). It is that part of the total electron density in
the m.o. that can be assigned to atom 1.
a
le
2. OVERLAP POPULATION
dI
The quantity 2nC
1
C
Z
SZ is referred to as the overlap population between
ce
atomic orbitals 1 and 2 for one molecular orbital. In a polyatomic molecuJe, the
O(
overlap population between atomic orbitals i and j is obtained by summing over
p!
all occupied molecular orbitals k:
In
(3-29)
an
mi
th
It is often convenient to have the atom-atom overlap population. This In
corresponds to the total overlap of all the atomic orbitals on atoro x with all sta
the atomic orbitals on atom y. Many m.o. programs present this as a reduced W!
n
'al
ns
he
In
een
lhe
Iver
-29)
fhis
1 aH
leed
3-8
overiap population matrix. This is
2nCC
j
Sij (3-30)
k(xy)
where k(xy) refers to the xy overiap population of every atomic orbital on x and
y summed over aH filled molecular orbitals. When one compares bonds with
similar ionic character, the overiap population is related to the bond strength.
3. GROSS ATOMIC POPULATION
This is a procedure for assigning all the electro n density in a molecule to
each of the individual atoms. Half of the bonding electron density (e.g., half of
2nC1 CzS1Z) is given to each of the atoms involved in bonding.
Gross atomic population = (nC/ + nCCjS) (3-31 )
all
m.o.'s
4. FORMAL CHARGE
The formal charge on an atom is equal to the core charge (nucleus plus all
non-valence electrons) minus the gross atomic population.
To give you sorne appreciation for the kind of information available from
a semi-empirical molecular orbital ca!culation, the output from an extended
Hckel m.o. calculation is presented in Table 3-1. The matrix summarizes the
wave function; e.g., from m.o. 12, we see that
flZ = -0.40 C(2)2pz - 0.56 C(1)2pz - 0.40 C(3)2pz
(Numbers in parentheses refer to the numbering in the figure of allyl on the
second page of computer output.) This is the lowest-energy filled pi-orbital. The
odd electro n in m.o. 9 is delocalized over both of the terminal carbons, and these
are the only two orbitals contributing to this molecular orbital.
One important concept to be gained from this calculation is the extent of
delocalization of the bonding in the sigma system, as can be seen by looking at
a sigma m.o. For example, none of the filled m.o.'s even vaguely resemble a
localized carbon-hydrogen sigma bond. Al! of the (J m.o.'s are very extensively
delocalized. The n-type atomic orbitals are orthogonal to the (J m.o. 's, and they
contain only contributions from the carbon pz orbitals. Net charges, orbital
occupations, and an atom-by-atom overiap population are evaluated in this
program from the wave functions calculated.
Extended Hckel calculations give reasonable wave functions for systems
in which the formal charges on the atoms of the molecule are small, 0.5. As
an example of the utility of such calculations, the results from a study of several
metallocenes(2) and bis-arene complexes(3) will be discussed. In all systems studied,
the correct ground state results; i.e., the unpaired electrons end up being placed
in molecular orbitals that are essentially the correct d orbitals. Certain ground
state spectroscopic properties (nmr and epr) are also predicted. This agreement
with experiment suggests that the wave functions are reasonably good. They are
Extended Hckel Procedure 75
76 Chapter 3 Molecular Orbital Theory and lis Symmetr y Aspects
TABLE 3-1 Wave Function from Extended Hckel Calculation of the Allyl
Radical
(The vertical numbers correspond to A. o. 's and the horizontal ones to M. o. 's)
A.O.'s M.O.'s
1
2 3 4 5 6 7 8. 9.
- 1.80 -0.00 0.24 -0.00 0.27 -0.00 0.25 -0.00 0.00
2 0.00 0.00 0.00 -0.00 0.00 -0.00 0.00 -0.97 -0.00
3 -0.5 1 -0.00 -0.35 0.00 -1.31 0.00 - 0.24 0.00 -0.00
4 0.00 - 1.28 -0.00 -0.68 - 0.00 - 0.29 -0.00 -0.00 -0.00
5 0.76 1.12 0.87 -0.38 -0.01 0.22 0.01 - 0.00 0.00
6 -0.00 - 0.00 -0.00 0.00 0.00 -0.00 0.00 0.65 -0.74
7 -0.43 -0.53 0.31 -0.58 0.30 0.62 -0.65 0.00 - 0.00
8 -0.68 -0.13 0.58 -0.89 -0.53 -0.54 0.15 - 0.00 0.00
9 0.76 -1.12 0.87 0.33 -0.01 -0.22 0.01 -0.00 -0.00
10 -0.00 -0.00 - 0.00 0.00 -0.00 0.00 - 0.00 0.65 0.74
11 -0.43 0.53 0.3 1 0.58 0.30 -0.62 -0.65 -0,00 -0,00
12 0.68 -0.13 -0.58 -0.89 0.53 -0.54 -0.15 0.00 0.00
13 0.28 0.00 -0.30 0.00 -1.17 0.00 -0.61 -0.00 0.00
14 -0,07 -0.48 -0.61 0.49 0.46 0.68 -0.59 0.00 0.00
15 0.15 -0,09 -0.75 0.82 -0.03 - 0.55 0.61 -0.00 -0.00
16 0.15 0.09 -0.75 -0.82 -0.03 0.55 0.161 0.00 0.00
17 -0,07 0.48 - 0,61 -0.49 0.46 -0,68 -0,59 0.00 -0,00
10 11 12. 13 14 15 16 17
-0,00 0,01 -0.00 0.00 - 0.09 0,3 3 - 0.00 0.48
el
2 -0.00 - 0.00 -0,56 0,00 - 0,00 -0.00 -0.00 0.00
3 -0.00 0.33 -0.00 -0.00 -0, 36 -0.17 - 0.00 0.01
4 -0.49 - 0.00 -0.00 -0.30 0.00 -0,00 0.16 -0.00
5 -0.14 0.05 0.00 -0.03 - 0.03 -0.20 0.44 036
el
6 - 0.00 0.00 -0.40 - 0.00 0.00 -0.00 0.00 0.00
7 - 0.12 -0.35 -0.00 0,37 -0.12 - 0.12 0.01 -0,00
8 0.41 0.00 -0.00 0.07 0,29 -0.14 0,02 -0.01
0.14 0.05 -0.00 0.03 -0.03 -0.20 -0.44 0,36
10 0.00 0.00 -0.40 0.00 -0.00 -0.00 0.00 0.00
e 11 0,12 -0.35 - 0,00 -0.37 -0.12 -0.12 -0.01 - 0.00
l2 0.41 -0.00 - 0.00 0.07 -0.29 0.14 0.02 0.01
l'
;)
~ O
00
00
00
00
!74
.00
100
00
1.
74
1.00
).00
1.00
0.00
D.OO
~ O O
0.00
17
0.48
0.00
0.01
-0.00
0.36
0.00
-0.00
-0.01
0.36
0.00
-0.00
0.01
3-8
TABLE 3-1 (continued)
13 0.00 -0.40 -0.00 0.00 0.27 0.32 0.00 0.08
14 0.37 0.26 0.00 -0.15 0.27 -0.15 0.17 0.04
H 15 -0.07 - 0.33 0.00 0.36 0.02 -0.23 0.19 0.05
16 0.07 -0.33 0.00 -0.36 0.02 -0.23 -0.19 0.05
17 -0.37 0.26 -0.00 0.15 0.27 -0.15 -0.17 0.04
M.O.' s 10 lO 17 have 2e-
9 has le-
1 lO 8 empl y
Atomic Orbilals 1-4, 5- 8,and 9- 12 areca rbon orbital s in the order 2s, 2p" 2px' 2py fo r each atom.
A.O.'s 13 lO 17 a re hydrogen Is.
M.O. Energy (eV) Occ .
53.22 o
2 36.55 o
3 2831 O
4 22.97 o
5 18.76 O
6 7.30 o
7 5.19 O
8 - 4.63 o
9 -10. 16 1
10 -12.67 2
11 -13.83 2
12 - 14.03 2
13 -15.01 2
14 -15.96 2
15 - 19.40 2
16 -22.83 2
17 - 27.54 2
Coordinate
System
y
:H(5)
:\
: C--H
/ (2) (6)
01)
.........H-c............. - X
(4) \\
, C--H
/(3) (7)
;H
(8)
/
Extended Hckel Procedure 77
Gross Atomic Population
Atomic
Orbital Occupations
1.13
2 0.98
3 0.91
4 0.96
5 1.17
6 1.01
7 0.96
8 0.89
9 1.17
10 1.01
1I 0.96
12 0.89
13 0.98
14 1.00
15 0.98
16 0.98
17 1.00
Atom
Number Net Charges
1 0.013
2 -0.020
3 -0.030
4 0.015
5 0.000
6 0.016
7 0.017
8 0.000
(eont inHed)
,
i
78 Chapler 3 Molecular Orbital Theory and lIs Symmelry Aspecls
Reduced Overlap Populalion Malrix Alom by Alom
1 2 3 4 5 6 7 8
5.236 1.411 1.141 0.836 - 0.117 - 0.075 -0.075 -0.117
2 1.141 5.604 -0.216 -0.097 0.821 0.812 -0.013 0.009
3 1.141 -0.216 5.604 -0.097 0.009 -0.013 0.812 0.821
4 0.836 -0.097 - 0.097 1.360 -0.020 0.005 0.005 -0.020
5 - 0.117 0.821 0.009 -0.020 1.402 -0.094 0.000 -0.000
6 -0.075 0.812 -0.013 0.005 -0.094 1.334 - 0.000 0.000
7 -0.075 - 0.013 0.812 0.005 0.000 -0.000 1.334 -0.094
8 -0.117 0.009 0.821 -0.020 -0.000 0.000 -0.094 1.402
then analyzed in detail to provide information about the bonding interactions
responsible for bondingthe hydrocarbon ring to the metal. An interesting result
involves the extensive mixing ofthe ringsigma orbitals with the metal orbitals
in these systems.
3-9 SCF-INDO (INTERMEDIATE NEGLECT OF
DIFFERENTIAL OVERLAP)
Before discussing the INDO ca1culation, it is appropriate to discuss in more
detail sorne ofthe approximations that have been employed without mention in
the methods discussed for many-electron systems. The wave function will be
consideredfirst. Thegroundstateofourmoleculeis described bya wavefunction
'I', which, when substituted into equation (3-4), would give us the energy, if the
equation could be rigorously solved. In the LCAO approach, we are attempting
torepresent'I'byacombinationof one-electronfunctions(i.e., molecularorbitals),
eachofwhich dependsonlyon thecoordinates ofoneelectron. Forann-electron
system, the ground state wave function is given by simply taking the product of
the occupied one-electron orbitals, i.e.,
'I'(1,2 ... n) = 1/J(1)1/J2(2) '" I/JII(n) (3-32)
ThesubscriptonI/J labeistheorbitalusedandthenumberinparenthesesdescribes
the electron. Physically, this amounts to making the untenable assumption that
electron 1 is independent of the n - 1 other electrons in the system. We shall
have to correct or pay the consequences for this later.
If the H's werewrittenasthesumofone-electronoperators,theSchrodinger
equationcould besolved bya simpleseparationofvariables.Thiswouldamount
toignoringcompletely theexistenceofthe otherelectrons ;e.g., the e
2
/rij electron
repulsion terms would not be included. What one does is to use one-electron
operators, and correct for the potential experienced at an electron p from the
P
d
el
el
H
ar
ca
In
pr
He
ele
fi el
att
wh(
elec
is f(
are
bec
e
2
/r
befo
cale
func
then
field.
00
IS
re
in
Je
l O
he
ng
tS),
of
3-9 SCF-INDO (Intermediate Neglect 01 Differential Overlap) 79
field ofthe atomic nuclei and the average field ofthe other n - 1electrons. We
label this field as V(P)' and it can be approximated as will be discussed shortl y.
Essential!y, then, our Hamiltonian is !J(p)' given by
(3- 33)
When !J(p) is used in a Schrodinger-type equation, we have :
!JcP)(l, 2 .. . n)'P(1, 2 .. . n) = 0"'P(1, 2 ... )
Notethatouroperator!J(P) can beseparated (separation ofvariables) intoa sum
ofone-electron operators F(p) , which give rise to a set ofequations ofthe form
(3-34)
Thet/! functionsaretheone-electronmolecularorbitalsobtainedbythevari ation
procedure. These are the wave functions we have been talking about when we
do Hckel or extended Hckel calculations. In these cases, al! of the electFOn-
electron repulsions are very indirectlylumpedmtotheparametersemployed,the
charge correction and the Wolfsberg-Helmholtz type of approximation. The
Hamiltonian is not explicitly defined.
In self-consistent field (SCF) methods, the Hamiltonian is explicitly written
and used. The V(P) term of equation (3-33) is an e
2
/ r j operator. In an INDO
calculation, theformalism is basical!y SCF(vide infra), but many ofthe resulting
integrals are ignored. In SCF calculations, the Hamiltonian for an n-electron
problem is written as:
(3-35)
Here,rj is the interelectronicdistanceand the i < j index n ~ u r s that electron-
electron interactionsare counted onl yonce.fl, the operatorfor electroni in the
field of the nuclei, consists of a kinetic energy term and an electron-nuclear
attraction term:
(3-36)
where V/ is the familiar kinetic energy operator for electron i, is the r
ik
el ectron-nucleus distance, and Zk is the charge on the kth nucleus. The energy
is found by a variational procedure, and successive sets oftrial wave functions
areused untilthisenergyis minimized.Thesecalculationsaremademoredifficult
becausethe operatorsdependonthe wavefunctions.Thatis, in ordertoevaluate
e
2
/rij we mustknowtheelectrondistribution,sowe mustknowthewavefunction
before we calculate the wave function. A starting wave function is guessed, the
calculationsarecarried out,and a new wave function is obtained.The new wave
function is then used to repeat the calculation. The procedure is iterated until
there are no further changes in the wave functions,i. e., we have a self-consistent
fiel d.This still is not a rigorous procedure because we are treating the electrons
1
in a molecule as if they experience a charge cloud from al! the other electrons.
In actual fact, the electro n motion is correlated; i.e., the motion of one electron
(
is governed by the instantaneous posi tions of the other electrons and not ther
average. This effect, called electron correlation, is often ignored, leading to

erroneous wave functions.
In any molecule of more than four or five atoms, even a limited basis set
(Le. , one in which only the valence atomic orbitals on each atom are employed)
gives rise to a huge number of integrals when all interactions (kinetic energy,
nuclear-electron, nuclear-nuclear, and electron-electron) are taken into account.
The various calculation procedures CNDO (complete neglect of differential
overlap) CNDO-2, INDO (intermediate neglect of differential overlap), and so
forth, differ in the types of integrals that are ignored. At present, INDO s the
most popular of these approximate methods.
We can illustrate the types of integrals encountered by considering the
following four orbitals taken from a large molecule:
k
j
Electron repulsion integrals of the form
are the most numerous and require the most computer time to integrate
numerically. This integral represents the l /r repulsion between the electron density
in the regon where epi and ep j have differential overlap and the electron density
in the region where epk and epi have dfferential overlap. The differential overlap
for electron 1, for example, is simply defined as
lt is important to emphasize that although an overlap integral may be zero,
an integral such as
El,"
(orII
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
3-9 SCF-INDO (Intermediate Neglect 01 Differential Overlap) 81
TABLE 3-2. INDO Calculation tor Allyl
(One atomic unit of energy is defined as twice the energy of the first Bohr orbit in the hydrogen
atom; i.e., twice the ionization potential of a hydrogen atom.)
Electronic Energy - 60.0089
Energy Satisfied
Eigenvalues and Ei genvectors
eV ..... -52.19 -42.62 -36.32 -33.74 -30. 21 -25.56 - 23.36 - 23.17
Eigenvalues A.U. ..... - 1.915 - 1.566 - 1.335 -1.240 - 1.110 - 0. 976 - 0.659 - 0.851
(orbital energies)
2 3 4 5 6 7 8
1 e s -0.62 -0.00 -0.34 0.02 0.00 0.00 0.00 -0.10
2 e Px -0.13 -0.00 0.29 0.48 -0.00 -0.00 -0.00 0.40
3 e Py -0.00 0.42 -0.00 0.00 -0.45 -0.00 0.33 0.00
4 e
pz -0.00 0.00 0.00 -0.00 0.00 -0.72 0.00 -0.00
ile
ity
5
6
2
2
e
e
s
Px
-0.45
0.08
0.51
-0.08
0.27
0.30
-0.06
0.20
0.03
0.44
-0.00
0.00
0.16
0.24
0.06
-0.36
ity
lap
7
8
2
2
e
e
Py
pz
0.19
0.00
0.11
0.00
0.21
-0.00
-0.43
-0.00 -
0.25
0.00
0.00
- 0.49
-0.42
- 0.00
0.02
-0.00
9 3 e s -0.45 -0.51 0.27 -0.06 -0.03 -0:00 -0.16 0.06
10 3 e Px 0.08 0.08 0.30 0.20 -0.44 0.00 -0.24 - 0.36
11 3 e Py -0.19 0.11 -0.22 0.43 0.25 -0.00 -0.42 -0.02
12 3 e pz 0.00 -0.00 -0.00 -0.00 0.00' -0.49 0.00 -0.00
13 4 H S -0.20 -0.00 -0.33 -0.28 0.00 0:00 0.00 -0.47
14 5 H S -0.13 0.30 0.15 0.33 0.00 -0,00 -0.40 0.27
15 6 H S -0.13 0.23 0.34 -0.05 0.38 0,00 0.17 -0.31
16 7 H S -0.13 0.23 0.34 -0.05 -0.38 0,00 -0.1 7 -0.31
17 8 H S -0.13 0.30 0.15 -0.33 -0.00 0.00 0.40 0.27
- 8.53 - 7.05 - 7.07 - 0.08 - 0.20 0.81 1.79 4.48 5.76
Elgenvalues -0.314 - 0.068 - 0.051 -0.033 -0.029 0.030 0.066 0.165 0.212
9 10 11 12 13 14 15 16 17
1 e s 0.00 0.43 0.00 - 0.19 0.00 0.00 0.43 0.30 - 0.00
2 e Px 0.00 -0.09 -0.00 - 0.20 0.00 0.00 -0.31 0.60 -0.00
3 e Py - 0.00 0.00 - 0.29 - 0.00 0.00 -0.12 0.00 0.00 0.65
4 e pz 0.00 - 0.00 0.00 0.00 0.69 0.00 -0.00 0.00 0.00
5 2 e s 0.00 -0.26 0.35 0.37 - 0.00 0.25 0.07 -0.10 -0.18
6 2 e Px 0.00 - 0.22 0.29 - 0.24 0.00 -0.23 0.37 0.02 0.32
7 2 e Py -0.00 0.08 -0.08 0.14 -0.00 0.37 0.16 0.42 0.34
8 2 e pz 0.71 0.00 -0.00 -0.00 -0.51 0.00 0.00 - 0.00 0.00
a
9 3 e s -0.00 -0.26 -0.35 0.37 - 0.00 -0.25 0.07 -0.01 0.18
10 3 e Px -0.00 - 0.22 -0.29 -0.24 0.00 0.23 0.36 0.02 - 0.32
11 3 e Py - 0.00 - 0.08 - 0.08 - 0.14 0.00 0.37 -0.16 -0.42 0.34
12 3 e pz -0.71 0.00 0.00 -0.00 -0.51 -0.00 0.00 - 0.00 -0.00
13 4 H S -0.00 -0.50 -0.00 -0.16 0.00 0.00 -0.43 0.33 - 0.00
14 5 H S 0.00 -0.08 0.08 -0.48 0.00 -0.49 0.01 - 0.16 -0.04
15 6 H S -0.00 0.39 -0.49 -0.04 0.00 -0.06 -0.33 -0.08 -0.19
16 7 H S 0.00 0.39 0.49 -0.04 -0.00 0.06 -0.33 - 0.08 0.19
17 8 H S -0.00 -0.08 -0.08 -0.48 0.00 0.49 0.01 -0.19 0.04
Binding Energy =-2.6884 A.U. =-73.15 eV Dipole Momen! = 3.09 Debyes
is not necessarily zero.Forexample, when the operatorOp is l/r!N ' we have the
electron-nuclear attraction integral , which cannot be assumed to be zero.
Note that <Pk and <PI overlap very httle, so the differential overlap
J<Pk(2)<p(2) de 2 is almost zero everywhere. The value ofthe integral is thus very
smal!. If a systematic method were developed to set certain ofthese differential
overlaps to zero, the number ofsuch three- and four-center integrals would be
drastically reduced. This is just what the various NDO schemes do.
For purposes ofcomparison with the results from the Hckel calculation
andtheextendedHckeloutput,thecomputeroutputfrom theINDOcalculation
onallylis presented inTable 3-2. Theeigenvalues ofthe energy aregiven aboye
each molecular orbital in units ofelectron volts and atomic units.
It is ofinterest to examine 1/19 in the INDO output:
[ t is normalized, since
Yo
dia,
the
hyd
of '
E
4
the
lap
ery
tial
be
lion
lion
3-10 Some Predictions from M.O. Theory 83
= (0.71)2(1 - O+1)
= 1
Now look at t/J9 in the extended Hckel calculation:
It is the same orbital with the same symmetry, but it has a different coefficient.
Is it still normalized? Yes, because extended Hckel does not neglect differential
overlaps, so
and the normalization procedure as used aboye will yield a different coefficient.
Ofthe various INDO programs available, the one referred(4) to as INDO/ I
or ZINDO is particularly good for reproducing geometries of inorganic sys-
tems.(5) The method has been used(6) to calculate points on the potential energy
surface ofaJkane hydroxylations and alkene epoxidations by metal oxo species.
The results lead to reaction mechanisms consistent with those proposed from
experimental observations.
3-10 SOME PREDICTIONS FROM M.O. THEORY ON
ALTERNATELY DOUBLE BONDED HYDROCARBONS
Youprobablyhaveseenexamplesofthesuccessesofm.o.theoryfor homonuclear
diatomics, e.g., the prediction ofparamagnetic O
2
, Onefurther success involves
the prediction of the structures of even numbered, alternately double bonded
hydrocarbons. The systems C
4
H
4
, CsH
s
,and C16H1 6are more stable as a set
ofalternating double bonds than they are as a delocalized pi-system. On the
otherhand, C
6
H
6
, C1oH10' C
14
H
14
,and C
18
H
1S
(Le." 4n +2, when n = 1,2,3,
...)are aromatic.
The m.o. results for these even numbered, alternately double bonded
hydrocarbonsshowasinglydegeneratelowenergyorbitalandasinglydegenerate
high energy level with doubly degenerate levels in between:
C
4
C
6
C
s
C
ltI
C
J2
C
H
elc.
+ +
E
+ +
* **
+ +
* ** **
*
*
* ** **
* *
* **
*
*
*
*
Note that the molecules with two unpaired electrons are stabilized much less
than the other molecules because the highestenergy electrons are in non-bonding
m.o. 's. These molecules will in fact be more stable if they undergo a distortion
in which the delocalized molecular orbital is con verted into two localized doubJe
bonds, as shown below:
+ + -0:=:::=:---
------**
* ---------------
Delocalized Two
4-membered ring double bonds
3-11 MORE ON PRODUCT GROUND STATE WAVE
FUNCTIONS
The product wave function written in equation (3-32) is not complete. If we write
a wave function, interchange of the labels on the electrons 1, 2, ... n cannot
change any physical property associated with the electro n density, '11
2
, of the
system. In order for 'P
2
to be unaffected, the effect of the interchange on '11 must
produce 'P so that '11
2
is unchanged. To demonstrate the problem, we shall
define a permutation operator which switches the electron labels. For a
two-electron system IY. and f3 in orbitallj; l' we can write
(3-37)
The permutation operator switches the electron labels in parentheses to
(3-38)
The result is not related to our initial wave function by 1.
However, consider the wave function
(3-39)
Now
(3-40)
This result (equation (3-40)) is related to our starting wave function by -1. Since
we have the result P'P = -1'P, we have an antisymmetrized wave function. Had
we chosen
J.
the result would have been +1. This is a symmetrized wave function. Later we
shall show that the antisymmetrized function must be chosen in order that the
Pauli exc1usion principie apply.
e
>t
le
st
IU
a
\7)
38)
-39)
One can write the correct antisymmetrized wave function for a 2n-electron
system by constructinga Slater determinant and expandingit. The determinant
is constructed as follows:
ji (l )cx(l) jI(l)P(I) jI2(I)cx(l) .....'jIn(I)P(l)
\}' = N ji 1(2)cx(2) ji 1(2)P(2)
ji 1(2n)cx(2n) ji n(2nlP(2n)
Expanding this determinant by the method ofcofactors produces the antisym-
metrized wave function. Try it for the two-electron system justdiscussed.
The properties of determinants are consistent with several properties of
electronsin molecules. Forexample, ifrows ofa determinantare changed, so is
the signo Exchanging rows corresponds to the use ofthe permutation operator,
e.g., equation (3-40). Thus, the antisymmetry property is built into the determi-
nant. Further, there is a theorem stating that if two columns ofa determinant
are identical, the determinant vanishes. Thus, a non-zero wave function cannot
beconstructediftwoelectrons with thesamespin areplaced in thesameorbital.
1. M. 1. S. Dewar, " The Molecular Orbital Theory of Organic Chemistry," McGraw-
Hill , New York, Chapo5, 1969.
2. M. F. Rettig and R. S. Drago, 1. Amer. Chem. Soc., 91, 3432 (1969).
3. S. E. Anderson, Jr., and R. S. Drago, Inorg. Chem., 11,1564(1972).
4. W. Anderson, W. D. Edwards, and M. C. Zerner, Inorg. Chem., 25, 2728 (1986) and
references therein. The program is available by contacting M. C. Zerner.
5. a. T. R. Cundari, M. C. Zerner, and R. S. Drago, Inorg. Chem., 27, 4239 (1988).
b. W. P. Anderson, T. R. Cundari, R. S. Drago,and M.C. Zerner, Inorg.Chem. , 29, 1
(1990).
6. a. T. R. Cundari and R. S. Drago, Intern.1. Quantum Chem. , 24, 665 (1990).
b. T. R. Cundari and R. S. Drago, Inorg. Chem., 29, 487 (1990).
References 85
REFERENCES
CITED
-40)
~ we
lt the
M. 1. S. Dewar, " The Molecular Orbital Theory ofOrganic Chemistry," McGraw-Hill, ADOITIONAL
New York, 1969.
READING
1. M. Anderson,"IntroductiontoQuantumChemistry,"W.A. Benjamin,New York,1969.
A. Streitwieser,"MolecularOrbitalTheoryforOrganicChemists,"Wiley,New York, 1961.
A. Liberles, "Introduction to Molecular Orbital Theory," Holt, Rinehart and Winston,
New York, 1966. (A simpleapproach to Hckel theory with manyworkedexamples.)
W. Kauzman, "Quantum Chemistry," Academic Press, New York, 1957.
1. A. PopIe and D.L. Beveridge,"ApproximateMolecularOrbitalTheory," McGraw-Hill,
New York, 1970.
W.G.RichardsandJ. A. Horsley,"AbInitioMolecularOrbitalCalculationsforChemists,"
Oxford University Press, New York, 1970.
COMPILATIONS W. G. Richards, T. E. H. Walker, and R. K. Hinkley, "A Bibli ography of Ab lniti o
Molecular Wave Functions," Oxford Universi ty Press, New York, 1971.
W.G.Richardsetal.,"BibliographyofAblniti o MolecularWaveFunctions-Supplement
for 1970-73," Oxford University Press, New York, 1974.
A. Hammett, Specialist Periodical Reports, The ChemicaJ Society, London, England.
H. Hulbronnerand C. Straub,"Hckel MolecularOrbitals, Springer-Verlag, New York,
1966.
A.StreitwieserandJ. Brauman,"SupplementalTabJesofMolecularOrbitalCalculations,"
Volumes 1and Il, Pergamon Press, New York, 1965.
EXERCI SES 1. Usingthe Hckel wavefunctions reported in this chapter,calculate theformal charges
on the carbons and the C-Cbond ordersfor
a. the allylcation
b. the all yl radical
2. a. Using projection operators, work out the symmetry-adapted linear combinations
ofpi orbitals for the allyl radical.
b. Use these linear combinations to obtain a set oforthonormal molecular orbitals.
c. Sketch the shapes ofthe n and n* molecular orbitals.
d. Compare your results with those obtained from the Hckel calculation described
in this chapter.
3. a. Using projection operators, work out the symmetry-adapted linear combinations
ofpi orbitals for cyclobutadiene.
b. Use these linear combinations to obtain a set oforthonormal molecular orbitals.
c. Sketch the shapes ofthe n and n* molecular orbitals.
d. Would any more information be obtained from a Hckel calculation? lf so, what?
4. Forthe n system ofborazole, B3N3H6, obtain:
(1)
,,:- B,
(6) NY' N (2)
I \\
(5) B"" /B(3)
-"':::: N
(4)
a. the total representation
:s
ns
s.
b. all ofthe wave functions
c. the normalization factorfor each wavefunction;and indicatewhich wavefunctions
can mix.
5. Propargylene is a linear diradical with the following valence bond structure:
H-C=C-C-H -> Z-axis
Using the three 2px and three 2px orbitals ofthe carbons as a basis set,
a. How many m.o.'s will be produced?
b. Doa simple Hckel calculation to determine the energies ofthe m.O.'s froro par t a.
c. Wha t are the a.o. coefficients ofthe two largest energy m.o.'s?
d. Calculate the bond order between two adjacent carbons.
6. The ion Re zCl
s
2- is made up of two square planar ReCI4- unitsjoined by a Re- Re
bond. The two pl a nes are paralleland the chlorines are eclipsed (as viewed down the
Re- Re bond, which we define as the z-axis). The symmetry is therefore D 4-h '
a. Determine the symmetries of the m.o.'s obtained using the two Re d ' orbitals as
z
the basis set. Use projection operators to determine these m.o.'s and sketch them.
b. Repea t part a using the two d
X
'-y2 orbitals as the basis set. These orbitals point
directly at the chlorines.
c. Applying this same procedure to the d
xy
orbitals, one obtains
' /' (h )= -'- (d (1) +d (2)
'1' 2g xy xy j2
./, ( ) _ ' (d (1) d (2)
'1' 1 eg - J2 x z + Xl
Ij ( )_ ' (d ( 1) d (2)
z eg - yz y z J2 +
Ij (e )= -'- (d (J) _ d (
2
)
1 u xz x z J2
./, (e)= _1_ (d (1) _ d (2)
'1'2 u yz yz J2
Sketch a plausible energy level diagram. Fill in the electrons and determine the
Re-Re bond order. (Hint: the bonding orbital obtained in part b participates
in dSp2 hybrids that are filled bychlorine electron pairs.The otherorbitals must be
filled by Re electrons.)
E)(ercises 87
d. Ignore the chJorines and treat the ion as ir it beJonged to Dooh' What are the
symmetries orthe 10 m.o.'s obtained aboye? (Note: this ilJustrates theorigin orthe
terms a-bond, n-bond, and so forth.)
H
7. Consider the H3+ molecule in both the linear (H-H-H)+ and triangular (/")+
states. H H
3. Utilizingsimple Hckel m.o. theory with the hydrogen 15 orbitalsas a basis set,set
up theseculardeterminantandcomputetheenergiesofthem.o.'sforeachgeometry.
b. From yOl:r ca1culation, predict which geometry would be most stable ror H3+ and
rorH
3
-
c. Consider only the linear geometry again, using the hydrogen 15 orbitals as a basis
sel. How many molecular orbitals will be rormed? Substitutetheenergies round ror
the m.o.'s in part a into the secular determinant and find the orlhonormal set or
LCAO m.o.'s.
8. 3. Two possible structures for the ion 13- are
9.
e
a.
b.
c.
Using a basis set 01" p, and Py orbitals, si mple Hckel molecular orbtals can be
calculated ror the two structures. Ignoring any n bonding,ca1culate the energies or
the three sigma m.o.'s ror the linear case, using the three atomic p, orbitals shown
aboye. (Do not ca1culate coefficients.)
b. Making the assumptions that f3 = Sq}iben,qj = Sq/l;neacqj and CI. =Sq/lben,qj =
Sqll;nearq j' which structure is more stable ir the total energy or the
p-orbital lone pairs and the m.o.'s in the bent configuration is 16C1. + 2f3? (Hint:
Therewill be six non-bondingp-orbital lone pairs,which will contribute 12C1. to the
total energy orthe linear structure.)
d
IS
Dr
of
an be
gies of
shown
ni<P j ::;;:
of the
/(Hint:
~ to the
Exercises 89
9. Consider the trigonal bipyramidal CUCI
S
3- anion:
3-
Choose axes at the Cl- ligands such that z points upward, paraJIel to C
3
. For the
in-planeCI- nuclei ,let x point toward theCu
2
+. Thus,[rom the bottom thexy-system
for the Iigands looks like the foJIowing:
I
r:>
~ 3
y
Choose the x and y axes as you wish for the axial CI- Iigands.
a. Findthetotal representation ofthep orbitalsofthefive chlorinesanddecomposeit
into irreducible representations.
b. Usea priori reasoning to determinetheeffectonanequatorialPx orPy orbitalofthe
projection operatorPl. '" whereX" denotesanydoubleprimed irreduciblerepresenta-
tion. (Hint: Whatdo these irreducible representationshave in common?)
c. Operateonanequatorialpz withPE' tofind asymmetry-adaptedlinearcombination
with E' symmetry.
I
General Introduction
lo Speclroscopy
4-1 NATURE OF RADIATION
There are many apparently different forms of radiation, e.g., visible light , radio
waves, infrared, x-rays, and gamma rays. Accordi ng to the wa ve model, all of
these kinds of radiation may be described as oscillating elect ri c and magnetic
fields.Radiation, traveling in the z-direction for example, consiSIS of electric and
magnetic fields p rpendicular to cach other and Lo the z-directio n. These fields
are represented in Fig. 4-- 1 for plane-polari zed radiation. Polarized radiat ion was
selected for simplicity of repre' nta tion, since all other components of the clectric
field except those in the x-z-plane have beeo filtcred out. The wave travels in the
z-direction with the velocity of light, c(3 x 10 1o cm sec - 1). The intensi ty of the
radiation is proportional to the ampltiude of the wave given by the projection
on the x- and y-axes. At any given time, I he wave has difli rent electric and
magnetic field strengths at different poi nts along the z-axis. The wavclength, }"
of the radiation is indicated in Fi g. 4-1, and the variation in the magnitude of
thi s quantity accounts for the apparently di fferent forros of radiation listed above.
If the radiation consists of only one wavelength, it is said to be monochromatic.
Polychromatic radiation can be separated into essentially monochroroatic beams.
For visible, u.v., or IR radiation, prisms or gratings are employed for this purpose.
Radiation consists of energy packets called photons, which travel wilh the
velocity of light. The different forms of radiation have differeot energies.
x
y
FIGU RE ~ Electric and
magnetic field components 01
plane-polarized
electromagnetic radiation.
Electric field
component
x-z plane)
con
Will
by
maf
Lhe
di /fe
stalt
matl
whel
specc
r j t,
of en
radia
spon
e lrre
an a(
Radi
reqw
(4-.2u
ous
90
4-2
I
-
dio
(lf
~ t i
lOd
:lds
\Vas
'trie
the
the
lion
and
h, i_,
le of
love,
atie.
ams,
)Ose.
llhe
z
4-2 Energies Corresponding lo Various Kinds 01 Radialion 91
In ourdiscussion ofrotational,vibrational,andelectronicspeetroscopy,our
concern wi\1 be with the interaction oftbe electric field component ofradiation
with tbe molecularsystem, This intcraction results in theabsorptionofradiation
by the molecule. In epr and nmr the concern is with the interaction with the
magnetic component of radiatiu!1_
In order for absorption to occur, the energy of the radi at ion must match
the energy di fference between the quanti?ed energy levels tha t cor respond to
different states of the molecule, lfthe energy differcnce between two of these
states is represen ted by f\.E, the wavelength of the radiation, le, necessary for
matching is given by the equation:
f\.E= he/), or }. = he/f\.E (4-1)
where h is Planck's cons tan t. 6_623 x 10- 27 erg sec molecule 1, a nd e is t he
speed oflight in cm sec-
1
, givi ng6.E in units ofergmolecule-
l
Equat ion (4- 1)
relatesthewavea ndcorpuscularmodels for radi ation,Absorptionofonequantum
ofenergy, he/}" will raise one mol eeule to the higher energy state,
As indicated by equation (4-1), the di ffe rent forms of electromagnetic
radiat on (i_e" di fferent A) differ in energy, By considering the energi es corre-
sponding to various kinds of radiati on and compa ring these with l he energies
c rresponding to the differentchanges in the state t hata molecule can undergo,
an appreciati n can be obtai ned forthedifferenlkindsofspectroscopicmet hods.
4-2 ENERGIES CORRESPONDING TO VARIOUS KINDS
OF RADIATION
Radiation can be characterized by it' wavelength, }., its wave number, V_or its
frequency, v_ The rel at ionship between these qua nt it ies is givcn by equa tions
(4-2a) and (4-2b):
_ L c(cm scc -
1
)
v(sec ) = ----:c,--- (4-2a)
A(cm)
1
ii( cm-
1
) = - -
(4-2b)
A(cm)
The quantity has units ofreciprocal centi meters. ror which the oflicia l IUPAC
nomenclature is a kaiser ; 1 00 cm- are equa! to a kil okaiser (kK). From
equations(4-1)and (4-2), the relationship ofenergy to frequency, wave number,
and wavel ength is:
6.E(ergs molccule -
I
) = hv = hcj).. = he\! (4-3)
I ndescribinganabsorpt ionband,onecommonly findsseveraldiffe rentuni ts
beingemployed bydifferentauthors. Wavenumbers,v, whicharemostcommo nly
mpl oyed. have units ofcm-
l
a nd aredefined by equation ( 2b). Vari ous units
areemployed forA. Theseare relat ed asfo ll ows: Icm = 10
8
(angst roms)= 10
7
nanometers = 10
4
I1 (microns)= 10
7
mJl (milli microns). The reJati onship to vari-
ous common energy units is given by : 1cm-
1
= 2_858 ca ljmolt; of par-
92 Chapter 4 General Introduction to Spectroscopy
. l (cm-' I
Radio
frequency
Microwave
>-
Far
CCJ
IR
oc
w
z Near
w
IR
Visibl e
Near UV
Far
UV
X ray
'Y ray
10-2
10- 1
- 10
10
2
10
3
10
4
- 10
5
- 10
6
10
7
- 10
8
FIGURE 4-2 Wave numbers
01 various types 01 radialion.
tieJes = 1. 986 x 10-
16
erg/molecule = 1.24 x 10-
4
eY/ mole. T hese convers ion
units can be employed to relate energy and wavelength; or Ihe equation
~ E k c a l mole - 1) x -1.() = 2.858 x 10
5
(4-4)
can be derived to simplify the calculation of energy from wavelength.
Wave numbers corresponding to various types of radiation are indicated in
Fig. 4-2. The small region of the total spectrum occupied by thc visible portion
is demonstrated by this figure. The higher energy radiation nas the smaller
wavelength and the larger frequency and wave number (equation (4-3. The
following sequence represents de reasing energy:
ultraviol et > visible> infrared > microwave > radio-frequency
4-3 ATOMIC ANO MOLECULAR TRANSITIONS
In an atom, the change in sla te induced by Ihe quantized absorpt ion of radiat ion
can be regarded as the excitation of an electron from one energy state to another.
The change in state is from t he ground stal e to an exci ted state. In mos t cases,
lhe energy required for such excilalion is in lhe range from 60 lO 150 kcal mole' 1
Calculation employing eq uat ion (4-3) readily show t hat radi ati on in lhe
ult raviolet and visibl e regions wiU be involved. Atomic spect ra a re often examined
as emission spectra. Electrons are excited to higher sl ates by thermal or electrical
energy, and the energy emitted as the atoros return to the ground state is mea ll red.
In molecular spectroscopy, absorption of energy is usuall y mea ured. Our
concern wil l be with three types of molecular transi ti ons indll ced by electromag-
netic radiation : electronic, vibrational, and rotat ional. A cha nge in elecl l'onic
state of a molecule occurs when a bonding or nonbonding electron of tbe molecule
in the ground state is exci ted into a higher-energy empty molecular orbital. F or
example, an electron in a n-bonding orbital or a carbonyl group can be excited
into a n* orbital, producing an excited state wil h configuration (J2n
1
n* l. T he
electron distributions in the two states (ground and excited) involved in an
electronic transition are different.
The vibrational energy sta tes are characterized by the directions, frequencies,
and amplitudes of the motions that the atoms in a molecule undergo. As an
example, two different kinds of vibrations for the S . 2 molecule are illustrated
in ig. 4-3. The atoms in the molecule vibrate (relative to their center of mass)
in the directi ons indicated by the arrows, and the two extremes in each vibrati onal
mode are indicated. In the vibration indicated in (A), the sulfur-oxygen bond
length is varying, and this is refer red to as the stretching vibration. In (B), the
motion is perpendicular to the bond axis and the bond length is essent ially
constant. This is referred to as a bending vibration. In these vibrations, Ihe net
effect of all at omic motion is to preserve the center of mass of the molecule so
that there will be no net translational motion. The vibrations indicated in Fig.
4-3 are drawn to satisfy this requirement. Certain vibrations in a molecule are
referred to as normal vibrations or normal modes. These are independenl,
self-repeating displacements of the atoms that preserve the center of mass. I n a
normal vibration, all tbe atoms vibrate in phase and with the same frequency.
It is possible to resol ve lhe most complex molecular vibration into a relatively
sr
SIJ
pr
W1
of
me
no
of
ofl
vib
whc
!/l.
vib.
osci
and
n
n
:r
le
Dn
eL
es,
1
he
lcd
,cal
ed.
pur
ag-
mic
:ule
For
I
ted
The
an
eles,
5 an
ated
,ass)
bnal
,ond
the
lially
e net
le so
Fig.
e are
'dent,
. In a
lency.
tively
4-3 Atomic and Molecular Transit ions 93
i
FIGURE 4-3 Two different
S
, / S ~
'\ ./~ ""-- l'
vibrations tor the S0 2
O -L- O O --v O
molecule. (The ampli tudes
and angle detormations are
exaggerated to i 11 ustrate the
O
/ \
O
J \-
mode.)
(A)
(B)
small number of such normal modes. For a non-linear molecule, there are 3N - 6
such modes, where N is the number of atoms in the molecule. In Chapter 6, the
procedure for calculating the total number of normal modes and their symmetries
will be given. The normal modes can be considered as the 3N - 6 internal degrees
of freedom that (in the absence of anharmonicity) could take up energy
independently of each other. The motion of the atoms of a molecule in the different
normal modes can be described by a set of normal coordinates. These are a set
of coordinates defined so as to describe the normal vibration most simply. They
often are complicated functions of angles and distances.
The products of the normal modes of vibration are relat ed to the totaJ
vibrational state, I/I v, of a non-linear molecule as shown in equation (4-5).
(4-5)
n = l
where n indicates that the product of the n vibrational modes is to be taken and
I/In is the wave function for a given normal mode. There exists for each normal
vibration (I/In) a whole series of excited vibrational states, i, whose harmonic
oscillator wave functions are given by:
(4-6)
where i = O, 1, 2 Hi is the Hermite polynomial of degree i; a
i
= 2nvJ h;
Ni = [ aJ (2iil Jn)JI !2; and q is the normal coordinate.
From this, the following wave functions are obtained for the ground, first,
and second excited states:
(4-7)
(4-8)
(4-9)
When 1/10 is plotted as a fll llction of displacements about the normal
coordinate, q, wi th zero taken as the equi librium internuclear distance, Fig. 4-4
is obtained. This symmetric function reslllts because q appears only as q2 The
;
94 Chapler 4 General Introduction to Spectroscopy
o
q
FIGURE 4-4 A plot of the
ground vibrational wave
function versus the normal
coordinate.
same type of plot is obtained for the ground state of all normal modes. It is
totally symmetric; accordingly, the total vibrational ground state of a molecul e
must belong to the totally symmetric irreducible representation, for it is t he
product of only totall y symmetric vibrational wave functions.
The vibrational excited state function f I has a functional dependence on q
that is not of an even power, and accordingly it does not necessarily have al
symmetry. When one normal mode is excited in a vibrational transition, the
resulting total state is a product of all the other totally symmetric wave functions
and the wave function for this first vibrational excited state for (he excited normal
mode. Thus, the total vibrational state has symmetry corresponding to the
normal mode that is excited.
The rotational states correspond to quantized molecular rotation around an
axis without any appreciable change in bond lengths or angles. Di fferent rotat ional
states correspond to different angular momenta of rotation or to rotations about
different axes. Rotation about the e
2
axis in S02 is an example of rotat ional
motion.
In the treatmenl of' molecular spectra, the Born-Oppenheimer approximation
is invoked. This approximation proposes that the total energy of a system may
be regarded as the sum of three independent energie : electronic, vibrational, and
rotational. For example, the electronic energy of the system does not change as
vibration of the nuclei occurs. The wave function for a given molecular state can
then be described by the product of three independent wave functions : f e' , f vi b'
and froto As we shall see later, t his approximation is not completely valido
The relative energies of these different molecul ar energy slates in typical
molecules are represented in Fig. 4-5. Rotational energy states are more cIosely
spaced than are vibrational states, which, in turn have smaller energy differences
than electronic states. The letters v
o
, VI' etc., and v
o
', VI " etc., eaeh represent the
vibrational levels of one vibrational mode in the ground and first electrooic
exeited states, respectively. Ultraviolet or visihle radiation is commonly required
to excite the molecule into the excited electronic states. Lower-energy in.frared
suffi ces for vibrational transitiolls, while pure rotational transit ions are observed in
the stilllower-energy microwave and radio-frequency regions.
Electronic transiti ons are usually accompani ed by changes in vibration and
rotation. Two ueh transitions are indicated by arrows (a) and (b) of Fig. 4- 5.
In the vibrational spectrwn, transitions to different rotati onal levels also occur.
As a result, vi brational fine structure is often detected in eleetronic transitions.
FIGURE 4--S Energy states of
a diatomic molecule.
>-
el
o:
w
Z
UJ
=t 1
;II ::
:: VI
r' V
o
Rot ati onal states
Ground e lectronic state
-=-- ---v;
=-----v
2
1st excited electronic state
v;
Ro
res
tra
sta
In o
reqll
in ~
mole
elect
OCCU
se/ec,
to as
be oc
modc
bym
cmi
Ihe m
transi
topic
di CUI
Spect
BoltZJl
lh
Here,
4-5
IS
ule
the
ne
al
the
ons
mal
the
jan
onal
Jout
anal
~ t u n
may
,and
ge as
ecan
ypical
losely
renccs
nt the
tronic
qllired
lFared
rvcd in
on and
ig. 4--5.
,occur.
sitions.
'onic state
licstate
4-5 Relaxation and Chemical Exchange Influences on Spectral Line Width 95
Rotational fine structure in electronic transitions can be detected in high
resolution work in the gas phase. Rotational fine structure in vibrational
transitionsis sometimes observedin theIiquid stateandgenerallyin the gaseous
state.
The energy level diagram in Fig. 4--5 is that for a diatomic molecule. For a
polyatomic molecule, the individual observed transitions can often be described
by diagrams ofthis type, each transition in effect being described by a different
diagram.
4-4 SELECTION RULES
In order for matter to absorb the electric field component ofradiabon, another
requirement in addition to energy matching must be met. The energy transition
in the mol ecule must be accompanied by a change in the electrical center ofthe
molecule in order that electrical work can be done on the molecule by the
electromagnetic radiation fiel d. Only if this condition is satisfied canabsorption
occur. Requirementsfor theabsorption ofIight by matter aresummarized in the
selection rules. Transitions t hatare possible according to t hese rules are referred
toasallowed transilions,and thosenotpossibleasforbidden transitions.lt should
be noted, ho ever, t hat the term "forbidden" refers to rules set up for a simple
model and, while the model is a good one, "forbidden " transitions may occur
by mechanisms not included in the simple model. The intensity oC a bsorpt ion or
emissionaccompanyinga transitionis reJated lo the probabiJityoft he transi lion
the more probabletransi ti ons giving rise to more intenseabsorption. For bidden
transitions have low probabi Ji ty and give absorptions oC very Jow intensi ty.This
topic and the symmetry aspects of this topie wilJ be treated in detail when we
discuss the variolls spect roscopic methods.
4-5 RELAXATION ANOCHEMICAL EXCHANGE
INFLUENCES ON SPECTRAL UNEWIOTH
Spectral transitions involve different atomic or molecular energy states. The
Boltzmann expression indicates the probabiJit y, Pi' tha t any molecule is in lhe
ithstateasafunctionoft hegroundstateenergyEa andtheexcitedstateenergyE.
e- (E,- Eo)/kT
p = ------
I e-(E,-Eo )/kT
-
I
Here, k is the Boltzmann constant (1.3807 x 10-
23
JK ) and T the absolute
temperature.
When the energy difl'erences of the states are large as they are in most
el eetroni candvi brat ionaltransitions,only thegroundstateis populateda troom
temperature. When a photon is absorbed, the molecule changes lO the excited
state and then reJaxes back to its ground state by a radiative process that emits
radi ationor increasesthekinetieenergy(temperature) oft he sample.In time, t he
Bol tzmann equilibri um is reestabli shed. When the cnergy di fference ofthe stales
96 Chapter 4 General Introduclion lo Speclroscopy
is small compared to kT at room temperature (as is the case for states involved
in an nmr transition), the states are populated in accord with the Boltzmann
expression. A dynamic system results in which molecules in the excited state
exchange energy with other identical molecules. The fraction of molecules in the
two states is constant, but a given molecule exchanges between the different states.
The process of switching energy states is called relaxation and the efficiency of
interchange is govemed by the relaxation mechanism, which in tum govems the
Iifetime of the molecule in a given state. When a molecule is excited by the
absorpt ion of energy, these relaxation mechanisms determine the lifetime of the
excited state as the system returns to the Boltzmann equilibrium. The na tural
line width of a spectraJ line depends upon the lifetime of the excited state vi a the
uncertainty principie.
or
1
v ~ (4-10)
2n
As the lifetime, t, decreases, the ra nge of freq uencies possi ble, i.e., the natural
line width, increases.
Next, consider the consequences of chemical reactions on the wi dths of
spectral hnes. When two or more chemical1y distinct species coexist in rapid
equilibrium (two conformations, or rapid chemical exchange, e.g., proton exchange
between NH
3
and NH
4
+, or other equilibria), one often sees absorption peaks
corresponding to the individual species in sorne forms of spectroscopy; but with
other methods, only a single average peak is det ected. A pr ccss may cause a
broadening of the spectral line in sorne spectral regions, while th same process
in sorne other spectral region has no effect.
Consider the case in which two different sites give rise to two distinct pea ks.
As the rate of the chemical exchange comes c10se to the frequrcncy v of the
spectroscopic method, the two peaks begin to broaden. As the rate becomes
faster, they move together, merge, and then sharpen into a si ngle peak. In
subsequent chapters, we shall discuss procedures for extracting rate data over
this entire range. Here we shall attempt to gain an appreciation for the time
sea les corresponding to the various methods by examining the rates that result
in the line broadening of a sharp single resonance and the merging of two distinct
resonances.
First, we shall be concerned with the broadening of a resonance line of an
individual species. If t is the liretime of the excited state, we have:
If there is sorne chemical or pby ical process that is fast compared to the excited
sI ete Iifetime, t can be shortened by this process and the line will be broadened.
In
by l
widt hl.
4-5 Relaxation and Chemical Exchange Influences on Spectral Line Width 97
n

r
lf
'
e
e
e
le
O)
of
,id
gc
ks
ith
:a
"ss
ks.
Ihe
1es
In
ver
me
ult
nct
an
ited
ned.
In infrared, for example, it is possible to resolve* two bands correspondi ng to
different sites that are separated by 0.1 cm-
I
, so we can substitute thi s value into
equation (4--10) and find that lifetimes, corresponding to this are given by:
= 0.1 cm-
I
x 3 x 1010 cmjsec = 3 x 10
9
sec-
1
1
dt = = 5 x 10 - I I sec
(2)(n)(3 x 10
9
sec -
1
)
Therefore, we need a process that wi U give rise to lifetimes of LO - II ee or less
to cause broadening. Since lifetimes are the reciprocals of fi rst order rat e constants,
I
this means we need a process whose rate constant is at least 10
11
sec- in order
to detect a broadening in the infrared bando Diffu ion-controlled chemical
reactions have rate conscC'.nts of only 1010, so for systems undergoing ch mical
exchange, the chemical process will havc no inftucnce on the infrared line shape.
Rotat ional motion occurs on a time scale that causes broadening of an infrar d
or Raman li ne, and il is possible to obtain information about the motion from
the line shapeO
J
The inversion doubling of ammonia is also fast enough to affect
the Raman and microwave spectra.
In nmr, typical resolution is Hz (cycle per second) which, when
substituted into the aboye equation, shows that a process with a li feti me of about
2 sec (or less) or arate constant of about 0.5 sec -
I
(or more) is needed to broaden
the spectral li neo This is in the range of many chemi eal exchange r actions.
Next, we shall consider the rate at which processes must occur to res ult in
a spectrum in which onl y an average line is detect d for two species. Tn order
for this to occur, the species must be interconverting so fasl that the li fet ime in
either one o[ the states is less than so that only an average line results. This
is calculated by substituting the difference between the frequencies of the two
states for dv in equation (4--10). In the infrared, a rate constant of 5 x 10
13
sec- I
or greater would be requi red to merge two peaks that are separated by 300 cm - l.
1
l1t = -,-::--,---,---=--=----::-;-co;---- --;-:- = 2 x 10- 14 sec
x 10
12
(2)(n)(9.0 se 1)
In nmr, for a system in which, for example, the two proton peaks are separated
by 100 Hz, one obtains
1
l1t = = 2 x 10 - 3 sec
(2)(n)(1oo sec 1)
Thus, an exchange process involving this proton that had a rate constan! of
5 x 10
2
sec- would caus(. these two resonances to appear as one broad lineo
As the rate constant beco mes much larger than 5 x 10
2
(e.g ., by raising the
temperature for a process with a positive activation enthalpy), the broadened
By resolve, we mean th at one can detect the existence of two di slincl maxima. We are using
this quantily 10 roughly estimate t.v, the time scale of the spectrosco pic melhod (i. e., the naturalline
width).
98 Chapler 4 General Introducti on to Spectroscopy
TABLE 4-1 Kinetic Techniques and the Appropriate Lifetimes'
General
Applications
conventional knetcs
st op ftow
nmr
esr
temperature jump
Miissbauer (iran)
ultrasonies
ftuoreseent polarzation (the depolarizatioo
is measured)
IR and Raman loe shapes
photoelectron spectroscopy
10 sec or longer (determned by abilty to
mx reagents)
10 -
3
see or longer (faster mxng is possble)
10 - 1 to 10 .; see
10-
4
to 10 8 see
0.1 to 10-
6
sec
10-
7
sec
10 -
4
to 10-
8
see
10 - 8 tolO - 9 see
10- 11 see
10- 18 see
* rr some of these technques are unfamilar at prcsent, do not be coneerned. This will
provi de a ready reference after you encounter thcm in your study.
single resonance begins to sharpen. Eventually, as lhe process beco mes very fast ,
the tine width is no longer inftuenced by the chemical process. The radiat ion is
too slow to detect any chemical changes that are occurring and a sharp average
tine resul ts. Tbis is anal ogous l O lhe eye being too low to detect the electronic
sweep that produces a television pictm e.
In x- ray diffraction, the frequency of the radiation is 10
18
sec-
1
Si nce this
is too fast, compared with molecular rearrangements, all we would detcct for a
dynamic system would be disorder, i.e., contributions [rom each of lhe domina nt
conformations.
In M6ss ba uer spectro copy, we observe a very high encrgy process in wh ich
a nucleus in the sample absorbs a y- ray from the source. The liretime of the
nuclear exci ted state, for ron is constant al 10-
7
seco ThllS, if there is a chemical
process occurring in an iron sampl e that eqll ili bratcs two iron atoms wit h a first
order rate constant greater than 10
7
sec -
I
lhe Mossbauer spectrum will reveal
only an average peak. (n dichl orobi phenanthroline iron (nI), the equilibrium
mixture of high spin (five lI npaired elect rons) and low spin (one unpaired electron)
iron complexes int ercon vert so rapidly (t hey have a IifetLme < 10-
7
sec) that only
a si ngle iron species is observed in the spectrum. For a ruthenium nllcleus, t he
lifetime of the nucl ear excited state is 10- 9 sec; thi s determines the time scal e for
experiments wit h t his nucleus. A similar situation perlains in x-ray photoelect ron
spect roscopy. The ti me scale of an electron is not influeneed by chemical processes
and the liretime for the res ulti ng excited state is constant al about 10-
18
seco
Table 4-1 slIllunarizes the m thods used in kinet ic studies and the ranges
of lifetimes Ihat can be invcstigated.
The foll owing general applications of spectroscopy are elementary and pert ain
lo both vibrali onal and electronic spect roscopic methods: (1) determination of
concentration, (2)" fin gerprinti ng," and (3) determinat ion of l he nu mber of species
in sol ut ion by the use of i osbestic points.
Mea
Ir Ihe
By e'
I'lHo
Deter
of kir
th c(
st ndl
seopie
1
and tt
law:
\'here
or the
coeffi Cl
moj ari
The m
must t
emplo]
lO lhc
ru nge
11
IIC
"a
Inl
ch
:he
cal
Irst
cal
Uffi
on)
,nly
[hc
for
ron
sscs
c.
19C5
rtain
)tl of
Iceies
Determinatian af Cancentratian 99
4-6 DETERMINATION OF CONCENTRATION
Measurement of the concentrations of species has several important applications.
lf the system is measured at equilibrium, equilibrium constants can be determined.
By evaluating the equilibrium constant, K, at several temperatures, the enthalpy
I1H
o
for the equilibrium reaction can be calculated from the van't H oll equation:
- I1H
o
log K = 2. 3R T + e
Determination of the change in concent ra tion of materials wi th time is the basis
of kinetic studies t hat give informa t ion a bout reaction mechanisms. In view of
the contribution of results from equi librium and kinetic st udies to our under-
standing of chemical reactivity, the determination of concentrations by spect ro-
scopic methods wil! be disc llssed.
The relationship b tween the amounl of light absorbed by certai n systems
and the concentration of the absorbing species is expressed by t he Bcer- La mbert
la w:
/0
A =logO - = f,cb (4-12)
1
where A is the absorbance, l o is the intensity of the incident lighl, J is lhe intcnsity
of the transmitted light, F. is t he molar absorp tivit y (sometimes caIled extinction
coefficient) at a gi ven wavelength and lempcrature, c is the concent rati o n (the
molarity if e is Ihe molar absorptivit y), and b is the lengl h of the absorbi ng sy. lt: m.
The molar absorpti vity varies with both wavel ength a nd temperaturc, so t bese
must be held consta nt when usi ng equat ion (4-12). When matched ceIls are
employed to eliminate scattering of [he incident beam lhere a re no exceplions
to the relationship bel ween absorbancc and b (the Lambert law). F or a given
concentration of a certai n substance, lhe absorbance is a!ways directi pro por-
tional to l he length of l he cel!. T he part of equation (4- 12) rel ating absorbance
and concentrati o n (logO / 0/ 1 = f,C, for a consta nt cell length) is referred to as
Beer's law. M any systems have been found that do not obey Beer's law. T he
anomalies can be a ttributed to change in the composi tion of t he y [em wi t h
concentration (e.g., differenl degrees of ionization or dissociat ion of a solute at
different concent rations). For al! systems the Beer's law relationship must be
demonstrated, ra t her Ihan ass umed, over the enti re concentration range to be
considered, If Beer 's law is obeyed, it becomes a simple ma lt er to use equatio n
(4-12) ror the determinal ion of the concent ra tion of a known substance if it is
the onl y material present tha t is absorbing in a particular regi on of t he spectrum.
The Beer's law rel at ionship is test d and G dctermined by measuring the
absorbances of several solut ion ' of d iffere nt known concent ratio ns covering the
range to be considered. For each solut ion, f, can be calculated from
A(l cm cell )
(; = ------::--:--
(4-1 3)
c, molarity
:
l
'
100 Chapler 4 General Introduction to Spectroscopy
where the units of e are liters mole - 1 cm - l. For a solution of this material of
unknown concentration, the absorbance is measured, e is known (4-13), and e is
ca1culated from equation (4-1.2).
There are sorne interesli ng variations on the application of Beer's law. If the
absorption of two species should overlap, this overlap can be resolved math-
ematically and the concentrations determined. This is possible as long as the two
C values are not identical at all wavelengths. Consider the case in which the e
values for two compounds whose spectra overlap can be measured for the pure
compounds. The concentration of each component in a mixture of the two
compounds can be obtained by measuring the absorbance at two differcnt
wavelengths, one at which both compounds absorb strongly and a second at
which there is a large difference in the absorptions. Both wavelengths should be
selected at reasonably ftat regions ofthe absorpt ion curves ofthe rure compounds,
if possible. Consider two such species B and C, and wavelengths }'l and }' 2' There
are molar absorptivities of eB for B at }' l> eB for B at ,1 2' and similar quantities
Al ). 2
ce . and ce for C. The total absorbance of the mixture at }' l is Al' and that at
Al ,1.2
}'2 is A
2
. It follows that:
Al = xCB + YCe (4-14)
Al Al
and
A
2
= XCB + YCe (4-15)
,1 2 }. 2
where x = molarity of B and y = molari ty of C. The two simultaneous equations
(4-14) and (4-15) have only two unknowns, x and y, and can be solved.
A situation often encountered in practice involves an equilibrium of the type
O + E <=t DE
Here the spectra of, say, O and DE overlap but E does not absorb; if the
equilibrium constant is small, pure DE cannot be obtained, so its molar
absorptivity cannot be determined directly. It is possible to solve this problem
for the equilibrium concentrations of all species, i.e. , to determine the equilibrium
constant :
[DE]
(4-16)
K=[OJ[EJ
Let [OJo be the initial concentration of O. This can be measured, as can [EJo,
the initial concentration of E. The molar absorptivity of DE, cOE' cannot be
determined directly, bul it is assumed that Beer's law is obeyed. It can be seen
from a material balance that:
[DJ = [OJo - [OEJ (4-17)
[EJ = [EJo - [OEJ (4-18)
so
The te
Substi
but eo
[OJo v
When
equati(
The ad
an( e
DE
differen
sets of.
neous
sets of

lS
IC
'0
ire
at
be
:ls,

at
14)
15)
os
pe
the
olar
,lem
-ium

4- 17)
4- 18)
4-6 Determination 01 Concentration 101
so
K = _ ___[-'-O_E-=J____
(4-19)
[DJo - [OEJ)([EJ
o
- [OEJ)
The total absorbance consists of contributions from [OJ and [OEJ according to
(4-20)
Substituting equation (4-17) into (4-20) and solving for [OEJ, one obtains
but eo[OJ
o
is the initial absorbance, AO , of a solution of O with concentration
[OJo without any E in it, so
A - AO
[OEJ= -- (4-21)
eOE - eo
When equation (4-21) is substituted into the equilibrium constant expression,
equati on (4-19), and this is rearranged, we have(2)
(4-22)
The advantage of this equation is that it contains only two unknown quantities,
eOE and K-l . Furthermore, these unknowns are constant for any solution of
different concentrations [OJo and [EJ
o
that we care to make up. For two different
sets of experimental conditions (different values of [OJo and [EJ
o
) two simulta-
neous equations can be sol ved ; eo is eliminated, and K is obtained. If several
sets of experimental conditions are employed, al! possible combinations of
simultaneous equations can be considered by employing a least-squares computer
analysis(3 - 7) that finds the best values of K - 1 and eOE to reproduce the
experimental absorbances. These least-squares procedures usual!y provide an
error analysis that is most important to have (vide infra).
There are several advantages to a graphical display of the simultaneous
equations that are being analyzed. The graph is constructed(2) by taking a solution
ofknown [OJo, [EJ
o
, and A, and calculating the values of K-
1
that would result
by selecting several different values of eOE near the expected value. These results
are plotted, as in Fig. 4-6, by the line [OJo[EJ
o
*. The procedure is repeated for
other initial concentrations, e.g. , [OJo'[EJ
o
' and [OJo"[EJ
o
" The intersection of
any two of these Iines is a graphical representation of the solution of two
simultaneous equations. The intersection of al! the calculated curves should occur
at a point whose val ues of K- I and e satisfy all the experimental data. This
common intersection justifies the Beer's law assumption used in the derivation
because it indicates a unique value for e for al! concentrations. As a result of
experimental error, a triangle usually results instead of a point. The bes! K - I
aod e to fit the data are then fo und by a lea -t - qua res procedure. References 6 and
I
,
:
4-7
102 Chapler 4 General Inlroduclion lo Speclroscopy
[Dlb'[Elb'
[Dlo[El
o
[DJo[Elo
FIGURE 4-6 Graphical solution 01 K-l
equation (4-22) .
7 describe the least-squares procedure and error analysis. When the experiment
described aboye is not designed properl y, a set of concentrations of D and E are
employed that result in a set of parallel lines for the K - 1 US o e plots. The slope
of one of these lines is given by taking the partial derivative of the K - 1 expression
in (4-22) wit h respect to eOE - eD:
(4-23)
Since the first term is generally small, we see from equation (4-23) that if
experimental conditions are selected for a series of experiments in which [DEJ
or the value of A nearly doubles every time [OJo or [EJo i, doubled, then lhe
various resulting K -1 USo c plots will be nearl y parallel. The values of K -
1
and
c obtained from the computer analysis of thi s kind of data(6) are thus highly
correlated and should be considered undefined, for the simul taneous equations
are essentially dependent ones. The K -
1
USo e plots have been described in terms
of the results from the error anal ysis of the least-squares calculation, and the
reader is referred to reference 7 for details.
The approach described aboye for the evaluation of equilibri um constants
is a general one that applies to any form of spectroscopy or any kind of
measurement in which the measured quantity is linearly related to concentraton
(i. e., in which a counterpart to equation (4-20) exists). Similar analyses have been
described for calorimetric data(S) and for nmr spectral data(7)
There have been many reports in the Jiterature of attempts to solve
simultaneous equations for equilibrium constants for two or more consecutive
equilibria:
A + B:;;=:AB step 1
AB + ABz step 2
Usuall y GA
.
B' CAB
z
, and the stepwise equilibrium cons tants K 1 and K z are unknown.
In most inslances, even t hough the reported paramele rs fit t he exp rimental data
well , the system is undefined. Careful exami nalion often shows that many other,
very difTercnt combinations of parameters aLso fit the data. To solve this problem,
one musl find a regio n of the spect rum in which AB ma kes the main contri bution
to t he absorbance and anolher in which AB makes the predominant contri butio n.
Onl:
rigO
expe
AB
2
in df
ff tw.
lfl ere
are el
held e
ratio
in wh
long I
absorl
the ab:
Thcin
The e
regard
\Vere
e nsist
el
c.
el;
Ji
4-7 IsosbestiG Points 103
mt
are
-23)
at if
D ]
11 the
I and
tighly
Itions
lerU1S
Id lhe
Istants
ind of
ralion
ebeen
solve
cutive
Iknown.
Ital data
iy other,
Iroblem,
ibution
ribution.
Only by working at both wavelengths can one solve for all the unknowns in a
rigorous fashion. This is impossible in many nmr, u.v.-visible, and calor;metric
experiments because properties related predominantly to the individual AB and
AB
2
species cannot be monitored separately. This problem has been discussed
in detail in the literature(4) and several examples are given there.
4-7 ISOSBESTIC POINTS
Irtwo substances at equal concentrations have absorption bands that overlap,
therewill besomewavelengthat whichthemolarabsorptivitiesofthetwospecies
are equa!. lft he sum ofthe concentrations ofthese two materials in solution is
held constant, there will be no change in absorbance at this wavelength as the
ratioofthetwomaterials is varied. Forexample,assumea reaction A +B--+ AB,
in which only A and AB absorb; the sum of [A] plus [ABJ will be constant as
long as the initial concentration ofA is held constant as B is varied. Since the
absorbance ofthe solution is given by
(4-24)
theabsorbancewill beconstantwhenCA =[;All and[ A] plus[ AB]is heldconstant.
Theinvariant point obtained for this system is referred to as the isosbestic point.
The existence ofone or more isosbe tic points in a system provides information
regarding the number ofspecies present. For example, the spectra in Fig. 4- 7
were obtained(9) by keeping the total iron concentration constant in a sy_ tem
consisting of:
Curve 1 2.1 moles ofLi CI per Fe(DMA)6(Cl0
4
)3
Curve 2 2.6 moles ofLiCl per Fe( DMA)6(CIOJ3
Curve 3 3.1 moles ofLiCI per Fe(DMA)6(CI0
4
h
Curve 4 4.1 moles ofLCI per Fe(DMA)6(CI0
4
h
whereDMAis theabbreviation for N ,N-dimethylacetamide. Point s A and Bare
isosbest ic poi nts; t heir existenee suggests that the absorption in thi s region is
es enti al ly accounted for by two species. Curve 4 is characteristic ofF Cl
4
-. A
st ud y ofsolut ions more dil ute in chloride establishes t he exist ence ofa species
Fe(DMA)4CI2+, which exists at a 2:1 ratio of CI- to Fe'll and absorbs in this
region. The isosbestic points indi cate that the sy tem can be described by the
species F e(DMA)4C1 2+ and FeCI
4
- over the region from 2:1 to 4:1 ralios of
CI - to Fe
1u
The addi tion compound FeCI
3
DMA probably does not exist in
Fe
lll
appreciable concentrat ion in thi system, i.e., at total concentrations of
2 x 1O-
4
M.Cu rve 4in thi ssp clrum doe not passt hrough the isobe tic points.
Small devial io ns(e.g. , curve 4a l pointA)maybe duetoexper imental inaccura y,
changes in ol ven t prop rties in di tTerent Soluli ons, or a small concenlra tion of
a third species, proba bly FeCI
3
DMA, present in all systems except that
represented by curve 4.
T he concl usion thal only two spceies a re presenl in appreciabl e concent ra-
tions could be in error ifFeCI
3
DMA or other speci es were present that had
molar abso rptiv t ies dentical to Ihal of the aboye two ions a t l he isosbestic
points. However, ifequil ibrium consta nts for the equilibri um
104 Chapter 4 General Inlroduclion lo Spectroscopy
r
al
U
c:
o
.Cl
....
o
.Cl
'"
o
FIGURE 4-7 Spectra 01 the O'
c:
.;
Fe(DMA)4CI 2 +-LiCI system in
o
Q)
N,N-dimethylacetamide as ....
u
solven!. oS
280 300 320 340 360 380 400
"")..{mp)
are calculated from these different curves at different wavelengths, the possibility
of a third species is eliminated if the constants agree.
An interesting situation results in which an isosbestic point can be obtained
in solution when more than two species with differing extinction coefficients exist
if the base (or acid) employed has two donor (or acceptor) si tes. For example, if
DMA were to coordinatc lO an acid A to produce an oxygen-bound complex
and a nitrogen-bound one, the mixture of complexes AN (nitrogen bound), AO
(oxygen bound), and free A (an absorbing Lewis acid) wilI give ri se to an isosbestic
point.(JO) The absorbance for such a system is given by equation (4--25) :
(4--25)
The equilibrium constant expressions are given by
[ AO] [ AN]
and
Ko = [ A] [B] K = [A] [B]
[ AO] + [ AN] [AS]
(4--26)
Ko + KN = [A] [ S] = [A] [S]
where w
coordin
The frac
Now the
or
Sinc the
overlapp
though t
can exist,
4-7 Isosbestic Points 105
\
,
-i
400
oility
lined
exist
le, if
nplex
', AO
estic
(4--26)
where we define [AO] + [AN] = [ AS] . The fraction of complex that is oxygen-
coordinated, X AO' is given by
[ AO]
X
AO
=
KO
Ko + K
[A] [S]
[AS]
[AO]
[AS]
(4-27)
[A] [B]
The fraction that is nitrogen-coordinated is similarly derived as:
[AN]
X = -- (4-28)
AN [AS]
Now the total absorbance, abs, becomes
or
(4-29)
Since the sum of [A] and [ AS] i' constant, and there must be a poi nt in the
overlapping spectra at which 6 = 6' , an isosbeslic poinl \ViII be obtained even
though three absorbing species exist. This is true beca use
K X
AN
X = K = a constant
AO o
We have taken two absorbing species whose ratio is a constant, independenl
of the parameter being varied, and \Ve ha ve translated them into what is effecti vely
a single absorbing species via equation (4-29). The general criterion is th us that
2 + N absorbing species will give rise to an isosbestic point if there are N
independen t equations of the form
[Y] = k
30)
[Z]
where Y and Z are two of t he absorbing species in the system and the value r
k is independent of the parameter being varied.
As an examplc of the application of this criterion, consider an acid that can
form two isomers with a base, AS and A*S (e.g ., Cu(hfach forming basal and
apical adducts); let thi s acid form an addllct with a base that can form two
isomers wit h an acid, AS and AB* (e .g., N-methyl imidazole bOllnd t hrough the
amine and imine nitrogens). Fivc absorbing species (A, AB, A*B, AS*, and A*B*)
can exist,
A + B -. AB
A+ B -.A*B
A + B -. AB*
A+ S -. A*B*
106 Chapter 4 General Introduction to Spectroscopy
so three constants are needed. The equilibrium constants are
[AB] [A*B] [AB*] [ A*B*J
K 1 = -[ A-]-[B-J
K
2 K J = -=-[ A_]_[ B-=--]
K4 [ A][B] = [AJ[BJ =
We now note that thiee independent ratios exist, which are independent of[B]:
K 1 [AB] K3 [AB*]
[A*B] K4 [A*B*J K
2
Therefore, an isosbestic point is expected if [A] o is held constant and [B]o is
varied. Any other ratioofequilibrium constants,e.g., K tIKJ, is not independent
of the three ratios written. The general rules presented here apply to a large
number of systems. However, rote application of rules is no substitute for an
understandingofthe systems underconsideration.
4-8 JOB 'S METHOD OF ISOMOLAR SOLUTIONS
By examining th spectra ofa series ofsolution ofwidely varying mole ratios
ofA to B, but with the same totalnumber ofmol ofA +B the stoichiometry
of complexes formed bet ween A and B in solution can often be d termined.
Absorbance at a wavelength of maximum eha nge is plotted against lhe mole
ratio ofA to B; the latteris usuaJly used as the abscissa. The plots have at leas t
one extremum, often a maximum. In simple cases, the extrema occur at mole
fraetions corresponding to lhe stoiehiometry of the complexes that form in
solutionY1- 13)
4-9 "FINGERPRINTING"
This technique is usefu l for the identificaton ofan unknown compound (hat s
suspected to be thesameas a knowncompound.Thespectraare compared with
respect to /; val ues, wavelengt hs ofmaximllrn absorption, and band shapes.
In addi tion to this direct comparison, certain funct ional groups have
characteristie absorptions in va rious regions ofthe spcctrum. For example, the
carbon 1grollp wil! generalIy absorb at certain wavelengths in the ultraviolet
and infrared spectra. Its presence in an unknown compound can be determincd
[roml heseabsorptions. Often onecan vendeterminewhet herornotlheca rbon I
group is in a conj ugated system. These d tails wi Ube considered later when t he
spectroscopic methods are discussed individualIy.
Spectroseopic m th ds provide a convenient way of deteeting certain
impuri ties in a sample.Forexample,the presence ofwat r in a systemeaneasily
be detected by its charact eristic infrared absorption. Simi larly,a product can be
tested for absence of start ing material if t.he start ing material has a fu nct ional
group with a characteristic absorption that disappears d uring the reaclion.
SpectraI procedures are speedier and less costly lhan elemental analyses. The
presence of contami nants in smal! amounts can be detected if thei r mola r
absorptivities are la rge en ugh.
L E
lht
2. N.
3. T.
4. T.
5. P.
6. R.
7. F.
8. T.
9. R.
10. R.
11. W.
12. M.
13. E
LA S(
OCCL
lO o
a. O.
b. 11
c. 3(
2. Col n1
J. um
a. )6
b. 12
4. eun
5. Th
\Vale
accor
Xo
cons
6. For
as:u
lo(+-
Bl
() IS
denl
rge
r an
Exercises 107
1. E. F.Johnson and R.S. Drago, 1. Amer. Cbem.Soc. , 95,1391 (1973), and references REFERENCES
thcrein.
CITED
2. N.J. Rose and R. S. Drago,1. Amer. Chem.Soc. ,81,6138 (1959).
3. T.D. EpleyandR. S. Drago,1. Amer.Chem Soc.,91, 2883(1969),andreference therein
4. T. O. Maier and R. S. Drago, Inorg. Chem., 11, 1861 (1972).
5. P. J. Lingane and Z. Z. Hugus, Jr., Inorg.Chem., 9,757 (1970).
6. R. M.Guidry and R. S.Drago, 1. Amer. Chem. Soc., 95, 6645 (1973).
7. F.L. Slejko, R. S. Drago, and D. G. Brown, 1. Amer. Chem. Soc. ,94, 9210 (1972).
8. T. F. Bolles and R. S. Drago, 1. Amer. hem. Soc.,87,5015 (1965)..
9. R. L. Carlson, K. F. Purcell, and R.S. Drago, Inorg.Chem., 4, 15 (1 965).
10. R. G. Mayer and R. S. Drago, Inorg. hem., 15, 2010 (1976).
11. W. Likussar and D.F. 80ltz,Anal. Chcm.,43, 1265 (1971).
12. M. M. Jones and K. K. Innes, J. Phys.Chem., 62, 1005 (1958).
J3. E. Asmus, Z. Anal. Chem., 183, 32J,401 (1961).
'alios
nclry
ned.
mole
leasl
mole
rm in
lhal is
wilh
les.
IS have
le, the
raviolet

arbonyl
the
certain
an casily
;l can be
nctional
rcaction.
The
[ir molar
1. A series of different molecular transitions require the following energies in order to EXERCISES
occur. Indicate the spectral region in which you would expect absorption ofradi ation
to occur,and the wavelength or the radiation
a. 0.001 kcal mole- l.
b. 100 kcal mole-
1
c. 30 kcal mole- l .
2. Convert the wavelength units in part a ofexercise I to wavenumbers (cm 1).
3. Convert the following wavcnumbers to Iland :
a. 3600 cm- l.
b. 1200 cm-
1
4. Convert 800 mil to cm- 1
5. TheB value for compound X is 9000 liters mole- I cm- l. A0.1molar olution ofX in
water, measured in a 1cm cell, has an absorbanceof0.542. Itis known that X reacts
according to the equation:
Xobeys Beer's law,and Yand Zdo not absorb in this region. What is tIle equilibrium
constantfor this reaction?
6. For the eq uilibrium

assumethatonlyeabsorbsandIhatBe cannotbe measured. Derive ancquationsi mil ar
to (4-22) for thissystcm.
108 Chapter 4 General Introduction l o Speclroscopy
7. a. Useequations(4-14)and(4-15)and valuesofAl = 0.3,A, =0.7,E
o
= 5, E
o
= 12,
- A l .12
Ee = 13, and Ee., = 2 to construct a plOl similar to that in Fig. 4-6 to ilJustra te
Al A _
the gra phieal solution of-the two simultaneous equations.
b. Construel the same plot as in par! a, using A = 0.3, A
2
= 0.7, Eo = 5, E
B
= 12,
J, I A,2
= 3, and Ee = 5. Compare your eonfidenee in lhe two answers, realizing that 8
e
A .12
there are 2 to 3% error in the A and E values.
e. Equation (4-22) is sO.newhat analogous to that used in par ts a and b, for the first
term is generally sma ll under the eonditions used in a spectroscopic study. Often
investiga torf, v.urk in a coneentration range in which, holding [ DJ
o
constant and
doubling[EJ
o
' they double lhe amou nt ofeomplex formed or they double A - A o.
What would the two lines in the K- US. E plot look Iike?
8. A prot on is being rapidly exehanged between B and B', .e.,
Thefrequencydifferencebet weentheHi peaksofBH+ and B' Hr inthenmrspeet r um is
100 Hz (cycles per second).
a. Wha trateof exchangewouldberequiredforthetwo peakstoappearasasi ngle eak?
b. Wouldaslowerorfaster ratebe requiredtoobservetwoseparateresonancesthatare
broadened by the exchangc process?
c. What is lhe approximate maximum rate ofchemieal xchangc that could occurand
still have no effect on the nmr speetrum?
9. A system A + ~ C + O is investigated spectroscopically. Species A, e, and o all
haveabsorbanees tha tovc rlap.Sineetherearemorethan two absorbingspeeies, would
o ne expeet to find anisosbest ie poin t if this were theonl equil ibri um involved ? Prove
your answer.
Prior
is poten
>
.,

c:
UJ A
Zero
point
energy
O
5-1
12,
ate
12,
.hat
lirst
,rtcn
and
.,iD
Electronic Absorption
Spectroscopy
umis
atare
Ir and
DaH
would
Pro\'c
5-1 VIBRATIONAL ANO ELECTRONI C ENERGV LEVELS
IN A OIATOMIC MOLECULE
Prior to a discussion of e1ectronic absorption speclroscopy, the information
summarized by a potential energy curve for a diatomic molecule (indicated in
Fig. 5-1)wil! be reviewed. Fig. 5- 1is a plotofE, the total energy ofthe system,
versus r,the internucleardista nce a nd is oneofmany typesofpotential functions
referred lo as a Morse potenti al. The curve is expressed mathemat ically by
Al! terms are defined in Fig. 5-1 except L, which is the reduced mass,
(m 1m
2
)! (m 1 + m
2
)
As the bond distance is varied in a given vibrat ional state, e.g., al ong A- B
in the V
2
level , the molecule is in a constant vibrational energy lev 1. Al A and
B wehave, respectively,theminimumandmaximumvaluesrorthe bond di stance
in this vibrationallevel. At these points the atoms arechangingdirection, so the
vibrationaJ kinetic energy is zero a nd t he total vi brational energy of th system
is potential. At re, the equilibrium internuclear distance, the vibrational kinetic
A ..------"'j,r,
Dissoci ation
\-----,',v
1
Energy, D
______l
Internucleardistance,r
>
:>
FI GURE 5-1 Morse energy
e '"
w
curve for a iatom ic molecule.
Introduction
109
11 0 Chapter 5 Electronic Absorption Spectroscopy
energy is a maximum and the vibrational potential energy is zero. Each horizontal
line represents a different vibrational energy state. T he ground state is V
o
and
excited states are represented as VI' V
2
, etc. Eventually, if enough energy can be
absorbed in vibrational modes, the molecule is excited into the continuum and
it dissociates. For most compounds, nearly all the moleculcs are in the V
o
level
at room temperature because the energy difference Vi - V
o
is usually much la rger
than kT (thermal energy), which has a value of 200 cm - 1 at 300 K. (Recall the
Boltzmann expression.)
Each excited electronic state aJso contains a series of different vibrational
energy leveJs and may be represented by a potentiaJ energy curve. The ground
electronic state and one of the many excited electronic states fo r a typical dia tomic
molecule are illustrated in Fig. 5-2. Each vibrational level, v" ' is descri bed by a
vibrational wave function, t/! vib' For simplicity only four levels a re indicaled. The
square of a wave function gives the probability distribution, and in thi case t/! vib
2
indicates probable internuc\ear distances for a panicular vibrational state. This
function, t/!vib
2
, is indicated for the vari ous levels by the dotted li nes in Fig. 5- 2.
The dotted line is not related to the energy axis. The higher th is lin , the more
probable the correspond ing inlernuc\ear d islance. The mo t proba ble distance
for a molecule in the ground state i re' while t here are lwo most probable
distances corresponding lO the two maxima in the next vibrationaJ energy level
of the ground electronic state, three in the third, etc. I n lhe exci ted vibrati naJ
levels of Ihe ground and excited eleclronic states, lh r i high probabil ity of the
moJecule having an internucIear distance at the end of the potential function.
FIGURE ~ Morse curves
lor a ground and excited
>
E'
state 01 a diatomic molecule,
Q)
e
W
showing vibrat ional
probabi l it y lunction, f;Vib
2
, as
dotted lines.
o
Intemuclear distance, r
e
..

..c
~
..c
<
5-2
e
d
~
~ r
al
1d
!le
a
he
ib
his
,-2.
ore
lee
ble
.vel
~ n a l
Ihe
on.
5-2 Relationship 01 Potentfal Energy Curves to Electronic Spectra 11 1
Wavelength, A
0-+0
FIGURE 5-3 Speclrum
corresponding lo lhe polential
energy curves indicaled in Fig.
5-2.
5-2 RELATIONSHIP OF POTENTIAL ENERGY CURVES TO
ELECTRONIC SPECTRA
An understanding of elect ronic absorption spect rosc py reqllires coos:ideration
of lhree additional principies:
l. In the very short time required for an electronic transi ti on to take place
(about 10-
15
sec), lhe atoms in a molecule do not have time lo changc positi on
appreciably. This statement is referrcd lo as lhe Franck-Condon principie. * Since
the electronic transi tion is rapid the molecule wiU find itself wi lh lhe same
molecular configura tion and vi brational kinetic energy in the excited stale that
it had in the ground slate al the moment of absorption of the phOtOD. As a r sult,
aJ1 electronic transit iollS are indi ca ted by a vertical lin 00 l h Morse potenlial
energy diagram of lhe ground and exciled states (see lhe arr ws in Fig. 5-2); i.e.,
Ihere is no change in internuc\ear distance duri og lhe transiti n.
2. There is no general selection rule that restricts the change in vibrational
state accompanying an el ctronic transition. Frequently transition OCcur rrom
lhe ground vibrational level or l he ground electronic state lO many di fferen t
vibrational levels of a par ticular excited electronic state. Such transitions may
give ri se to vibrational fine structure in tbe broader peak of the electronic
transition.
The thre transitions indicated by arrows in Fig. 5-2 could give rise to three
peaks. Sin e nearl y aH of th molecules are present in the ground vibrational
level, nearly all tran iti on' that give rise to a peak in lhe ab orption spectrum
will arise from v
o
.
t
Transitions from tbis grollnd leve! (va) to vo', VI" or v
2
' are
referred to as O-+ O, 0 -+ \, or 0 -+2 transitions, respectively. Tt can be shown(l)
tha! lhe relative iotensit y of the various vibralional sub- bands depeods upon lhe
vibrational wave function for the variou levels. A lransition is favored if the
This principie was originally proposcd by Fra nck. It was given a quantum mechanicaJ
inlerpreta tion and extended by CondO no
t In the gas phase, various rotational levels in the ground vibrational state will be populatcd
and transitions to variolls rotationalle els in the exciled tate wi l! occur, giving ri se to fine Sl rUClure
\11 the spectrum. Thi fine slructure is absenl in Solulion because c()lIision of the solute with a solvenl
molccule occurs before a rOl alion is completed. Rot alional fine structure wil! no! be discussed.
112 Chapter 5 Electronic Absorption Spectroscopy
probabilities of the ground and exeited states of the molecule are both large f r
the same internuclear distance. Three such transitions are indicaled by arrows
in Fig. 5- 2. The spectrum in F ig. 5- 3 could result from a substance in solution
undergoi ng the Une transi to ns indicaled in Fig. 5- 2. The O--> Otransition is the
lowest energy- Jong st wavelengt h transilion. The differences n wavelength at
which tbe peaks occu r represent the energy differcnces of the vibrational levels
in the excited state of the molecule. Much information about the structure and
configuraton of lhe excited state can be obtai ned from tbe fine structure.
Electroruc trans itions from bonding to anlibonding molecul ar orbitals are
oflen encountered. ln thjs case lhe potent al energy curve for the ground sta te
wi ll be quite different from thal of Ih excited state beca u e there is less bonding
electron densi ty in the exci led state. As a result, the equilibrium internuclear
distance wi l! be great r and lhe p tent ial energy curve wilJ be broader for the
excited statc. Because of this displa ement of t he excited state potential encrgy
curve, the O--> O and transitions to ot her low vibrational levels may nol be
observed. A transition to a higher vibrationallevel beeomes more probable. T his
can be visualized by broadening and displ aci ng the excited slate represented in
Fig.5- 2.
3. There is an additional symmetry requirement. which was neglected for
the sake of simpli city in the aboye discussion. It has been as um d that lh is
symme.t ry requirement is satisfied foc the lransitions involved ih this discussion.
Thi will be di scussed subsequently in the seclion 011 selection ru les.
The aboye discussion pertains t a diatomic molecule, but tbe general
princi pIes also apply to a polyatomic molecule. Often the funcli onal gcoup in a
polyatomic rnolecule can be treated as a di at omic molecule (for example, )<:=0
in a ketone or al dehyde). The elect ronic transition may occur in the functi onal
group between orbitals tha! are approximated by a combinati on ofatomic orbitals
of the two atoms, a" in a diatomic molecule. The actual energi s f the reslt ing
molecu lar orbi taJs of the functional group will, of course. be alTected by electronic,
conjugat i e, and steric effecls arising from lhe other atoms. This situation can
be und rs tood quali tati vel y in lerms of potential energy curves simi lar to those
discussed for the diatomic molecules. For more complex cases in which severa)
at oms in the molecule are invol ved (.e., a delocalized system), a polydi mensional
surface is required to represent the potential energy curves.
The energies required for el ectronic transi tions generally occur in the far
U.v., U.v., visi bl , and n ar infrared regions of the speclrum, depending upon the
energi es of the molecular orbital in a molecule. For molecules that contaio only
trong sigma bonds (e.g., CH
4
and H
2
0 ), the energy required for electronic
transi tions occurs in the far u.v. regon of lhe spectrum and requires special ized
instrumentatjon for detection. In fact, in the selection of sui table transparent
so/vents foc s!udy of the u.V. spect rum of the dissolved solute, such tcans ili ons
come nt play in d termining the cutoff poinl oC lhe solvent. On the other hand,
the col ored dyes used in clothing have extensively conjugatcd pi-systems and
uodergo electronic tcansitions in the visi ble region of the spectrum. Standard
instruments cover the region fr m 50,000 cm - 1 to 5,000 cm - l. T his spectral
region is subdjvided as follows :
Ull raviolet 50,000 cm - 1 to 26 300 cm - 1 (2000 to 3800 )
Visible 26,300 cm - 1 to J2,800 cm - 1 (3800 to 7800 )
Near infrared 12,800 cm - 1 to 5,000 cm - 1 (7800 lo 20.000 )
The r
rhe Jo
lo be
in C.
rcJali
orbil
of ' n
to illu
as"
I \\es
must el
elecl r
bOl h ti
are r (
indi \'id
chang
i enli
1(1 as a
Thc
transitil
of an el
ground
enllugh.
s[ale
rbital
electroD
excitati
arious
pro blem
tnmsitio
levels lb
This pro
H Nomenclature 113
ear
the
rgy
be
"his
in
ror
this
ion.
eral
in a
= 0
onal
)itals
lting
onic.
1 can
lhose
:veral
jonal
)c rar
m the
l only
tronie
alized
Jarent
il ions
hand,
IS and
mdard
pectral
5-3 NOMENCLATURE
In OUT previous discussion we were concemed only with transitions of an electron
fr om a given ground st ate to a given excited state. In an actual molecule there
are electrons in different kinds of orbitals (o- bonding, non-bonding, n bond ing)
wil h different energies in the ground state. Electrons from these different orbitals
can be excited to higher-energy molecular orbitalt; , giving rise to many possi ble
excited states. Thus, many transit ions from the ground state to different ex ited
states (each of which can be descr ibed by a different potenti al energy curve) are
po'sible in one molecule.
There are several conventions(2.3) used to designate these different electronic
transitions. A simple representati on introduced by Kasha(2) will be illustrated for
the carbonyl group in formaldehyde. A molecular orbital description orthe valence
in this molecule is:
The na and n
b
orbitals are the two non-bonding molecula r orbitals containi ng
the lone pairs on oxygen. Symmetry considerat ions do not requi re the lone pairs
to be degenerate, for there are no dou bly degenerate irreducible representat ions
in e
2v
' They are not accidentall y deg nerate ei lher, but differ in energy. The
relative energies of these or bitals are indi cated in Fig. 5 . The ordering of these
orbi tals can often be a rrived al by intelligent guesses and by looking at the spectra
of analogous compounds. Also indicated wit h a rrows are sorne tra nsi tions chosen
to illustrate the nomenclature. The transit ions (1), (2), (3) and (4) are referred to
as n -+ n*, n -+ 0-*, n -+ n*, and o- -+ 0-*, respectively. The n -+ n* transition is the
lowest energy-highest wavelength transi ti on that oceur in for maldehyde a nd
mo t carbonyl compounds.
Electron excitations can occur wit h or without a change in the spin of the
electron. If the spin is not changed in a molecule containi ng no unpaired elect rons,
both the exci ted state and ground state have a mult iplici ty of one; t hese sta tes
are referred to as singlets. The multiplicil y is given by two times the um of the
individual spins, m ' pl us one: 2S + 1 = 2Lm + 1. U the spin of the el ectron is
s s
changed in the t ransition, the exci ted state contains two unpai red clectrons wilh
identical magnetic spin quant um numbers, has a multiplicty of 3, a nd is referred
to as a triplet state.
There are sorne shortcomi ngs of this simple nomenclature fo r electronc
transitions. Jt has been ass umed that these transitions involve a si mple transfer
of an eledron from the ground state level l O an empty excited state level of our
ground st ate wave function. For many applicat ions, this description is precise
enough. In act ual fact, such transitions occur between states, and the excited
late is not act uall y described by moving an el ectroD iDtO an empty molecula r
orbi tal of the ground state. The excited state has, among other things, differen t
electron-electron repulsions than those in the system represented by simple
excitation of an elect ron into aD empty gr und stal or bital. In most molecules,
various kinds of el ectron-electron interactions in the excited state complica te t h
problem; in additioD to affecting the energy, they give rise to ma ny more
transi ti ons than predi cted by the si mple picture of electron prom ti 11 because
levels that would otherwi se be degenerate are spli t by ele tronic inleract ions.
This problem is particularly important in transi tion metal ion complexes. We
-a"
E
-"*1(1)
(4)
1(2) j": N
-4t-
n
b
E
R
--4t- n.
G
y
*"
*a
FIGURE 5-4 Relative
energies 01 Ihe carbonyl
molecular orbitals in H
2
CO.
shall return to discuss this problem more fully in the section on configuration
interaction.
In a more accurate(4) system of nomenclature the symmetry, configuration,
and multiplicity of the states involved in the transition are utilized in describing
the transition. This system of nomenclature can be brieft y demonstrated by again
considering the molecular orbitals of formaldehyde. The diagrams in Fig. 5-5
qualitatively represent the boundary contours of the molecular orbitals. The solid
line encloses the positive lobe and the dashed line the negative lobeo The larger
11: and 11:* lobes indicate [obes aboye the plane of the paper, and the smaller ones
represent those below the plane; the two lobes actually have identical sizes. To
c1 assify these orbitals it is necessary firs t to determine lhe overall symmetry of
the molecule, which is C2 " ' The next step is to consult the 2v character tableo
I .......- ,
/ \
a
I 1 a*
I \ I
I ' ..... _/

I
....-----.........:
'\
FI GURE Shapes of the
\
1 7T
molecular orbitals of
formaldehyde.
?'-
"- ....... _____A

I
Character tabJes for several common point groups are listed in Appendix A. The
C.2v character tabLe is duplicated here in Table 5- 1. By con ent ion, th yz- plane
is'Seledted tm oontarm thelfo\ilI toms f for rnaldebyde. Thc symmetry operations
iE, C
2
, CTV(X% pe.rf(l)1!mIlOlI (!I!D !.be 11: orbital produce the result +J, - J,
+1, - J . This resul t 11; ldentica1 to tluLt iisted Lor tbe irreducible rcpresentation
B in the table. Thc orbital is said to belong It <'fto transfOIDl as) t he symmetry
specie. b, the lowercase letter being .empl yed rora:n orbital and the uppercase
TABLE 5-1.
Character Tabl e l or the C
2
" Poi nt
Groupa
E e
2 O",; (x:.) (JI)'(y;: )
Al
Az
Bl
B
2
1 1 1
1 - 1 - 1
-1 1 - 1
-1 -1 1
z
Rz
x,R
v
y,R"
The
where
The x-axis isperpendicular lolheplane ofthe molecule.
!lln
-S
,lid
er
nes
o
of
le.
u*
n.
. The
plane
letters being reserved to describe the symmetry of the entire ground or excited
sta te. Similarly, if the na' n
b
, n*, (J, and (J* orbitals of formaldehyde are subjected
to the aboye symmetry operations, it can be shown that these orbitals belong to
the irreducible representations al' b'2, b
l
, al' and al' respectively. The two n
orbitals can be viewed as s and Py orbitals (Pz is used in the (J bond and Px in
the n). As a result, they lie in the yz-plane and possess al and b
2
symmetry. (The
al s-orbital can mix with Pz in the sigma bonding.) The difference in s-orbital
character causes the energies of the al and b
2
lone pairs to differ. Molecular
orbital calculations are consistent with these ideas. As mentioned in C hapter 2,
a and b indicate single degeneracy. The a representation does not change sign
with rotation about the n-fold axis, but b does.
The symmetry species of a state is the product of the symmetry species of each
of the odd electron orbitals. In the state that results from the n -+ n* transition
in formaldehyde, there is one unpaired electron in the n-orbital with b
2
symmetry
and one in the n*-orbital with b
J
symmetry. The direct product is given by:
E e2 (J "( x z' (J v' (yz)
bI X b2 = (1)(1) ( - 1)( - 1) (1)( - 1) ( - 1)( 1)
result = + 1 +1 -1 -1
The resulting irreducible representation is A
2
.* The excited state from this
transition is thus described as and the transition as A ( -+ A 2' A common A
2
convention involves wrili ng the high energy state first a nd la beling lh transi tion
A
2
<- A J' The spin multiplicity is usuall y incl uded, so the complete designation
becomes JA
2
<- JA
I
. Tbe ground state is Al beca use there is a pair of electrons
in each orbital. Common1y, the orbit als involved in the transitions are indicaled,
and the symbol becomes 1 A
2
(n, n*) <- 1 A l' Ir a non-specific, general symbol is
needed for a state symmetry species, r is employed.
Instead of representing the orbitaLs of formaldehyde symbolicall y, as in ig.
5-5, we could simply have been given lhe wave functi ons. We can deduce the
symmetry from '" by converti ng t he wave functi ns into a physical pict ure. Thc
foll owing equations describe t he formaldehydc n and n* orbitals:
where ({Jpo and ({Jp, are the wave functions for the atomic oxygen and carbon
p-orbitals, respectively. The atomic orbi tals are mat hematically combined to
produce the n and n* orbitals. Since oxygen is more electronegati vc (i.e., a > b),
it become el ar why it is often stated that an elect ron is transferred from oxygen
to carbon in the n -+ n* transition. W shaJl shortly rel um to a discu ion of the
experi mental spectrum of formaldehyde.
The actual procedure fo r detcrmining the symmetry of this state involves multiplication of the
orbital symmetries for all the electrons in the carbonyl group. However, all lilled orbitals contain
two electrons whose product must be Al' Thus, paired electrons have no effecl on the final result
for the excited state symmetry.
5--3 Nomenclature 115
5-4
116 Chapler 5 Electronic Absarptian Spectrascapy
Sorne ofthe molecularorbitals for benzene are represented mathematically
and pictoriaJly in Fig. 5-6. Notice that a difference in sign between adjacent
atomicorbitalsofthe wave function representsa node(pointofzero probability)
in the molecular orbital. Using the D611 character table, the symmetries of the
orbitals can be shown to be a
2
", e
lg
, e
2
", and b
2g
, for t/!, t/!2 + t/!3, t/!4 + t/!s and
t/! 6' respectively.
Inadditiontotheaboyeconventionsused tolabelgroundandexcitedstates,
aconventionusedfordiatomicmoleculeswill bedescribed.Withthisterminology
the electronic arraogement i indicated by summing up the contributions ofthe
separate atoms lo obtaio the net orbital angular momentum. Ifall electrons are
paired, the sum is zero. Conlributions are counled as follows: one unpaired
electron in a (J orbital is zero, one in a n orbital one, and one in a b orbital two.
For more t han one electron, the total is ILml. Ifthe tot al is zer , th state is
described as L, one as n, and two as ~ The mult iplicity is indicated by a
superscript,e.g., Ihe groundst ateofNOis 2IT.Aplusormi nus si n often foll ows
thesymboltoill ust rate,respectively,whetherthemolecularorbitalsaresymmet ric
orantisymmetric to aplane through the molecular axis.
a
C
fe""'" ' Cb
I I
ee, .......Cc
e
Letteringsequence tar a.a.'s d
zera nodes
Degenerate
set -
one node
rO': 1)
1 1 1 I
'-
Degenerate
set -
twanades
Threenodes
FIGURE 5-6 Shapes 01the benzene molecularorbitals.
mole
wouJ
tl1M
lo di
comp
excite
momen
.tate of
5-5 Configurat ion Interaction 117
Iy
nt
odes
nerate
t -
node
enerate
set-
lO nodes
uee nodes
If the energies of electronic transiti ns were related to the ground state
molecular orbital energies, the assignment of transitions to the observed bands
would be simp le. In formaldehyde (Fig. 5-4) the n --+ n* would be low r in energy
than the n --+ n*, which in turo would be lower in energy than (J --+ n*. In addition
to diffcrent elect ron-elect ron repulsions in different states, two ot her effects
complicate the picture by affecting the energies and the degeneracy of l he various
excited states. These effecls are spin-orbit coupling and higher-state mixing.
5-4 SPINORBIT COUPLlNG
There is a magneti interact ion between the electron spin magnetic moment
(signi fied by quant um number ms = 1/
2
) and the magnetic moment due to the
orbital motion of an elect ron. To understand the nature of this effect, c nsider
the nucleu as though it were moving about the electron (this is equival ent to
being on earth and lhinki ng of the SUD moving across the sky). We consider the
motion from lhis reference point b cause we are interested in effects al the elect ron.
Tbe charged nucleus circles the electron, and Ibis is equivalent in effecl to placi ng
the electron in the middle of a coil of wire carrying current. As movi ng charge
in a olenoid creat e a magnetic field in the center, th orbi tal motion described
aboye causes a magnetic field at the electron po it ion. This magnetic field can
interact with the spi n magnetic moment of the electron, givi ng ri e to spin-orbi t
interaction. The orbital moment may eit her complement or oppose the spi n
moment , giying rise to two different energy states. The doubly degenerate energy
state of lhe elect ron (preyi ously designated by the spin quant um numbers 1/
2
)
is split, lowering the energy of one and raising the energy of the other. Whenever
an electro n can occupy a set of degenerate orbitals that permit circulati on about
the Ducleus, this interacti on is possible. For example, if an electron can occupy
tbe d
yz
and d
x z
orbitals of a metal ion, it can circ\e lhe nucleu around the z-axis.
(A more complete discussion wiJl be gi yen in Chapter 11.)
5-5 CONFIGURATION INTERACTION
As mentioned before, electronic transitions do not occur between empty m lecula r
orbilals of the ground state configuration, but betwe n states. The energies of
lhe e sta tes are different from those of confi gurat ions deri ved by placing electrons
in the empty orbital of the ground state, because el ectron-electron repulsions in
the excited state di ffer from those in the simplified, "ground state orbi tal
description" of the exci ted state. A further complication ari es from confi guration
interaclion. One could attempt to account for the di fferent elecl r n-electron
repulsions in the excited state by doing a molecular orbit al calculation on a
molecule having the ground slate geometry but with the electron arrangement
of the excited configuration. This would not gi ve the correcl nergy of th state
because this configurati on can mix wit h a1l of the other confi gurations in the
molecule of lhe same symmetry by configuration interaction.
This mixing is similar in a ma thematical sense (though much smaller in
magnitude) to the interaction of two bydrogen atoms in forming the H
2
moleculc.
Assignment of
Transitions
118 Chapter 5 Electronic Absorpti on Spectroscopy
/ -- .,e
1b
=(1 - a
2
)1 12.,e;. - (1 - b
2
)1 /2., e;b
e ; ~
--e;.
"'"''''
",
Befare " ' -- .,e
1a
=a.,e;a + b., e;b
C.I. After C.I.
FIGURE 5-7 Energy levels before and after configuration
interaction.
Thus, we could write a seculardeterminant to account for the mixing oftwo BI
states, B'la and B'lb , as:
where H12 is the difficult-to-solve integral N(B l a)Flt/J(B lb) dr, whose al ue is
dependent upon the interelectron replllsions in the various states.Th cJoser in
energy the initial states El o and E
2
o, the more mixing occur . Solution of the
secular determinant gives u the two new energies after mi xing:
El = t [El o+ E
2
0 + ((Elof + (E
2
0) 2 - 2EoE
2
o + 4H/)1/2J
o
E
2
= ~ [ E l + E
2
- (( E l 0)2+ (E
2
)2 - 2E
l
oE
2
o + 4H12 2)1/2J
The energies ofthe initial (B'la , B'l b) and final(B la , B
l b
) tate are ill ustrated in
Fig. 5- 7along wit b the new wave funetions to describe the finaJ state. The wave
function is seen to be a li near combination ofthe two ini tial molecular orbitals.
Interacti on ofthissort canoccur with all themolecularorbitalsofB 1 symmetry
in the moleculc,complieati ng lhe problemeven further than is illustrated in Fi g.
5-7.
~ CRITERIA TO AIO IN BANO ASSIGNMENT
An appre iation for sorne ofthe difficulti es encountered in assigning transiti ons
can be obtained from reading the literat ure(S) and noting the changes in t he
a signmentstbat have beenmadeovertheyears.Accordi ngly,manyindependent
criteria are used in making the assignment. These inel ude the intensity of the
transition and the behavior oflhe ab,orption band when polarized radiat on is
employed. 80thofthese topie wi ll be considered in deta lshortly.Next we shall
de cribe somesimple ob ervation that aid in lhea ignmentofthe n 11: * and
11: ~ 11: * transtion'.
For n ~ n* transitions, one ob erves the foLlowing cha racterist ics :
1. The molar absorptivi ty oftbe tran ition is generall y less Ihan 2000. An
explanation for trus is offered in lhe section on intensity.
2. Ablue shift (bypsocbromic hift, orshift toward shorlerwavelenglhs) is
more
rorby
orlhe
3.
n
llue is
ser Jll
of the
ated in
le wave
lrbitals.
mrnetry
I in Fig.
lI1sitions
:s in the
~ p e n e n t
ty of the
iiation is
l \Ve shall
--> n* and
2000. An
lengths) is
~ Criteria to Aid in Bond Assignment 119
observed for this transition in high dielectric or hydrogen-bonding solvents. This
indicates that the energy difference between the ground and excited state is
increased in a high dielectric or hydrogen-bonding solvent. In general, for solvent
shifts it is often difficult to ascertain whether the excited state is raised in energy
or the ground state lowered. A blue shift may result from a greater lowering of
the ground state relative to the excited state or a greater elevation of the excited
state relative to the ground sta te. It is thought that the solvent shift in the n --> n*
transition results from both a lowering of the energy of the ground state and an
elevation of the energy of the excited sta te. In a high dielectric solvent the molecules
arrange themselves about the absorbing solute so that the dipoles are properly
oriented for maxi mum interaction (i. e., solvation that lowers the energy of the
ground state). When the excited state is produced, its dipole wi ll have an
orientation different from that of the ground state. Since solvent molecules cannot
rearrange to sol vate the excited state during the time of a transition, the excited
state energy is raised in a high dielectric solvent(6)
Hydrogen bonding solvents cause pronounced blue shifts. This is reported
to be due to hydrogen bonding of the solvent hydrogen with the lone pair of
electrons in the n orbital undergoing the transition. In the excited state there is
onl y one electron in the n orbital, the hydrogen bond is weaker and, as a result,
tbe solvent does not lower the energy of this state nearly as much as that of the
ground sta te. In these hydrogen bonding systems an adduct is formed, and this
specific solute-solvent interact ion is the main cause of the blue hift. (7 ) lf there is
more than one lone pair of electrons on tbe donor, the shift can be accounted
for by the inductive effect of hydrogen bonding to one eleclron pair on the energy
of the other pair.
3. Tbe n --> n* band often disappears in acidic media owing to protonation
or upon format ion of an adduct that ties up tbe lone pair, e.g., BCHI - (as in
CsHsNCH I - ), where B is the base molecule contai ning the n eJectrons. This
behavior is very characteristic if there is only one pai r of n electrons on B.
4. Blu - shifts occur upon the attacbment of an electron-donating group
to the chrom phore. For example in the series
'"
an increasi ng blue shift is observed in the carbonyl absorption bando A molecular
orbital treatment(8 ) indicates that th is shift results from raising the excited n*
level relative to the nIeve!.
5. The absorption band corresponding to the n --> n* transi tion is ab ent
in the hydrocarbon analogue of the compound. This would involve, for example,
comparison ofthe spectra of benzene and pyridine or of H
2
C= O and H
2
C=CH
2
.
6. UsuaLl y, but not always, the n --> n* transition gives rise to the lowest
energy singlet-singlet transiti on.
In contrast to the aboye behavi or, n --> n* transitions have a high intensity_
A sli ght red (bathochromic) shift is observed in high diel ctric solv nts and upon
introduction of an electron -donat ing group. It should be emphasized that in t he
aboye systems oruy the di fference in energy between t he ground and excited sta tes
can be measured [rom the frequency of the transition, so only the relat ive energics
of the t\Vo levels can be meas u red. Other considerati ons must be invoked to
determine lhe act ual change in energy of an individual state.
00 o.>Ull'-'-""
are
the "vnn..., . ..
120 Chapter 5 Electronic Absorpt ion Spectroscopy
The Intensity
O, Electronic
Transitions
5-7 OSCILLATOR STRENGTHS
As mentioned in the previous chapter, the intensity of an absorpt ion band can be
indicated by the molar absorptivity, commonly called the exti nction coefficient. A
parameter of greater theoretical significance is f, the oscillator strength of
integrated intensity, often simply called the integrated intensity:
f = 4.315 X 10-
9
fedv (5- 1)
In equation (5-1), e is the molar absorptivity and vis the frequency expressed in
wave numbers. The concept of oscillator strength is based on a simpl c1assical
model for an electronic transition. The derivation* indicates that f = 1 for a fully
allowed transition. The quantity f is eval uated graphically from equation (5- 1)
by plotting e, on a linear scale, versus the wa venumber vin cm - 1, and calculating
the area of the bando Values of f from 0.1 to 1 correspond to molar absorptivities
in the range from 10,000 to 100,000, depending on the width of the peak.
For a single, symmetrical peak, f can be approximated by the expression:
(5-2)
where e
max
is the molar a bsorptivity of the peak maximum and v1/2 is the half
intensity bandwidth, i.e., the width at e
ma
.l2.
\,,-
TRANSITION MOMENT INTEGRAL
The integrated intensity, f, of an absorption band IS related to the transition
moment integral as follows:
(5-3)
where D is called the dipole strength, fiel and I{! c,ex are electronic wave functions
for the ground and excited states respectively, NI is the electric dipole moment
operator (vide infra), and the entire integral is referred to as the transition moment
integral. To describe NI, one should recall that the electric dipole moment is
defined as the distance between the centers of gravity of the positive and negative
charges times the magnitude of these charges. The center of gravity of the positive
charges in a molecule is fixed by the nuc1ei , but the center of gravity of the
electrons is an average over the probability function. The vector for the average
distance from the nuc1ei to t he electron is represented as r. The electric dipole
moment vector, 1\1, is given by !Vi = Le'T, with the summation carried out over
For this derivati on. see Addit ional References. Barrow. pages 80 and 81.
all the
i ' giveo
By
t raosi

A
al'
an:
6- 2)
half
sition
(5- 3)
ctians
ament
wment
is

lasitive
af the
lverage
dipole
ut ayer
5--8
all the electrons in the molecule. For the ground state, the electric dipole moment
is given by the average over the probability function, or
By comparison of this equation for the ground state dipole moment with the
transition moment integral:
this integral can be seen roughly to represent charge migration or displacement
du ri ng the transition.
When the integral in equation (5-3) is zero, the intensity will be zero and,
to a first approximation, the transition wilJ be forbidden. In general, we do not
have good state wave functions to substitute into this equation to calculate the
intensity, for reasons discussed in the previous section. However, symmetry can
telJ us if integrals are zero. It is important to examine the symmetry properties
of the integrand of equation (5-3), for this enables us to make sorne important
predictions. These syrnmetry considerations will also lead to selection rules for
electronic transitions. The quantity M is a vector quantity and can be resolved
into x, y, and z components. The integral in equation (5-3) t hen has the
components:
f!/JeMAelex dv (5-4)
f!/JeMy!/JCex dv (5-5)
f!/JeMz!/Jeex dv (5-6)
In order to have an a llowed transition, at least one of the integrals in equations
(5-4) to (5-6) must be non-zero. If all three of these integrals are zero, the transition
is called forbidden and, according to approximate theory, should not occur at
al!. Forbidden transitions do occur; more refined theories (discussed in the section
on Spin-Orbit and Vibronic Coupling) give small values to the intensity integrals.
Symmetry considerations can tell us if the integral is ze ro in the fol1owing
way. An integral can be non-zero only if the direct product of the integrand
belongs to symmetry species A l. Another way of saying this is that such integrals
are different from zero only when the integrand remains unchanged for any of
the symmetry operations permitted by the symmetry of the molecule. The reason
for the aboye statements can be seen by looking at sorne sim ple mathematical
functions. First, consider a plot ofthe curve y = x, shown in F ig. 5-8(A). Symmetry
operations of the e
2v
point group on this figure tell us that this function does
not have Al symmetry. The integral fy(x) dx represents the area under the curve.
Since y(x) is positive in one quad rant and negative in lh other, the area from
Transitian Mament Integral 121
122 Chapter 5
(
Electronic Absorption Spectroscopy
+a to - a or from +00 to - 00 is zero. Now, plot a function y(x) such that y
is symmetric in x. One of many such functions is y = x
2
, shown in Fig. 5- 8(B).
This function is called " even" and does have Al symmetry, because it is
unchanged by any of the operations of the symmetry group to which the function
belongs. This can be shown by carrying out the symmetry operat ions of the C
2v
point group on Fig. 5-8(B). The integral does not vanish. The shaded area gives
the value for the integral ~ a y dx for y = x
2
, and it is seen not to cancel to zero.
Since y is a function of x
2
, we can take the direct product of the irreducible
representation of x with itself, r..: x rx ' and reduce this to demonstrate that this
is a totaHy symmetric irreducible representation. Next, the functi on y = x3, in
Fig. 5- 8(C), wiJl be examined. Symmetry considerations teH us that this is an odd
function, and we see that Jy dx (for y = x
3
) = O. Does r:c X r x x r x = Al? The
integral over aH space of an odd function always vanishes, as shown for the
examples in Figs. 5-8(A) and 5- 8(C). The integral over all space of an even
functioll generally does not vanish.
- a a
(A) (B) (e)
FIGURE 5-8 Plots 01 some si mple lunctions, y = f(xl. and thei r symmetries.
Thus, to determine whether or not the integral is zero, we take the direct
product of the irreducible repr entations of everyt hing in the integrando Jf the
direct product is or contai ns Al ' the int gral is non-zero and the transition is
allowed.
The application of these ideas is best ill ustrated by treati ng an example.
Consider the n ~ n* lransit ion in formal dehyde. The ground state, Ii ke all ground
states contai ning no unpaired eleclrons, is A l ' The excited state is also
Al (b 1 x b1 = Al)' The components M.. , NI y' a nd NI z tran form as the x, y, and
z-vectors of the point group. The table for the C
2v
point group indicates that
NI x' the dipole moment vector Iying along the z-axis, is A l ' Since
Al x Al X Al = Al ' the intcgrand t{le IM: t{le1ex for the n ~ n* is Al' and the n ~ n*
transiti on is aJlowed.
For an n -> n* transition, the ground state is Al and the exci ted state is A 2 '
The character table indicates tha t no dipole moment component has symmct ry
A
2
Therefor , none of the three integrals [equations (5-4) to (5-6)J can be Al>
and the t ransi tion is for bidden (A 2 x A 2 is the only product of A 2 tbat is Al)'
As was ment ioned when we int roduced this topie, the transi tion moment
integral can be used to deri ve sorne importanl selection rules for ele tronic
transit ions.
wherc
(whcre
refer to
agai n lo t
,
his
ircct
Ir Ihe
ion is

lround
s also
y,and
es Ihat
Since
n*
eS A
2

iI1metry
be Al'
[S A}.
noment
ectronic
5-10
DERIVATION OF SOME SELECTION RULES
1. For molecules with a center of symmetry, allowed transitions are 9 ---> u
or u ---> g. (The abbreviat ions 9 and u refer to gerade and ungerade, which are
German for even and odd, respectively.) The d- and s-orbitals are g, and p-orbilals
are u. AII wave functions in a molecule with a center of symmetry are 9 or u. AlI
components of the vector NI in a point group containing an in version center are
necessarily ungerade.
rt/Jg x r x rt/Jex = r
op
ti x ti X u=u forbidden
ti x ti X g=g allowed
9
x u x g=u forbidden
9
x ti
>(
u=g all owed
This leads to the selection rule that 9 ---> ti and u ---> 9 are allowed, but 9 ---> 9 and
ti ---> U are forbi dden. Therefore, ti ---> d transitions in transi tion metal complexes
with a center of symmet ry are for bidden. Values of G for the d-d tran itions in
N i(H
2
0)/ + are
2. Transitions belween states of different multi plicity are forbldden. Con-
sider a si nglet ---> triplet transition. Focusing on the el ectron being excited, we
have in the singlet ground state t/Jext/J/3 and, in the excited state, t/Jext/Jex or t/J/3t/J/3,
where ex and /3 are the spin coordi nates. The dipole strength is given by
(where dO" is the volume element in the spin coordinates and the i and I subscri pts
refer to initial and final states). We can rewrile Ihe integral correspondi ng to D as
Since the second term is the product of + L/ 2 and - 1/2 spi n il is aJways odd
and zero, i.e., the spins are orlhogonal. The G for absorption bands involying
transi tions between states of different mul tiplici ty is generaJly less than one. Sine
Sexo: dO" = I and S/3/3 dO" = 1, in working out the intensit y integral w nly haye
to w rry about the electron t hat is und rgoing the tran ition, and we can ignore
all the electrons in the molecule that do not change pino
3. Transi tions in rnoleculcs wi thout a center of symmetry depend upon the
symmetries of the initial and finaJ states. lf the direct product of t bese and . any
one of Mx. Mi" or M: is A, the transi tion is allowed. If all integrals are odd,
the lran ilion is forbidden.
SPECTRUM OF FORMALDEHYOE
We can summarize the aboye ideas and illustrate their utility by returning
agai n to the ultrayiolet spectrum of formaJdeb yde. T he yarious possible excited
Spectrum of Formaldehyde 123
124 Chapter5 Electronic Absorpt ion Spectroscopy
states arising from electron excitations from the highest -energy filled orbitals
(no, n
b
, and n) are given by:
a2b2b/b* = A
2
(n
b
-> n*)
a2b/b/a* = B
2
(n
b
-> 0"*)
a2bb/b* = A (n -> n*)
a2bb
2
2
a* = B
(n -> 0"*)
ab2b
2
2
b* = B
(na -> n*)
ab2b2aU = A
(no -> 0"*)
Two bands are observed, one with 8 = 100 at 2700 and an extremely intense
oneal1850. Weseefr omFig. 5-4thatthelowest-energytransitionsarn
b
-> n*
and n->n*, better expressed as A->A
2
and A1->lA. The
Al-> Az(n
b
-> n*) is forbidden, and accordiogly is assigned to the band at
2700A. Bolh A -> B1(na -> n*)and A -> A(n -> n*)areallowed.Theformer
may contribute lO the observed band al 1850A or may be in the far u.V.
The integrands for 1A -+ B(n -+ 0"*), A -+ !B2(n
b
-+ 0"*), and
A -+ A(n
o
-> 0"*) are all A,leading to all owed tran.ili ons.These are expected
tooccuratveryshortwavelengthsinlhefarultravi oletreg n.Thisisl hepresently
heJd viewoftheassignmentofthisspectrum,anditcanbeseenthatthearguments
are not rigorous. We shall subsequentl y show how polarization studies aid in
makingassignments more rigorous.
Next, it is informative to discuss the u.V. spectrum ofacetaldehyde, which
is quite similar to that of formaldehyde. The n
b
-+ n* lransition has very low
intensity. However, acelaldehyde has essymmetry; this point group has only
two irreduci ble representat ions, A andB, with Ihe x- andy-vectors lra nsforming
as A and the z-vector as B. AccordingJy, all transitions will have an integrand
with A symmetry and will be allowed. Though the n
b
-+ n* transitionis allowed
by symmetry, the value oflhe transition moment integral is very small and lhe
intensity is low. The intensity ofthi s band in acetaldenyde is greater Ihan that
in formaldehyde. Wecanwell appreciatethe fact thatalthough monodeuterofor-
as in
maldehyde [DC(O)H] does nol have C
2
" symmetry, it will have an electronic
spectrum practically identical to that offormaldehyde.These are examples ofa
rathergeneral typeofresult, which leads to theideaoflocalsymmetry. According
tothi sconcept,even thoughamoleculedoesnothave thesymmetryofapa rticular
point group, if the groups attached to the chromophore have similar bonding
interactions,(e.g. CH
3
andC
2
H
5
) themolecule for manypurposescan be treated
as though it had this higher symmetry.
5-11 SPIN-ORBIT ANO VIBRONIC COUPlING
CONTRIBUTIONS TO INTENSITY
Thediscrepancy between the theoreticaJ prediction thata transition is forbidden
and the experimental detection ofa weak band assignable to thi s transition is
attributable to the approximations ofthe theory. More refined calculations that
ineludeeffects from spin-orbit coupling often predict low intensiliesfor otherwise
se
n*
~ h e
at
~ e r
and
~ t e
ntly
ents
in
ieh
~
low
only
l11ing
Jand
Jwed
d the
I that
'ofor-
.ronic
s of a
,rding
icular
nding
reated
,idden
ion is
IS that
erwise
S-11 Spin-Orbit and Vibronic Coupling Contributions to Intensity 125
forbidden transitions. For example, a transition between apure singlet sta te and
apure triplet state is forbidden. However, if spin-orbit coupling is present, the
singlet could have the same total angula r momentum as the triplet and the two
states could interact. The interaction is indicated by equation (5-7):
(5-7)
where lf and 3f correspond to pure singlet and triplet states, respectively, f
represent the actual ground state, and a a nd b are coefficients indicating the
re\at ive contributions of the pure states. If a b, the ground state is essentially
singlet with a slight amount of triplet character and the excited state will be
essentially triplet. This slight amount of singl t character in the predominantly
triplet excited state leads to an intensit y integral for the singlet-triplet transition
that is not zero; this explains why a weak peak corresponding to the multi plicity-
forbidden transition can occur.
Another phenomenon Ihat gives inlensity lo sorne forbidden transitions is
vibronic coupling. We have assumed unt il now that the wave function for a
molecule can be factored into an electro nic part and a vibrati onal part, and we
have ignored the vibrational part. When we applied symmetry considerations to
our molecule, we assumed sorne symmetrical, equilibrium internuclear configu-
ration. This is not correct, for Ihe molecules in our system are undergoing
vibrations and during certain vibrations the molecular symmetry changes. F or
example, in an octahedral complex, the T
lu
and T
2u
vibrations shown in
Fig. 5-9 remove the center of symmet ry of the molecule. Si nce elcctronic
transitions occur much more rapidly than molecular vibrations, we detecI
transitions occurring in our sam ple from many geometries that do not have high
symmetry, e.g. , the vibra tionall y distorted molecules of the octahedral complex
shown in Fig. 5-9. The local symmetry is still very close to octahedral, so the
intensity gained this way is not very great; but it is large enough to allow a
forbidden transition to occur with weak intensity.
The electronic transition can beco me allowed by certain vi brational modes
but not by al!. We can understand this by rewriting the transition moment integral
to include both the electronic and the vibrational components of the wave function
as in eq ua tion (5-8):
(5-8)
As we menlioned in Chapter 4, aH ground vibrational wave functions are Al' so
the symmetry of f cf vib becomes that of fel ' which is also Al for molecules with
no unpaired electrons. (I n general discussion, we shall use the symbol Al to
represent the totally symmetric irreduci ble representation, even though this is
not the appropriate label in sorne point groups.) To use this equa lion to see
whether a forbidden transition can gain intensity by vibronic coupling, we must
take a product M(x,y,OrZ)fel
cx
that is not Al and see whether lhe re is a vibrational
ex
mode with symmetry that makes the product M (X,y, o,")fe/' fvib equal to Al'
ex
When fvib has the same symmetry as the product M (x,y,orz,f el"" the product
will be A l'
This dis'cussion can be made c\earer by considering sorne examples. We shall
eonsider vi brational spectroscopy in more detail in the next chapter. A non-linear
126 Chapler 5 Electronic Absorpti on Spectroscopy
r
FIGURE 5-9 T,u and T
2u
vibralions 01 an oclahedral
complex.
molecul e has 3N - 6 interna] for formaldehyde these are 3a
p
b l ' and
2b
z
For the forbidden transition IAI->IAz(nb->rr*), the vibrational wave
function of al symmetry does not change the direct product M(x..v.orz IA
z
so no
intensity can be gained by this mode. Excitation of the bI vibralional mode leads
to a d irect product t/Jele't/Jvib
ex
of b, x Az = Bz. Since My has Bz symmetry, the
tot al integral (St/Jelt/JvibMyt/Jel ex t/Jvibcx de) has Al symmetry, and the electronic
transition becomes allowed by vibronic coupling lO the b I mode.
It is informative to consider Co( NH
3
)6
3
+ as an example, for it contains
triply degenerale irred ucible representations. The ground state is lA Ig (a strong
d
6
field Oh complex). The excited states fr m d-d transitions are IT
lq
and
IT
29
Mx, My, and M
z
transfo rm as T
lu
' Fo r the 'A
, g
-> IT
I9
tr;,nsition une
oblai ns:
so
T he resulting direct producl representaLi o n has a dimensionality of nine (t he
identity is ) x 3 x 3 = 9) and the total representation is reduced into a li near
combinati on of A lu +Eu +T
lu
+T
zu
irreducible representali ons. W ith no A 19
component, the lA 19 -> I T
I9
tra nsition is forbid den. However, the vibra t io ns for
an octahedral complex have the symme tries of a
lg
, e
g
, 2t
lu
' t Zg, t
2u
' Since Ihe
direct products and t
z
.. x T
z
.. have A,g-components, this lransilion t
lu
x T
lu
becomes allowed by vibronic coupling. Fol' practice, lhe reader should take the
direCl products and factor the reducible representations discussed here.
5-12 MIXING OF d ANOP ORBITALS IN CERTAIN
SYMMETRIES
There is one further aspect of the intensity of eleclronic t ransitions that can be
understood via lhe symmet ry aspects of electronic tra nsitions. The elect ronic
spectra of tetrahedral complexes of e bal t( lI) co ntain two bands assigned to d-d
lra nsiti ons a l 20,000 cm - I a nd 6000 cm - 1, assigned as A
2
-> TIa nd A 2 -> T
2
lransitions resp ctively, with molar ab orplivities of 600 and 50. Since Ihe
M-componenls transform as we obtai n for the Az -> TI tran ilion
So fa ro
Ih
5-14
grealer.
5-13
1

Ind
ave
no
ads
the
)OlC
ains
rong
and
Olle
; (the
linear
o A Iq
ns for
ce the
lsiti n
kc the
can be
5-14 Change Transfer Transilions 127
so the transition is allowed. However, if only the d-orbitals were involved in this
transition, the intensity would be zero for the integrals
However, in the T
d
point group, the d
xy
, d
x z
and dvz orbitals and the p orbitals
transform as T
2
ancl therefore ean mix. Ir the two states in volved in the transition,
A
2
and TI' have differing amo unts of p-character, intensity is gained by having
sorne of the highly allowed p -> d or d -> p character associatecl with the traosition.
Consider the wnsequences of this mixing on the A
2
-> T
2
transition. T he
transition moment integrand for this transition is
which, as the reader should verify, can be reduced to A
2
+ E + TI + T
2
. Since
there is no Al component, the transiti on is forbidden. M ixing p-cha racter into
the wave functions wil l not help, for this type of transition is still forbidden.
Accordingly, the 8 for the A
2
-> TI transi tion is ten ti mes greater than lhat of
A2 -> T
2
The latter transition gains most of its intensity by vibronic coupli ng.
5-13 MAGNETIC DIPOLE ANO ELECTRIC aUAORUPOLE
CONTRIBUTIONS TO INTENSITY
So far, our discussi on of the intensity of electronic tra nsitions has centered on
the electric dipole component of the radiation, with the transition moment integral
involving the electric dipole operator, er. There is also a magnet ic di pole
component. The magnetic dipole operator transforms as a rota tion R R}.R ' and
z
the intensi ty from this effect may be regarded as arising from the rotation of
electron density. Transition moment inl gral s similar to those for electric dipole
transitions can be wri tten for the cont ribution from b th magnetic dipole and
electric quadrupole effects. In a molecule wilh a center of symmetiy, bot h of these
operators are symmetric wi th res pect to inversion, so 9 -> 9 and u -> u transitions
are allowed. Approximate val ues of the t ransition moment integral for a llowed
transitions for t hese different operators are: 6 x 10-
3 6
cgs unit s for a n electric
41
dipole transition, 9 x 10 - cgs unit s for a magnetic di pole transi tion, and
7 x 10-
43
cgs uni ts for a q uadrupole transition. T hus, we can see t ha! these Jatter
two effects will be important only when electric dipole lra nsitions are forbidden.
They do complicale the assignment of ery weak bands in the spectrum.
5-14 CHARGE TRANSFER TRANSITIONS
A transition in which a n electron is tra nsferred from one atom or grou p in lhe
molecule to aoother is called a charge-transfer transit ion. More accu rately stated,
th transition occurs bet ween molecular orbit als that are essent ially cente r"d on
di lfe rent a toms. Very intense bands r ul t, wi lh molar absorpti viti e of 10
4
or
greater. The freq ueocy at maximum abso rbancy, V
m
... often, but nol al ways,
occurs in the ultraviolet region. The anions CI0
4
- and S0 4- show very intense
bands. Since Mn0
4
- and Cr0
4
2
- have no d electrons, the iIl lense colors of these
ions ca nnot be explained on the basis of d-d transitions ; they are attributed to
charge-transfer transitions.(9) The transitions in MnO4 - and CrO4
2
- are m t
simply visual ized as an electron transfer from a non-bonding orbi tal of an oxygen
atom to the manganese or chromium (n --> n*), in effect reduci ng these metals in
the excited stateY O) An al ternat e descri pton for this transit ion involves excitation
of an electron from a n bonding molecular orbital, consisting essentially of oxygen
atomic orbitals to a molecular orbital that is essentiall y the metal atomic orbital.
1 n the case of a pyridi ne compl x of iridium(lll), a charge-transfer transition
that involves oxidat ion of Ihe metal has been reportedY 1) A metal )ect ron is
transferred fr om an orbi tal that is essentiall y an iridi um atomic orbital to an
empty n* ant ibonding orbital in pyridi ne.
In gaseous sodium chloride, a charge-transfer absorption occurs from the
ion pair Na +CJ- to an exci ted state described as sodi um and chJ rine atoms
having the same internuclear distance as the ion pair. A charge-t ransfer absor ption
al o occurs in the ion pair, N-methylpyridinium iodide(36) (see"Fig. 5-13) in which
an electro n is transferred from 1- to a ring antibondi ng or bital. The excited state
is represented in Fig. 5-13. A very in tense charge-transfer absorption is observed
in addit ion compounds formed between iodin and several Lewis bases. This
phenomenon will be discussed in more deLail in a Ja ter section.
5--15 POLARIZED ABSORPTION SPECTRA
If the incident radiation employed in an absorption experiment is polarized, only
those transiti ons with simi la rly oriented dipole moment vectors will occur. In a
powder, the molecules or complex ions are randomly oriented. AII allowed
transitions will be observed, for there will be a statistical dist ri bution of crystals
with dipole moment vectors aligned with the polarized radiation. However,
suppose, for example, that a formaldehyde crystal, wit h all molecules arranged
so that their z-axes are parallel, is examined. As indicated in the previous section,
the integrand t/t* Mzt/t has appropriate symmetry for the 1A(". ,,*) +-- 1A transition,
but t/t*Mxt/t and t/t *Myt/t do not. When the z-axes ofthe molecules in the crystaJ
are aligned parallel to Iight that has its electric vector polarized in the z-direction,
light will be absorbed for the 1A (". ,,*) +-- 1 A transition. Light of this wavelength
polarized in other planes will not be absorbed. If this crystal is rotated so that
the z-axis is perpendicular to the plane of pola rization of the light, no light is
absorbed. This behavior supports the assignment of this band to the transition
1Al+-- 1A l ' To determine the expected polarization of any band, the symmetry
species ofthe product t/tat/tb is compared with the components of M, as was done
before for formaldehyde. The polarization experiment is schematically illustrated
in Fig. 5-10.
In Fig. 5-10(A), absorption of radiation will occur if M
z
results in an Al
transi tion moment integrand for equation (5-6). No absorption will occur if it is
not Al regardless ofthe symmetries of the integrand ror the Mx or My components
[i.e. , equations (5-4) and (5-5)]. In Fig. 5- 10B, absorption will occur if the M,
component gives an Al transition moment integral. Even ir M, has an integrand
with Al symmetry, no absorption of the z-component wi ll occur for this
orientati on nd absorption wiJI not occur unless the My integrand is A l'
(A)
Sourc. *
NI
(S)
WI
'pectrw
excitatil
symmet
N0
2
- i
orbitals
po sibJe
In tb
firsl conSl
and ror
Accordingl
use polari
the ' rystaJ
when the z
OCCur when
I
se
'se
to
Dst
~ e n
,in
ion
en
tal.
ion
n is
an
the
only
In a
(A)
Plane polarized oscillation
Source
*
\
Nicol prism
(S) Plane
polarized
O ~ i i ~ 1
y
...----z
:
Wecanfurtherillustratetheseideasbyconsideringth
5-15 Polarized Absorption Spectra 129
z- axisofcrystal
FIGURE 5-10 Schematic
il l ustration 01a polari zed
x
single crystal study. (A) The
z-axis 01 the crystal is
parallel to t he oscill at i ng
electromagnetic plane
polarizedcomponen!.(S)The
z-axis 01 the crystal is
perpendicular to the
oscill atl ng el ectromagnetic
plane polar ized component,
andthey-axi s15parall altoil
e1ect ronicabsorpti n
spect rum of P tCl
4
2
-. The transiti ons are charge transfers invol ving electron
excitation fr m a mainlychlorinem.o. to theempty d ' _ y' orbitalon Pt(ll). The
x
symmet ryis D
4h
; using thesameapproach as thatemployedin Chapter 3on tbe
N0
2
- ion, on a basis set offour p= orbitals on chlori ne, we obtain symmetry
orbi tals for chlonne ofb
2u
' e
u
, and a
2u
symmetry. This lead to the following
possible charge-transfer transit ions:
b
2
.(n) -+bl g(d
x
' _yl) wi lh state labeis 1A Ig -+ 1A
2u
(here A
2u
is the
direct product ofb
2u
x bIg)
eJn) -+b Ig(d
x
' _y, ) with state labels lA
Ig
-+ 1E
u
a
2
.(n) -+b Ig( dx' _yl) with state labels lAIg -+ 1B
2u
In the D
4h
point group, Mx and My transform as E
u
' and M= as Alu- Ifwe
first consider the A
Ig
-+ A
2u
transition,we get for M :
z
and for Mx and My we get:
Accordingly, thi s transition is allowed and is polarized in the z-direction. Irwe
use polarized Iight and a single crystal, light will be absorbed when the z-axis of
thecrystalis paralleltolhez-directionofthelight ;buttherewi ll benoabsorption
when the z-axis is perpendicular to the Iight because the Mx and My integrands
are not Al'
For the band assigned to lAl g -+ IEu, the Al yEuEu product has an A
19
component, so this transition is also all owed. Since M yields AIgA2u Eu. which
z
does not have an A Ig component, there will be no absorption when the
z-component is parallel to the plane ofthe polarized li ght but absorption wiU
occur when the x and y-axes ofthe crystal are parallel lO the lighl.
130 Chapler 5 Electronic Absorption Spectroscopy
The A 19 ---7 B
2u
transition turns out to be forbidden. Thus, we see that by
employing polarized single crystal spectroscopy, we can rigorously assign the
2
twointensecharge-transfer bandsobservedin theelectronicspectrumofPtC1
4
- .
Jf the single crystal emplo yed in these experiments did not have ail of the molecular
z-axes aligned, the polarization experiments would /1.ot work.
Applications Most applications ofelectronic spectroscopy have been made in the wavelength
range from 2100 to 7500 A for this is the range accessible with most recording
spectrophotometers. Relat ivel yinexpensive commercial instrumentscan n w be
obtained to coverthe range from 1900 to 8000A.The nearinfrared region, from
8000 to 25,000 A,has also provided much useul informatio n. Spectra can be
examined thro ugh the 1900to 25,000Aregiononsamples ofvapors, pureliquids,
or s lutions. Solids can be examined as single crystaL r as discs fo rmed by
mixi ng the materi al wi th KCI or NaCl and pressing wi th a hydraulic press un til
a clear disc is formedo 2) Spect ra ofpowdered solids can also be examined over
a more Ii mited region (4000 to 25,000 A) as reftect ance spectra or on mull s of
the solid compounds. (12)
5-16 FINGERPRINTING
Si nce manydifTerenlsubstanees have verysimila r ultravioletand vi sible spcetra,
this is a poor regionfor productldentificati on by the"fingerprinting" technique.
Information obtained from this region should be used inconjunct ion wi th other
evidence to confinn the idenlity ofthe compound. Evidence for the presence of
fu nctional groups can be o tained by comparison ofthe spect ra with reported
data. For tbis purpo e, V
max
' :max' and band shapes can be employed.It is al so
important that the spectra be examined in a va riet y ofsol vents to be sure thal
the band shirts are in accord withexpectations (see discussion ofblue shi ft ).
.Spectral data have been compi led by Sadtler (see Additional Referenc ),
Lang,(13) andHersbenson,(14) andin"Organic ElectronicSpectralData."(\5,16) A
review article by Mason(l7) and the text by JafTe and Orchin(1) are excellenl for
this type of application. Ir a functional group (chromophore) is involved in
conjugati onor steric interactions,orisattached loelectron-releasinggroups,its
spectral properties areoflen difTerentfrom lhoseofan i.olated funet i nalgroup.
Thesedifferencescanoftenbepredictedsemiquantitati vclyformoleculesinwhich
such ~ cts areexpe ted to exist.(17)
The pectra of sorne representat ive compounds and exampl s ofthe etfect
ofsubstituents on lhe wavelength ofa transition will b descri bed briefly.
SAT RATED MOLECULES
Saturated molecules wilhout Jone pair elect rons undergo high-energy
(J ---7 (J'" transitions in the far ultraviolet. For example, methanc hasa maximum
at 121 9 andethaneat 1350Acorrespondingto thi s tran ilion. Whenlone pair
electrot
u dltiol
a l 2273
Tal
compou
oflransi
CAl
Th
LonJuga
forll1ed.
cmpty
nonconJU
unaffect
are low ~
Ihe carbQ
I
0111
5--16 Fingerprinting 131
,y
lC

ing
bc
. be
lids,
by
mtil
over
ls of
cctra,
lique.
other
nce of
)orted
is al so
lhat
TABLE 5-2. Frequencies of Electronic Transitions in Some
Saturated Molecules
Compound
Amn
t
max
Medlu.m
H
2
0 1667 1480 vapor
MeOH 1835 150 vapor
Mel O 1838 2520 vapor
MelS 2290,2100 140,1020 ethanol
S8
2750 8000 ethanol
Fl 2845 6 va por
Cl
l
3300 66 vapor
Br
l
4200 200 vapor
1
2
5200 950 va por
lCl 153 CCI
4
SC1
1
3040 1150 CCl.
PI
3
3600 8800 EllO
AsI3 3780 1600 pet. elher
electrons are available, a lower-energy n -+ (J* transition is often detected in
addition to the (J -+ (J*. For exarnple, in triet hylarnine two transitions are observed
at 2273 and 1990 .
Table 5- 2 contains a li st ing of abs rption rnaxirna for sorne sat urat ed
compounds and gives sorne indication of the vari ati on in the range and inten ity
of transitions in saturated rnolecules.
C ARBONYL COMPO ND
The carbonyl chromophore has be n very extensi vely sludied. Upon
conjugat ion of the carbo nyl group with a vi nyl group, four 1[ energy levels are
formed. The highest occupied 1[ level has a higher energy, and one of the lowes t
empty 1[* levels has a lower energy, lhan the correspondi ng levels in a
nonconjugat ed carbonyl group. The lone pajr and (J electrons are relat ively
lInaffected by conjugat ion. As a resuIt , lhe 1[ -+ 1[* and n -+ 1[. transit ion
ar lowered and the absorption rnaxirna are shifted lo longer wavelengt hs when
the carbonyl is conjugated. T he difference is great er for the 1[ -+ 1[* t han for th
n -+ 1[* transi tion. The n -+ (J* band is not affecteO apprecia bly and often li es
beneath the shifted 1[ -+ 1[* absorption bando As slated earlier, electron-donating
groups attached to the carbonyl ca use a blu ' hift in lhe n -+ 1[* transition and
a red shift in 1[ -+ 1[*.
It i of int erest lO compare lhe pectra of thiocarbonyl compounds wil h
those of carbonyl compounds. In the sulfur compounds. l he carbon-s ulfur 1[
interaction is weaker a nd, as a resul t, t he energy di fference between the 1[ and
rr*-orbi lals is small er than in lhe oxygen compounds. In addi ti on, lhe ionizalion
potential of lhe sulfur electrons in Ihe lhi ocarbonyl group is less Ihan t he ioni ' l ion
potential of oxygen electrons in a carbonyl. The n cl ectrons are of higher encrgy
in lhe thioca rbonyI and lhe n -+ 1[ * transiti on requres less en rgy in these
compounds lhan in carbonyls. The absorpt ion maximum in t hiocarbonyls occurs
at longer wavelengths and in sorne compounds is shifted nto the visible regon.
,
INORGANIC SYSTEMS
The SOz molecule has two absorption bands in the near ultraviolet at
3600 (e = 0.05) and 2900 (e = 340) corresponding to a triplet and singlet
n --+ n* transition. The gaseous spectrum shows considerable vibrationa l fine
structure, and analysis has produced information concerning the structure of the
excited state.(18)
In nitroso compounds, an n --+ n* transition involving the lone pair electrons
on the nitrogen occurs in the visible region. An n --+ n* transition involving an
oxygen lone pair occurs in the ultraviolet.
The nitrite ion in water has two main absorption bands at 3546 (e = 23)
and 2100 (e = 5380) and a weak band at 2870 (e = 9). T he assignment of
these bands has been reported,( 19) and this article is an excellent reference for
gaining an appreciation of how the concepts discussed in this chapter are used
in band assignments. The band at 3546 A is an n --+ n* transition eB 1 <- 1A 1)
involving the oxygen lone pair. The band at 2100 is assigned as
n --+ n*( 1B
2
<- 1Al)' and the band at 2870 is assigned to an n --+ n* transition
eA
2
<- 1 A 1) involving the oxygen Ion e pair.
The absorption peaks obtained for vari ous inorganic anions in water or
alcohol solution are listed in Table 5-3. F r the simple ions (8r - , CI-, OH- )
the absorption is attributed to charge transfer in which the electron is transferred
to the solvent.
There are many more examples of applications of electronic spectroscopy
to inorganic and organometallic systems. These are revi wed on a regular basis
in the Specialist Periodical Reports of the Chemical Society (London). When well
armed with the fundamentals, this source(20) provides more exar'1ples.
TABLE 5-3. Characteristic Absorption
Maxima for Some Inorgan ic Anions
J. ()
el -
Br-
1-
OH-
SH-
S20/-
S20 S2-
N0
2
-
N0 -
3
NzO/-
1810
1995
1900
2260
1940
1870
2300
2200
2540
3546
2100
2870
3025
1936
2480
10
4
11,000
12,000
12,600
12,600
5000
8000
4000
22
23
5380
9
7
8800
4000
5--17 1
The absl
5200 i
molecuh
occur (S
(lJ
u
e
O
O
O
.o '"
<t:
FIGURE!
(1) 1
2
in e
base con;
\
A bl
u\travio\
an oso
in the
Chaptcl
m asure
range o
Th
where \
include5
transfer
around
this gro
coefficle
transfer
shift tha
be expl
of iodin
on the b
in the t
molecu
iodine
The ort
and a/
25
at
glet
fine
the
'ons
an
,23)
1t of
e fM
llsed
1A \)
j as
ition
cr or
)H - )
ferred
scopy
. basis
:n well
5-17 Molecular Addition Compounds of lodine 133
5-17 MOLECULAR ADDITION COMPOUNDS OF IODINE
The absorption band maximum for iodine (core plus (T2n
4
n
4
n*4) occurs at about
5200 in the solvent CCI
4
and is assigned to a n* -> (T* transition. When a donor
molecule is added to the above solution, two pronounced changes in the spectrum
occur (see Fig. 5-11).
250 350 450 490520
Wavelength (m.u)
Q)
u
e
(1) o
D
O
(2)
VI
D
(3)
<t:
(4)
FIGURE 5-11 Spectra of iodine and base-iodine solutions.
(1) 1 in CCI
4
; (2, 3, 4) same 1
2
concentration but increasing
2
base concentration in the order 2 < 3 < 4.
A blue shift is detected in the iodine peak, and a new peak arises in (he
ultraviolet regio n that is due to a charge-transfer transition.(21) Th existence of
an isosbestic point at 490 mil indicates that there are only two absorbing species
in the system; namely, free iodine and the com plex B:!- 11. As indicated in
Chapter 4, a ]: 1 equilibrium constant can be calculated from absorbance
measurements for this syslem. The constant value for K obtained over a wide
range of donor concentrations is evidence for the existence of al: 1 adduct.
The bonding in iodine adducts can be described by the equation :
I/JO = al/J cov + bl/Jel
where I/J el ineludes contributions from purely electrostatic forces while I/J coy
ineludes contributions from covalent interactions (these are described as charge-
transfer interactions). In most adducts b > a in the ground state and t he band
around 2500 arises from a charge-transfer transition in which an electron from
this ground state is promoted to an excited state in which a > b. In view of these
coefficients, the charge-transfer band assignment can be approximated by a
transfer of a base electron, n
b
, to the iodine (T* orbital. These facts and the blue
shift that occurs in the normal n* -> (T* iodine transition upon complexation can
be explained by consideration of the relative energies of the molecular orbit als
of iodine and the complex (Fig. 5-12). In Fig. 5- 12, n
b
refers to the donor orbital
on the base, and (JI * and nI * refer to the free iodine antibonding orbital s involved
2 2
in the transition leading to iodine absorption. The (Te' n/, and (T/ are labels for
molecular orbitals in the complex that are very much like the ori ginal base and
iodine orbitals because of t he weak Lewis acid-base inleraction (2 to 10 kcal).
The orbitals n
b
and (TI * combine to fo rm molecular orbitals in the complex, (Te
a nd (Te *, in which (Te> t\e bonding orbital is essentially n
b
and (Te * is cssentially
E
N
FIGURE 5-12 Sorne of the molecular
E
orbitals in a base-iodine addition
R
compound.
G (3)
Y
(JI *. Since (J/ is slightl y higher in energy than the corresponding (JI *, the
2 2
transition in complexed iodine [arrow (2) in Fig. 5-12J requires slightly more
energy than the corresponding transition in free 1
2
[arrow (1)] and a blue shift
is observed. The charge-transfer transition occurs at higher energy in t he
ultraviolet region and is designated in Fig. 5-12 by arrow (3).
Sorne interesting correlations have been reported, which claim that the blue
shift is related to the magni tude of the base-iodine interact ion, i. e., t he enthalpy
of adduct format ion. (2I
J
Thi s would be expected qualitatively from the lreatmen!
in Fig. 5- 12 as long as the energy of n/ differs v ry little from [hat of ni * or
2
else its energy changes in a linea r manner with the entha lpy, t1H. A rigorous
evaluation of this correlat ion wit h accurate data on a wid range of different
types of Lewis bases indicates that a rough general t rend exi !s, but that a
quantitative rel ati on (as good as t he accuracy of the data) does not exist. A
relationship involving the charge transfer band, the ionizat ion potential of the
base, lb ' and the electron affinity of the acid, Ea' is also repo rted(22 .2 3J :
(5- 9)
where t1 is an empirically determined constant for a related ser ies of bases.
The enthalpies for the for mation of these chargc-t ransfer complexes are of
interest and significance to both inorganic and organic chemists. For many
inorgani c systems, especia ll y in the areas of coordinat ion chemistry and
nonaqueous solvents, information a bout donor and acceptor interactions is
TABLE 5-4. Equilibrium Constants and Enthalpies of
Formati on tor Some Donor-1
2
Adducts
Donar K(lIter mole - 1) - H(kcal mole
1)
C
6
H
0.15 (2. 5) 14
Toluene 0.16 (25) 1.8
CH )OH 047 (20) 1. 9
Dioxa ne 1.14 (17) 3.5
(C
2
H
s
) 20 0.97 (20) 4.3
(C
2
H
s
hS 180 (25) 8. 3
CH
3
C(O)N(CH 3) 2 6. 1 (25) 4.7
Pyridine 270 ('Le ) 7. 8
(C
2
H
s
bN 51 30 (25) 12.0
se
re
ar
wl
ca
by
bel
pm
ber
eH
ha
effe
me
boru
ket
has t
erm
Th (
Ih
ami
\\ilh j
5-18
~ n
rT,* , the
,tly more
blue shift
y in the
I the blue
enlhalpy
.reatment
lflI2*or
ngorous
.diflcrenl
ut that a
1exist. A
li al 01' lhe
1.
(5- 9)
oases.
xes are 01'
For many
listry and
tions is
5-18 Effect of Salvent Palarity an Charge Transfer Spectra 135
essentia l lo an understanding 01' many phenomena. Since lhe aboye adduct s are
soluble in CC1
4
or hexane, the thermodynamic da ta can be interpreted more
readiJy than results obtained in polarsolvents, where large solvation enthalpies
and entropies are encountered. Sorne typical results from donor-I
2
systems in
which such solvationeffectsare minimal illustratethe wide range ofsystems tha t
can be studied, and a re contained in Table 5-4.
The following few examples iJlustrate the informa tion that can be obtained
by studying entha lpies 01' association in non-polar, weakl y basic solvents.
1. The donor properties 01' the JT electron systems 01' alkyl-substituted
benzenes have been reported(24)
2. A correlation 6( the heat 01' formation 01' iodine adducts 01' a series 01'
para-substituted benzamides with the Hammett substituent constants
(25
) 01' the
benzamides is reported.
3. The donor prop rl ies ofa series 01' carbonyl compounds [(CH3)2CO,
CH
3
C(0)N(CH
3
lz, (CH
3
)2 C(OlN(CH
3
l
2
, CH
3
C(0)OCH], CH
3
( )SCH
3
J
have been evaluated and interpreted
(26
) in terms 01' conjugative and inductive
effects 01' the group attached to the carbonyl fun ctional group.
4. The donor properties of sulfoxides, sulfones, and sulfi tes have becn
if1vestigated(27) The results are interpreted to indicat e t hat sulfur-oxygen JT
bonding is Jess effect iv in these systems than carbon-oxygen JT bonding is in
ketones and acetates.
5. Theeffect01' ringsizeonthedonorpropert ies 01'cycJi cet hersa ndsulfi des
has been investigated(28) It wasr und thatforsaturatedcycJic sul fides,ofgeneral
formula( H2lnS, thedona rpropert iesofsulfurarein theordern = 5 > 6 > 4 > 3.
The orderror t he analogousethercompounds is 4> 5> 6> 3. Explanati ons of
these effects are offercd.
6. The donor pr perties 01' a series 01' primary, secondary, a nd tertiary
amines have been evaluaLed.(29.30) T he order ofdonor t rengt h 01' amines varies
wil h th acid studied. Explanat ions ha ve been offered, which are based up n the
relative importance 01'covalenta nd electrostaticcontributions to the bondi ngin
various adducts.
In addition to iodine, several other Lewi s acids form charge-transfer
complexes that a bsorb in (he ultra violet or vi si ble regions. For example, the
relative aci dit i of 1
2
ICI, 8r
2
, S02' and phenol towa rd (he donor N,N-
dimethylacetamide have b en eval uated. Factors a ffecting the magnitude 01' t he
interaction
( 3 1
) and info rmat ionregardinglhebondingin theadductsarereported.
Good general reviews ofcharge-t ransfer complexes are a vail a ble.19.32. 33.34.3 5)
5-18 EFFECT OF SOLVENT POlARITY ON CHARGE-
TRANSFER SPECTRA
The ion pair N-methylpyridi nium iodi de undergoe a charge-t ransfcrtrans iti oIl
that can be represcnted(36)a in Fi g. 5-13. It has been found t hat the po iti on
ofthe charge-t ransfer band is a function oft he olvating bility oft he sol vent.
A hift t o lower wavelengths is detected in tbe better solvating solvent . The
posit ionsoft he bands ar reportedas tran ition energie ,E
T
. T ransi lion energies
(kcal mole- j l a re calculated from lhe fre uency as described in Cha pter 4. The
transili on energy i referred to as the Z-va luc. Sorne typical da ta are reported
l
TABlE 5-5.
Z-Values l or Some
Common Solvents
Solvenl Er or Z vaJue'
HO 94.6
CHJOH 83.6
2HSOH 79.6
CH JCOCH
J
65.7
(CHl )2 NCHO 68.5
CH] N 71.3
P yridi ne 64.0
CHJSOCH
J
71.1
H
2
NCHO 833
CHCI
1
64.2
I soctane 60.1
The ET or Z value is the transition
energy in kcal mole -, at 25C, I
atm pressure, for the compound 1-
ethyl - 4 - carbomethoxypyridinium
iodide.
FIGURE 5-13 Ion pair and charge
transl er excited sta te 01
N-methylpyridinium iodide.
(Jr ,I,-
N
7
e
I
'I
'
CH
3
CH
3
Ion palr Exclted state
in Table 5- 5. An explanation for tne observed s hift has been proposed.(36a
1
The
dipole moment of t he ion pair, C
5
H 5NCH 3 +1- , is reported to be perpendicul ar
to t he dipole moment of the excited state (Fig. 5- 13). Pola r solvent molecules
will align their di pole moments for maxi mum interaction wit h the ground state,
lowering t he energy of the ground state by s (vati on. The dipol moment of lhe
solvent molecules will be perp ndicular to t he dipole mament of t he ex:::ited state,
producing a higher energy for the excted state than would be found in the gas
phase. Since solvent molecul es l;annot rearrange in the time required for a
traosition, the rel at ive lowering of the ground state and rai si ng of the xcited
state increases the energy of the transiti on, E , over thal in the gas phase (Fig.
5- 14), shifting the wavelength of absorption lO higher frequencies. Hydrogen-
bonding sol ven t ' re often found to increa.e ET more tha n would be cxpected
by comparing thei r dielect ric constants wi th those of other solvenls. This is due
to the formati on of hydrogen bonds wi th lhe solut e. The use of the dielectric
constant to iofer sol va ting abi li ty can lead to difficully because lhe local dielectric
constan t in the vicinity of the ion may be very different [ro m the bul k di lectric
constant.
~ a ~ e d
FIGURE 5-14 Effect 01 solvent on the
transition energy, E
T

I
ET
Exclted
state
Ion palr
I
ET
Ion palr
G8S ph8se Solutlon
Th data obtained [rom these spectral shitts are employed as an empirical
measure of the ionizi ng power of the solvent. The res ults can be correlated wi th
a scale of "solvent polari ties" determi ned fro m Ihe efTect of solvent on the rate
of sol vol ysis of t-butyl chloride.<36a
1
O ther applications of these da ta to kinetic
and spectral studies are reported. <36b
l
Solvent effects are quite complicated, and
these correlations at best provide a semiquantitative indi cation of the trends
expected.
Significant difTerences exist between " solvating power" inferred from the
djelectric constant and tlle results from spect ral and kinetic parameters. Although
methanol and formamide are found 10 have si milar Z-values, the dielecl ric
constants a re 32.6 and 109.5, respecti vely. Sol vent cffects cannOl be understood
solely on lhe basis of t he dielectric con tant. Specific Lewis acid-base interactions
make t he problem more complex than t he simple dielectric model.
solv
con
from
inter
hept
is aH
In so
5--19
Cons
mol (
8 0th
states
pertUI
byan
5--20
Plane-
intensi
and le
when i
facing
the rol
re Iv
log th
plane-J
of Ihe
rec m
zation
where
ete
he
ular
ules
:ate,
. thc
tate,
: gas
or a
ited
(Fg.
,I gcn-
~ t e d
s due
ectric
cctrc
cclric
xci led
lale
on pair
nprcal
:ed wth
the rate
) kinetic
.led, and
le trends
rrom the
i\lthough
dielectrc
lderstood
Icractions
The band postons for the n ----; n* transtons n certan ketones n varous
solvents are found to be lnearly relaled to the Z-values for the solvents. A
constant slope s obtaned for a plot of ET versus Z for many ket ones. Devatons
from lnearty by certan ket ones in this plot can be employed to provde
nterestng s,tructural informat on about the molecul ar confo rmat on. Cyclo-
heplanone, for exampl e, does not gve a lnear plot of ET versus Z. The devation
s attributed to solvent effects on the relatve proporton of the conformers present
in solutOl.
5-19 STRUCTURES OF EXCITED STATES
Consi derable information is a vail able about tbe structure of exci ted states of
mol ecules from analysis of the rotationaJ band contours in the electronic spectra.
Both geometrical nformation aod vibrational information about the exci ted
states of large molecules can be obtai ned.(37) By studying and analyzing tbe
perturbation made on the vibrational fin e structure of ao electronic transition
by an electric field, the di pole moment of the excited state can be obtained.(38)
5-20 INTRODUCTION
Plane-polarized li ght consists of two crcularly polarized components of egual
intensity. The two types of circularl y polarized lght correspond lO right-haoded
and left-handed springs. Ci rcularly polarzed lght s defined as rigbt-handed
when ts electrlc or magnetc vector rotales cl ockwise as vewed by an observer
faci ng the direction of t he lght propagati on (i.e. , the so urce). The freq uency of
the rotation is related to the fr equency of the ligh. P lane polarized ligbt can be
resolved nto ts two circul ar components, and the two componeDts when added
together produce plane-polarized Iight in an opticaJl y is t ropic medurn. lf
plane-polarized light is passed through a sample for whi ch the refracti ve ndces
of the Ieft- and right-polarized componenls d ffer, the components will, upoo
recombination, give plane-polarized radiati on n whch the plane of lhe polari-
zation has been rotated through aD angle a, given by
(5-10)
where the subscripts refer to left and righ t, n is the appropriate refraclive index,
and Ais the waveleogt h of Iight employed. The units are radians per unt length,
with the length units gi ven by those used for A.
lf (he concent ration of an optically actve substance, e' , is expressed in uruts
of g cm - 3 (corresponding lo the densit y for apure substance), Ihe specific rotation
[IX] s defined as:
a
(5- 11)
[ a] = e' d'
Optical Rotary
Dispersion,
Circular
Dichroism, and
Magnetocircular
Dichroism
where d' is the thickness of the sample in decimeters. The molar rotation [M]
is defi ned as :
[M] = M[a] x 10-
2
= Ma x 1O-2/c' d' (5- 12)
where M is the molecular weight of the optically active componen!. (The quantity
10-
2
is subject to conventi on and not always included in [M].)
The optical rotatory dispersion curve, ORD, is a plot of the molar rotation,
[a] or [M], against A.. When the plane ofpolarizati on rotates c10ckwise as viewed
by an observer facing the direction of propagation of the radiation, [a] or [M]
is defioed as positive; a counterclockwise rotation is defined as oegative.
The technique whereby one determines that an oplically active substance
absorbs ri ght and left circularly polarized light differently is called circular
dichroism, CD. AlI optically active substances exhibit CD in the region of
appropriate electronic absorption bands. The molar circular dichroism el - e
r
is
defined as
- k k
l r
e - e = --- (5-13)
I r e
where k, the absorpt ion coefficient, is defi ned by T = lo 10 -kd with Jo and 1 being
the intensity of the incident and result ant light and d being the cell thickness.
The CD curve resul ts when we pl ot GI - C
r
ver us )..
Wherever circular dichroism is observed in a sample, the resulting radi alion
is not plane polarized but is ell iptically polarized. The quantity IX in the aboye
equat ions is then the angle between the initial plane of polarization and the major
axi s of the ellipse of the resultant ligh!. One can define a quanlity q/ (in radians),
the tangent of which is the ratio of the major to minor axes of the ellipse. The
quaotity q/ (i n radians), the tangent of which is the ratio of lhe major to minor
axes of l he elli pse. The quantity ifJ' is u ed to approximate the ell ipti city ; when
il is expressed io dcgrees, it can be converted to a specific elli pticity [ifJ] or mol ar
ellipticity [e] by
(P'
(5-14)
[ifJ] = c'd'
and
[e] = M [ifJ] 10 2 (5- 15)
where the symbols are as defi ned in equations (5- 11) and (5- 12). The quanti ty
[e] is related to el - C
r
by the fo Bowing equalion:
(5- 16)
Thus, ooe often sees l he CD curve plotted as [e] versus X
Wi th CD one can measure only the optical acti vity if t bere is aD
accompanyingele tronic absorption bando On l he otbe.. hand, ORD is measurable
[Ot
FIG
0-(-
eth)
b tt
D-f -
rcgic
vlsib
moJe
chror
a Iral
the re
the d-
curve
of eh
Wc ha
nn e/eC'
0plical
.c.,
5-21
5-21 Seleclion Rules 139
2)
ity
on,
",cd
M]
ncc
lar
~ of
;r IS
13)
when
molar
(5- 14)
(5- 15)
ity
(5- \6)
+
1)
J /"'\-
[a:l
O ~ - - - - - - ~ / ~ ~ ~ ~ _ ~ _ - - _ - - - - - - - - - - - - - - - ~
I
I
-\1
...1
I I I I
300 500
:>dm.)
FIGURE 5-15 ORO (---) and CD (-)curves lar
0-(-). [Rh(enb1
3
+ (en is an abbreviat ian lar
ethylenediamine).
both inside and outside the absorption bando*The ORO and eo curves of
0-(- )-[Rh(en) 3] 3, a re ill ustrated(391 in Fig.5-15.Throughoutmostofthevisible
region, the ORO curve is negative. However, the O curve associated with the
visible d-d transitions al "'"300m.t is clearly positive.AHt hechromophores in a
molecu)e cont ri bute lo the rota tory power a t a gi ven wave)englh, bUI only the
chromophorethat absorbsat the givenwavelcng hcontributes to t h D. Thus,
a transition in Ihe fa r u.v.can makea signi ficantcontribulion lo lhe rotatio n in
the region ofd-d transi Li onsin theORO.The negat ive effect in (he U.v. dominates
thed-d c ntribution through mosl ofthe visible region, and lhe negative ORD
curve r sults.Formostoftheapplications to bedi scussed here,CDislhemethod
ofchoice.
5--21 SELECTION RULES
We have previously given [equation (5-3)] the lransi lion moment integral for
an electricdjpole tran il ion,a nd we ment ioncd thal a magneticdipole transiti o n
int egral has a similar fo rmoIn order for an electronic transi tion lOgive rise to
opt icalact ivity, IheIransilionmustbe both elect ricand magneticdipolea llowed,
i.e.,
where R is the rota l ional strength, M
/'-.
D is the magncti c dipole operator, and M
islhe eleCl ricdipole peralor. Ifa nelcctronic a bsorption band i observed, (here
muol be some mechanism for maki ng t hi s allowed ; it then becomes important
Dis theabsorptiondilIerencebetweenleft anu ri ght circul arl ypolari zcd light for anelectronic
transi ti on.ORDISrelaledlolhedifTe rencc belweentheindiccs ofrefractionforlenand rightcircular ly
polarizcd light. Thc two effeclS are in tcrrelated via the Kro ni g- Kra mer. rela tion.
'461
140 Chapter 5 Electron ic Absorption Spectroscopy
to be concerned with the magnetie dipole seleetion rules. The sign and magnit ude
of the aetivity ean be ealculated(40) by evaluating bot h the eleet rie a nd magnetie
dipole integrals.
5-22 APPLlCATIONS
The use of CD in band assignments is an obvious applieati oo of our previous
diseussion of the seleetion rules. F or example, oetahedral nickel( I1) eomplexes
ha ve three bands assigned as 3 A 29 to 3T
29
, 3Tg(F), a nd 3Tg( P) in order of
incr asing energy. Sinee the magnetic dipole operator (the magnetie di pole
t ransforms like the rotati ons RxR yR ) in Oh is T
I9
only the 2 A
2g
-> 3T
29
transi tion
5-23
is magnetic di pole allowed. Aecordingly, it is fOll nd in t he CD speet rum of
Ni(pnh2 + (pn = pr pylene diamine) that the low-energy band has a maximum
(t: - 8
r
) value of 0.8, while those for t he oth r ba!1ds are less than 0.04. This
eonfirms t he original band assignments.
A seeond type of application nv lves using CD to show that certain
a bsorption bands have contribulions from more than one el e tronic transition.
The CD bands a re usually narrower and can be positive or ncgative. This idea
is ill ustrated in Fig. 5-16, where the absorpti on curve a nd CD curve for
.1( +)-Co( nh 3 + in aqueou oluti on a re shown. (41 )
Co(TIl ) complexes wit h 0" ymmetry commonly ha e two a bsorptions
assigned to IT
I9
and IT
2g
. The .ymmet ry of Co(enh 3+ is D
3
, so the Ir nsilion
to t he T states are expected lo sbow sorne splitt ing . This is not det ctcd in the
absorpti on spectrum, as seeo in Fig. 5-16. However. lhe effects f lower ,'ymrnel ry
are observed in the CD spectrurn. The rnagnetic dipole selection rules for DJ
predict that t he low-energy band wi ll have two rnagnetic dipole all owed
components, I A
I
-> I A
2
and I A
I
-> l Ea . The I A
I
-> IEb transi tion of lh high-
energy band is rnagnetic di pole bul l he 1 A1 -> 1Al tra nsition is no1. In
the CD, two cornponents (+ and - ) re seen in lhe low-energy band and one
in l h high-energy band, a predicted for a D3 di stortion. Applications of t hese
ideas can be u ed to indicate the syrnrn lry of molecules in sol uti on and in uniaxial
single crystals.
FIGURE 5-1 6 The
's
absorption spect rum (soli d
'"
en
2
o
1\
Hne) and CD curve (dashed
I \
line) 01 (+ )-Co(enh
3
+ in
I \
aqueous solution.

\ -1
\
j
je
tic
OUS
:xes
r of
pole
Ilion
n of
nutn
This
:rtain
;ition.
.idea
ve for
'Ptions
silions
I in the
nmetry
for D3
allo
wed
le high-
not. In
and ooe
ofthes
. uniaxial
2
o
-1
~ 2 3
Anotherapplicationinvol vesusingthesignoflheCDlOobtai n theabsolute
configuration ofa molecule.(42)Thisapplicat ion has been part icularly successful
for organiccompounds. (43) I n organicsystems,absolute confi gurations areoften
assigned by analogy to known systems. Particular care must be cmployed in
determi ning what consti tut es an analogous compound.t
44
.45) By usi ng complete
operat or-matrices ror Ihe electric and magnetic dipole componenls, the signs of
thetri gonal cornponentsin sorneCo(lII)and Cr(IIJ)complexeshavebeen rel a ted
to the absolute configurations ofthe complexes.(''O)
Fi nally, optically acti ve transitions are p lari zed, and the polarizat ion
information can be used to support l he assignment oft he electronic spectrurn.
5--23 MAGNETOCIRCULAR DICHROISM
When plane-polarized lighl is passed through any substance in a rnagnet ic fi eld,
Ho. whose component in the direction ofthe light propagation i non-zero, the
substance a ppears lo be optical! active. Left and right circularl y polarized light
donotinteractinequi valentways. Foratoms,forexample,leftcircularlypola rized
(Icp) li ght induces a transition in which l1m] is -1, while for right ircularly
polarizcd (rcp) light l1m] i + 1. Note Ihal m] has the same relationship lO J as
mI has to l. If one obser ved a transition from an S statc where J = O to a I P
statewhereJ = 1, the twotransit ionsin Fig.5- 17 would occurasa consequence
ofthis selection rule. (46)
If the absorpt io ns of left and right circularly polarized li ght corresponding
to these transitions are measured separately, lhe curves in Fig. S-J 7(B) are
obtained.Here V
o
is the band maximumfOI" lhe absorpt ion bando When the rncd
curve is plotted, the result in Fig. 5- 17(C) is obtained, provided that t he band
width is much greater lhan the Zeeman spli tt ing ofthe excited state. A curve of
this sort is ref, rred to as an A- term and can ari e only for a t ransition in which
J > Oror oneofthestates involved. Thesign ofthe A- term in molecules depends
upon the sign of the Zeeman spli tting and Lhe molecular selection rules ror
CifCUlarly polarized light.
mJ
---.-
'"T"""--+-
Icp
+1
~ ~ / o
-
~ 1
rcp
'S
(A) (B) (e)
FIGURE 5-17 The transitions and expected spectrum for 's-+ 'p in the mcd
experi ment. (A) the transtions ; (B) spectra for left (e,) and right (e.-) clrcularly
polarized radiation; (C) the mcd spectrum (el - er) circularly polarized radiation ; (C)
the mcd spectrum (e, - sr) ; A-term behavior.
Magnetocircular Dichroism 141
Next consider a transition from a Ip to a IS state. Figure 5- 18 summarizes
this situation. The ~ m = +1 transition for rcp light is now that of I1IJ from -1
to O. Because the mJ states are not equally populated, but Bol tzmann popul ated,
the two transitions will not have equal intensity, as shown in F ig. 5-18B. T he
relative intensities will be very much temperature dependent. The resultant mcd
curve, shown in Fig. 5-18C, is referred to as a C-term. The band shape and
intensity are very temperature dependent. An A-term curve usually occurs
superimposed upon a C-term curve.
lp
FIGURE 5-1 8 The transitions and expected spectrum for lp-> I S i n the mcd
experiment. (A) the trans itions ; (8) spectra for left and right circularly polarized
rad iation; (e) the mcd spectrum; C-term behavior.
A third type of curve (B-term) results when there is a fi eld-ind uced mi xing
of the states involved (t his phenomenon also creates temperal ure independent
paramagnetism, TIP, and will be discus ed in more detai l in the chapter on
magnetism). This is manifesled in , curve that looks li ke a C-curve but that i
tempera ture independent. Si nce this mixi ng is present to ome e tent in all
mol cules, al/ substances ha ve mcd activity. The magni t ude of tht: exlernal magncli c
field intensi t y will determine whelher or not the signal is bs rved.
The following cha racteristics summarize the ba is for det cl ing and
quali tativel y interpreting mcd curves :
1. An A-term curve changes sign al t he absorption maximum, while B-
and e - curves maximize or rninimize at the ma imum of t he eleelr nie abs rplion
bando
2. A e-Ierm curve's intensity is inversel y pr portional to the a bsol ule
lemperature, while a B-term is independent of temperalure.
3. An A-Ierm spectrum is possible only if the ground or exci ted state
invol ved i lh electronic tran ilion is degenerale and has a ngular momentum.
4. A C-term spectr um i possible only ir l he ground state is degenerate and
has angular m mentuill .
As can be anticipated mcd measurements are of considerable ut ility(46.47
l
in assigni ng the e1ect ronie spectrum f a compound. Furlhermore, lhe magnitude
of the parameter provides information about many subtle electronic effects.(47
l
The molecul ar orbital origin of an electron involved in a t ran ition can be
48
determined. The lowest energy band in RU0
4
( l i' c1early a n oxygcn to rUlhenium
charge-transfer bandoOne ca nnot eterminc from th electronie p cl rurn whet h r
the oxygen elect ron involvcd in t he transition carne from a ti n or t
2
n typ of
oxygen l
as ti (o
In the 2
intensit )
com
thi s
rizes
1 - 1
ated,
Thc
mcd
land
rccurs
oxygenmolecularorbital.ThesignofthemcdA-termestablished(48) thetransition
as ln(oxygen)--> ex'_ y' ."t ' (ruthenium). Another significant adyantagc of mcd is
In the assignment of spin-forbidden electronic transitions that haye ycry low
intensity in the electronic absorption spectrum. The assignment s of the
components in a six-coordinate chromium(III) complex haye been made with
this technique(49) Other applications haye becn summarized in reyiew
articles(46.47) Mcd has been extensiyely applied(46b) to proyide information
rcgarding the symmetries, angular momenta, electronic splittings, and
yibrational-electronic intcractions in excited electronic states.
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Wiley, New York, 1962.
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6. H. McConnell, J.Chem. Phys., 20, 700 ( 1952).
7. G.1. Brealey and M. Kas ha, J. Amer. Chem. Soc., 77,44 2 (1955).
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tra nsi tions, see A. B. Lever, J. Chem. Ed., 51,612(1974).
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1955. 137.
12. R. P. Bauman, "Absorption Spcctroscopy," Wiley, New York, 1962.
13. L. Lang, "Absorption Spectra in the Itraviolet and Visible Region," Vols. 1-20,
Academic, Ncw York, 1961- 76.
14. H. M.Hers henso n,"Ultraviolet and VisibleAbsorptionSpectra- Index for 1930-54,"
Ac,demic, el'.' York. 1956.
15. "Orga nic ElectronicSpectral Data," Vols. 1-10,Interscicncc, Ncw York. Compi lati on
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16. "ASTM (American Society for Tes!i ng MateriaJs)Coded IBM ards ror UJtravioJ et
and Visibl e Spcctra " ASTM, PhiJadclphia, 1961.
17. S. F. Mason, Quart. Revs., 15,287 (1961).
18. N. MetropoJi s, Phys. Rev., 60, 283, 295 (1941).
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1- (1967- ), pccialist PeriodicaJ Report, Chemica JSociet . London.
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45. A M. Sargeson, Transition Metal Chemistry,3, 303 (1966).
46. (a) A. D. Buekingham and P. J Stephen , Ann. Rev. Chem. , 17, 399 (1 966); (b)
P J. Stephens, Ann. Rev. Phys.Chem., 25.201 (1974)
47. P. .Schatzand A. 1. McCaffery,Quart. Revs.,23,552 (1969), and references therei n.
48. A. H. Bowman. R.S. Evans and A. F. Schreiner,Chcm. Phys. Letters.29, 140(1974),
and refcrenees thercin.
49. P.1. Hauser, A. F. Schreiner and R. S. Evans, Inorg. Chem., 13, 1925 (1974), and
references therein.
ADDITIONAL A. The 10IJowing rcferences may be consulted lor rurlherstudy :
REFERENCES
/-l .H. Jafreand M.Orchin,"Theory andApplicationsof ltravi olet Spectroscopy,"Wiley.
ew York, 1962.
M. Orchin and 1-1 . 1-1 .Jaffe, " Symmetry, Orbitals and Spect ra," Wiley Interscience, Ncw
York, 1971.
C. Sandorfy, ..El cctronic Spectra and Quantum Chemist ry," Prcnti cc-Hall , Englewood
Cli ffs, N. J. , 1964.
R. P.Bauman,"Absorption Spcctroscopy," Wi ley, New York, 1962.
E. A. Braude and F. C. Nachod, " Delermination of Organic Structures by Physical
Methods," pp. 131- 195, Academic, New York. 1955.
G. Herzberg, "Molecular p ctra and Molecula r Structurc," Vals. 1 and 3. D. Van
ost rand Co., Princcton, N.J ., 1966.
J. N.
Y
A.F..
C(
G. W.
Y
A. 8.
..\ .P.I

-
1. Thl
l w(
du
tra.!
cp
a.
b. V
f.
c. rr
h
2. WhaI
rrcqu
H. Be
j).
ors
Exercises 145
1. N. Murrell, "TheTheory of Elcctronic Spectra of Organic Compounds," Wley, Ncw
York, 1963.
A. E.Gillam and E.S. Stern,"Introdllction to Electronic Absorption Spectroscopy," 2nd
ed., Arnold, London, 1957.
G. W. King, "Spectroscopyand Molecular Structure," Holt , Rinehart,and Wnston, ew
York.1964.
A. B. P. Lever, " Inorganic Electronic Spectroscopy," 2nd ed. El sevier, ew York, 1984.
A. P. Demchenko,"Ultraviolet Spectroscopy of Proteins," Springer-Verlag, Berln, 1986.
"Spectroscopy in Biochemistry"ed. J. E. Bell, CRC Press, Boca Raton, Fla., 1980.
:rlin..
wer.
Iskr
17\.
J,; in
odieal

'. ldCI11ic
I and A.
966) :(b)
;thcrcin.
() (1974).
74). <Ind
:.Wilcy,
3. D. Van
1. The compound is reported [1. Mol. Spectr. , 5, 118- 132 (1960)J to have
two absorption bands, one near 2700 and a second around 2300 . One band is
due to the 11 ->11* transiton oC the phcnyl ring and the other is a charge-tmnsfcr
transition from the lonc pairclectrons on arsenic to the ringoThe 2300 band is s lvent
dependent, and the 2700 band is not.
a. Which band do you suspect is 11
b. What effect would substitution ofone of the phenyl groups by CF
J
frequency of the eharge-transfer transition'1
have on the
c. In whieh of the following compounds would the charge-transfer ba
highest frequency,(C(,H5hp. (C6H5hSb, or (CfH' )JBi'?
nd occur at
2. What eOcet would changing the solvent from a nonpolar to a polar one have on the
frcquency for the following:
a. 80th ground and cxeited states are neutral (i. e., there is no eharge separal ion)"
b. he ground state is neutral and the excited state is
c. The ground state is polar, the excited stale has grcater charge 'cparation, and
the dipoJe moment vector in the excited state is perpendicular to the ground

d. The ground state IS polar and thc cxcited is
3. Would you have a betterehance ofdetecting vibrationalfine strueturein anelectronic
transition ofa solute in liquid CCl
4
or C IJeN Why?
4. Do theexcited,latesthat resul tfrom n ->71.* and Tt -> 71. * transiti ons in pyridinebelong
to the samc ir red ucible repre To wh ichspccies do they belong'l
5, Under what conditions can eleetronic transitions oecur in the infrared
Which compounds wo uld you examine to find ancxample ofIhis?
6. Explain why l he transition that occurs in the ion pair .N-methylpyri dinium iodide
doe not occur in the solvcnt-separated ion pair.
7, RecaJl thecenterofgravity ruleand explain why the blue shift in lhei dine transition
should be related to thc heal of intcraction ofiodine with a donor(see Fig. 5- 12).
EXERCISES
146 Chapter5 Electronic Absorption Spectroscopy
8. WhatisthepoJa rizationexpectedin the 1Al -> 1A
2
(n -> 1!*) transitionofforma ldehyde
from vibronic coupling? The vibrational modes have al' b
1'
and b
2
symmetry.
9. Two observed transi tions in octahedral cobalt(Il) complexes occur at 20,000 cm-
1
and 8000 cm- 1 with extinction coefficients of e 50 and 8, respectively. These
have been assigned to 4T -> 4T and 4T
l
!l -> 4T
2g
. lndicate whether or not
I9 I 9
vibronic coupling can account for the intensity difference. (The vibrations are a
lg
,
eg, ti'" t Zg' and t2J
10. The vibrations of OCI
4
2
- have symmctrics correspondingto al ' e, and 2tz. Explain
whether or not t he Az-> T
z
and Az -> TI d-d transitions can gain intensity by
vibronic coupling.
11. Consider the cyclopropene cati on shown below:
H
I
C
/ EB""
C--C
H
/ "-
H
a. Using the three out-of-plane p orbitals(labeled ({il' ({i2' and ({i3) as a basis set, do
a simple Hc.kel calculation to obtain the energies ofthe resultant m.o.'s in terms
of(1. and {J.
b. The symmetries of these m.o.'s in the D 3h point group are Az" and :;". Briet1y
describe two methods you could use to find Ij(A /1 in terms of ({i l ' (P2' and ({i 3'
c. Show whether the clcctronic transition to the first excited state is allowed. Hso,
what is it s polari zation7
d. What is the energy ofthis transition (in terms of(1. and {J)?
e. What complications are likely in the approach used in part d7
12. Pyrazine has DZh symmetry.Thesix pi -Ievels are shown bclow with a rough orderof
energies. The two unla beled levels are the non-bonding m.o.'s from the nitrogen lone
pairs.
b29----
a
b)
u
.. _____ ONONOr'
y
x is out ofplane
bzg -----
b _____
lg
b)u_____
11. What are the symmctries of the {wo non-bonding m.o.'s7
b. What is thc symmetry of the tate of lowest energy that arisc, rrom a 1! -> n*
transition7 (s it allowed? Irso, what is its pol arization7
c.
13. Int
is a
14. In
distt
The
of
to
a.
b.
c.
an
15.
Exercises 147
or mll
are a19'
Explain
by
set, do
interms
E". Brielly
and lP3'
. If so.
a 11: --+ 11:*
c. Whatis thesymmetry ofthe states thatarise from n --+ 11:* transiti onsfrom the two
non-bondinglevels to the lowes t11:* level ?Determinewhetherei theris allowed,and,
ifso,givethe polarization.lf ei theris forbidden,give thesymmetrytha tavibrational
mode would need in order to lend intensity via the vibronic mechanism.
13. In the RelCl
a
l
- ion, thetransitionofanelectron rromthe b
lg
orbital to theb
lu
orbital
is a d-d transi tion in a molecule with a center of inversion. Is it allowed? Explain.
fJ(b
lg
) = ~ (dx,.!11 +d x,.' ll)
14. In several coordination complexes of cis-butadiene, the 2,3 carbon-carbon bond
distance wasobserved to be appreciablyshorter than the normalsingle bonddistance.
The possibilityofbackdonation orelectrondensity from the metal into the11:* orbital
ofthe butadienewas proposed to account for this shortening.Thisexercise is designed
to provide sorne insights into the chemi stry of this ligand.
a. Do a simple Hckel calculation on the 11: orbit als of cis-butadiene. Obtain the
energies of the 1I:-symmetry orbitals.(Hint: set y = X2)
b. Work out the symmetries of the 11: and n* orbitals.
c. The coefficients ofthe n molecular orbital s are given as follows.
el el C
J
e
4
fJa
fJb
fJc
fJd
.60
.37
.37
.60
- .37
.60
- .60
.37
- .37
.60
.60
- .37
.60
.37
-37
- .60
(1) Assign the symmetry speeies ofeach mol ecular orbi tal.
(2) Arrange them in order ofincreasingenergy.
d. Dctermine the symmetrie. ofall four singly excited stales ofcis-butadiene. Which
transitions are allowed? Give their pol ari zations.
e. The lowest-energy 11: --+ n* transition is observed at ;. = 217 mIl in cis-butadiene.
Calculate ~
r. Calculate the 2,3 bond order for cis-butadiene and then calculate the 2,3 bond
orderwith two addi tional electrons in the lowestn* orbital. Doyour results agl'ce
with the conclusions regarding n back bonding?
IS. For lrClns-but adiene.
a. determine the symmet ies ofthe n molecular orbi tals.
b. determine the symmetries of all four si ngl y xci ted states. Whi ch transitions are
allowed? Give their polarizations.
c. compare the resu lts in parts a and bwith those obtained forcis-butadicne. Would
an HMO ealculalion differe nliale belween thcse lwo rotamers ')
148 Chapler 5 Eleclronic Absorption Spectroscopy
16. Consider the 1[ molecula rorbi talsobtained from the p, atomicorbi tals in NO)- .The
ground state orbital energies and symmetries are:
a
z
ll
-- --- e"
a
2
"
a. Obtain the state symmetries ofthe singly excited statcs.
b. Which clectronic transitions are allowed ? Explain.
c. NO)- hasfourvibrat ionalmodes,Al ', 2E', andA". Doesvibroniccouplingprovidc
a mechanism by which any forbidden transitions become all owed? Ex plain.
17. Show that the following two statements are equivalent for the point groups D
4
, C
3/
"
and T
d
:
a. In orderto observecirculardichroism,the transition from ground state to excited
stale muSI be simultaneouslyelectric dipole-allowed and magneticdipole-all owed.
(The magnetic dipole momentalong the ex axis transforms as a rotation about the
ex axis, R7.)
b. Tn order10 observe circular dichroism, the molccule must be optically active_
lh
[he rcsul
os illate
law
held [ ge
For
wherc X
Apl Ol 01'
he
Vibrati on and Rotation
Spectroscopy: I frared,
Raman, and Microwave
,vide
6-1 HARMONIC ANO ANHARMONIC VIBRATIONS
As discussed earlier (Chapter 4), quanta of radiation in the infrared region have
"nergies comparable to those required for vibrational transitions in mol ecules.
Let liS begin this discussion by considering the c\assical description of the
vibrational motion of a diatomic molecule. For this purpose it is convenient to
consider the diatomic molecule as t w masses, A and B, connected by a spring.
In Fig. 6- 1 A the equilibrium position is indicated. Ir a dlsplacemenl of A and B
is carried out, moving them to A' and B', [as in Fig. 6-1 B] . there will be a force
acting to ret ur n the syslem to the equili brium position. Ir the restoring force
exerted by the spring, f, is proportional to lhe displ accment r, . e. ,
I= - k t'1r (6- 1)
the resultant motion that develops when A' and B' are released and allowed to
oscillate is described as simple harmonic motion. In equation (6- 1), the Hooke's
law constant for the spring, k, is called the[orce constanr for a molecul ar system
held together by a chemical bond.
For harmonic oscillation of two atoms connected by a bond, the potential
cnergy, V, is gi ven by
where X is the di placement of the two masses from their equilibrium position.
A plot of the potential energy of the system as a funcLion of the dislanc x between
the masses is thus a parabola that is symmetrical about the cquil ibrium
intcrn uclea r distance, re' as the minimum (see F ig. 6-2). The fo rce constant. k, is
a measure of the curvat ure of Ihe pOlential well near re'
This cl assical springlike model does not hold for a moleculc beca usc a
molecular system cannot occupy a continuum of energy states, but can occupy
only discrete, quant ized energy le els. A quantum mechanical treatment of the
molecula r y tem yiel d lhe following equati n for the permitted energy states
of a mole ul that is a simple harmonic o, illalor :
El' = hv(v + (6-2)
Introduction
(A)
(B)
FIGURE6-1 Displacement 01
the equilibrium position 01
two masses connected by a
spring.
149
------
150 Chapler6 Vibration and Rot at ion Spectroscopy : Infrared , Raman , and Mi crowave
.---------------
,//
/'
FIGURE6-2 Potential
energy versus distance. x.
V
lor(A)aharmonicoscillator
(solid line) and (6) an
anharmonic oscillator
w
(dotted line) .
-
x
where u is an integer 0, 1, 2, ... , represe nting the vi bra ti onal quantum number
of the various states, Ev is the energy of the uth state, h is Planck 's constant, and
vis the Jimdamental uibrationji-equency (sec - 1) (i.e., the frequency for the transi tion
from state u = to u = 1). These states a re indicated for a ha rmoni c oscillator
in Fig. 6--3.
The potential energy curve of a real molecule (see Fig. 5- 1), reproduced as
a dotted li ne in Fig. 6--2, is not a perfect parabola. The vibrational energy levels
a re indicated in Fig. 5-J ; they are not equally spaced, as equation (6- 2) required,
but converge. The levels converge because the molecule undergoe anharmonic
rather tha n harmonic oscillation, i.e., al large displacements the resloring force
is less t han predicted by equati on ( l ). Note that as the molecule approachcs
di ssociation l he bond beco mes easier lo slretch than the harmonic oscillator
function would predict. This deviation fro m ha rmonic oscill ation occurs in all
molecules and becomes greater as the vibrati onal quant um number incrcases. As
will be seen la ter, the assumption of harmonic osci ll ati on will be sufficiently
accurale for certai n purposes (e .g., the descri ption of fundamental vibrations) a nd
is inlroduced here for thi s reason.
6-2 ABSORPTION OF RADIATION BY MOLECULAR
VIBRATIONS-SELECTION RULES
The interaclion of electromagnetic, infra red radia lion wit h a molecul e involves
interaction of the oscill ating eleCl ric ficld component of the radiat ion with an
oscillat ing electric dipole moment in the molecule. Thus, in order fo r molecules
lo absorb infrared radiation as vibrational excitation energy, there must be a change
in the dipole moment of the molecule as it vibrates. Con equentl y, the stretching
of homonuc1ea r diatomic molecul es will nol give rise to infrared absorptions.
According to thi s select ion rule, a ny change in directi on or magnitude of the
dipole during a vibration gives rjse lO a n osci ll ating dipole that can interact wit h
Ihe oscill ati ng electric field component of infr a red radiation, giving rise to
a bsorpl ion of radiarion. A vibrat ion that res ult s in a cha nge in di rection of Ihe
dipole is illustrated by lhe N- C- H bendi ng mode of HCN. There is hI t! change
in the magnitude of the dipole, but an apprecia bl e cha nge in di rcction occurs
when Ihe molecule bends.
T he second selection ruJe can be deri ved fr om lhe harmonic oscillator
approximati on. This selection rule, which is ri gorous for a harm nic oscillator,
6-3
The d
byeq
where
[l =
mo
a pa
calculate
FIGURE 6-3 Vibrational
stale corresponding lo a
normal vibrali onal mode in a
harmonic oscillator.
6-3 Force Constant 151
.-'
Imber
\. and
,sitio n
iHator
ced as
levels
uired,
monlc
g force
oaches
ciBator
s in a1l
LSes. As
iciently
ns) and
sta tes that in the absorption of radiation only transitions for which ~ V = + 1
can occur. Since most molecules are in the vibrati onal level at room V
o
temperature, most transitions wi ll occur from the state V
o
to VI' The transition
is indicated by arrow (1) of Fig. 6--3. The freq uency corresponding to this energy
is caBed the jimdamental frequency. According to this seJection rule, radiation
with energy corresponding to transitions indicated by arrows (2) and (3) in Fig.
6--3 will not induce transitions in the molecule. Since most molecules are not
perfect harmonic oscillators, this selection rule breaks down and transitions
corresponding to (2) and (3) do occur. The transition designated as (2) occurs at
a frequency about twice that of the fundamental (1 ), whereas (3) occurs at a
frequency about three times that of the fundamenta\. Transitions (2) and (3) are
referred to as the first and seeond overtones, respectively. The intensity of the first
overtone is often an order of magnitude less than that of the fundamental , and
that of the second overtone is an order of magnitude less than the first overtone.
6-3 FORCE CONST ANT
The difference in energy, ~ E between two adjacent levels, E" and Eu+ I is giveo
by equation (6--3) for a harmonic oscillator:
~ E = (2
h
n) (1) 1/ 2 (6-3)
where k is the stretching force constant and J.I. is the reduced mass
[,u = mA mB/(m A + mB) for l he diatomic moJecule A- B]. The relati onsbip bet ween
energy and frequency, ~ E = hv = he v, was presented in Chapter 4. The symboJ
\' will be used interchangeably for frequency (sec -
I
) or wavenumber (cm - 1), but
the units will be indicated when necessary. ]n the HCI molecule lhe a bsorption
of infrared ra tiation with v = 2890 cm-
1
corresponds to a Iransilion from the
ground state to the first excited vi brat ional state. This excited state corresponds
to a greater amplitude and frequency for the sl retching of the H- C1 bond.
Converting v to energy produces /l E of equation (6- 3). Since a1l other quantities
are known, this equation can be sol ved to produce : k = 4.84 X 10
5
dynes cm-
I
or, in otber commonly used units, 4.84 md l. In tbis calculation the reduced
mass is expressed in grams. Stretchi ng force constants for varous diatomic
molecule are summarized in Table 6-1.
The force constants in Table 6-- 1are cal culated by us ng equation (6-3), which
\Vas derived from the harmon c oscillator approximati on. When ao a nharmonic
oscillator model is employed, somewhat differeot va lues are obtained. For
example, a force coostant of 5.157 x 10
5
dynes cm - [ r ults for He\. The latter
value is obtained by measuring the fi rst, second, and third overtones and
evaluatng the anharmonci ty from the dev atoo of t hese freq ucn ies from 2, 3,
and 4 ti mes the fundament al, respectively. Since (hese overtones are often not
detected in larger molecul es, we sha1l not be concerned wit h the detai ls of the
anharmonicity calculaton.
The force constants for sorne other stretching vi brations of ioterest are list ed
in Table 6-2. F or la rger molecules, tbe nat ure of Ihe vibration t hal gives ri e to
a part icular peak in the spectrum is quite complexo Accordi ngly, one callnot
calcul ate a force con tant for a bond by substituting the "ca rbonyl frequency,"
,
,
'
152 Chapter 6 Vibration and Rotation Spectroscopy Infrared, Raman, and Microwave
TABLE 6-1 Stretching Force Constants
and roe!
for Various Diatomic Molecules
cryst al)
(Calculated by the Harmonic Oscillator
As
Approximation)
the freql
replaced
Molecule v (cm-
1
) k(dynes cm-
1
)
'W '111 a
8.8 x
105 the freq\
I-1 F 3958
HCI 2885 4.8 x 10
5
C-H
an'
HBr 2559 3.8 x 10
5
[12 x 2
1-11 2230 2.9 x 10
5
occur al
F u
892 4.5 x 10
5
2
deuleratt
Cl z"
557 3.2 x
105
Br
2
u 321 2.4 x 10
5
t hat in\'
La
213 1.7 x 10
5
a metal
10
5
CO 2143 18.7 x
vibra tior
NO 15.5 x 10
5
mass. L.
vibrall on
TABLE 6-2. Stretching
Force Constants for
Various Stretching
Vibrations (Ha rmonic
Oscillator Approximation)
Bond k (dynes cm 1)
4.5 X 10
5
:::C- C= 5.2 X 10
5
:::: =c:::
9.6 X 10
5
-c c- IS.6x 10
5
:::::C= O 12.1 x 10
5
- C N 17.7 x 105
-C- H 5.9 x 10
5
::;C- H 4. 8 X 105
a Observed by Raman spectroscopy.
for example, of a complex molecule into equation (6-3). This wil l become clearer
a ' we procced and is menti oncd here as a note of caution. The force const ant s
in Table 6- 2 result from a normal coordi nate anal ys is, which will al so be di scussecl
in more detail short ly. A la rger force constant is often interpreted as being
indicative of a stronger bond, but there is no sirnple relation between bond
dissociation energy and f urce constant. Wc defi ned the force constant earli er as a
measure of the curvature of the potential wcll near t he equ ili brium int crn ucJear
configuration. T he curvature is the rate 01' change of the slope, so the force
constant is the second derivative of the potential energy as a function of di sta nce:
(6-4)
k=
o
Here V is the poten tial energy and r is the deviation of t he internuclear
distance, at which r = O. rn a more compl icated molecule, r is repl aced by q,
which is a composite coordinate tha! describes t he vibration.
Triple bond have st relching force constants of 13 to 18 x 10
5
, doublc bonds
aboul 8 to 12 x 10\ and single bonds below 8 x 10
5
dynes cm - 1 Ln ge neral,
force constants for bending modes are often about a ten th as large as those for
stretchi ng modes.
The bands in the 4000 cm - 1 to 600 cm - 1 region of the spectrum most ly
involve st retc hing and bending vi bralions. Most of the intense ba nds aboye 2900
cm - 1 inv Ive hydrogen tretching vibration for hyd rogen bound to a low- ma s
a tom. T hi s frequenc range decreases as the X- H bond becomes weaker and
the atomic weight of X increases. T riple bond stretches occur in t he 2000 to 2700
cm - 1 regi on. Absorption bands assigned to double bond st ret ches occur in the
1500 to 1700 cm - 1 region. Band in this regia n of the spe t rum of an unknown
moleeule are a con iderabl e ai d in slructure determina tion. Ba nds in the 1500 to
400 cm -1 region fi nd uti lity in lhe fi nger pri nt type of applical ion.
Metal -Jigand vibrations usually oecur bel ow 400 cm - 1 and int o the far
infrared region. They are very ha rd to assign, since many ligand ring deformation
6-4 TI-
The posil
coorJ ina

offreedon
to Ira sil
int cratorr
x, y, and
molecule
three pri r
Thcrefo re
that resul
reprew/lt
3N - 6 de
energy inl
represC' ll tG
symmetry
the norm
Consequ
moleculm
according
center of I
the norrm
g l' l JI' ral riJ
Dile 01' I l
For (j
mode s. Th
6--4( B), wt
learer
ts
cussed
s being
'11 /J()I1/
li ras a
11uc'\car
le force
.islancc:
(6 - 4)
.rnuclear
:ed by lj,
blc bonds
general.
lhose for
un nlOstly
bove 2900
llow-mass
Icakcr and
10 2700
ccur in Ihe
unknown
lhe 1500 to
nlo the far
1cformation
and rocking vibrations as well as lattice modes (vibrations involving the whole
crystal) occur in this region.
As indicated by equation(6-3), the reduced mass is importantin determining
the frequency of a vibration. Ir, for example, a hydrogen bonded to carbon is
replaced by deuterium, there will be a negligible change in the force constant
but an appreciable change in the reduced mass. As indicated by equation (6-3),
the frequency should be lower by a factor of about 1/ 2. The frequencies for
C-H and C-D vibrations are proportional to [12 x 1/(12 + 1)r1/ 2 and
[12 x 2/(12 + 2)r1/2, respectively.Normally,avibrationinvolvinghydrogenwill
occur at 1.3 to 1.4 times the frequency of the corresponding vibration in the
deuterated molecule. This is of considerable utility in confirming assignments
that involve a hydrogen atom. The presence ofthe naturalabundance ofOc in
a metal carbonyl gives separate bands due to De o and 12e o stretching
vibrations in metal carbonyls (vide infra) because of the difference in reduced
mass. Use of metal isotopes also has utility in confirming the assignment 01
vibrations involving the metal-Jigand bond(l)
6-4 THE 3N - 6(5) RULE
Thepositionsofthe N atoms in a moleculecan be described by asetofCartesian
coordinates, and the general motion ofeach alom can be described by utiJizing
Ihreedisplacementcoordinates.Themoleculeissaid therefore, tohave3N degrces
offreedom. Certaincombination' oftheseindividualdegreesoffreedomcorrespond
lO translational motion of the molecule as a whole without any change in
interatomic dimensions. There are three such combinations which represent lhe
x, y, and z components of translalional motion, respectively. For a nonl inear
molecule there are three combinalions that correspond to rotation about the
Ihree principal axes ofthe molecule without change in interalomic dimensions.
Therefore,for a nonlinear molecule there are 3N - 6 norma! modes of [libra/ion
lhat result in a change in bond lengths orangles in the molecule. N ormal modes
represent independent selfrepeating motions in a molecule. They correspond to
3N - 6degrees offreedom thal, in the absence ofanharmonicit y,could take up
energy independently of each other. These modes form che bases for irredicuble
Since a molecule is fundamentally not changed by applying a
symmetry operation R, the normal mode RQ must have t he ame frequency as
Ihe normal mode Q. Thus, if Qis non-degenerate, RQ = 1{2 for all R's.
Consequently, Qforms (he basis for a one-dimensional representation in the
molecular symmet ry group. It can be shown (hat degencrate modes transform
according to irreducible representat ions ofdimensi nality.greater Ihan one.The
cente!" ofmass ofthe molecuJe does not change in the vi brations associ a(ed wit h
Ihe normal mode, nor is angular momentum involved in these vibral ions. AIl
oelleral vibrational motiol1 that a molecu/e may undergo can be resolved inCo eicher
Dile o,. a combination ol chese normal modf' !j .
For a linear molecule all che vibratiol1s can be resol ped into 3N - 5 normal
lIlodes. The additional mode obtained for a linear molecule is indicated in Fig.
6-4( 8), where pl ussigos indicate motion orth atoms ioto the pap r and minus
6-4 The 3N - 6(5) Rule 153
Vibrations in a
Polyatomic
Molecule
i
154 Chapter 6 Vibration and Rotat ion Spectroscopy : Infrared, Raman, and Microwave
(Al
Center 01
rotation
FIGURE 6-4 Rotational and bending
modes lar (A) non-linear and (B) linear
molecules.
+
+
B ------1. A - ---as
(B)
signs represent motion out ofthe paper. For th nonlinear molecule [Fig. 6-4(A)]
the motion indicated corresponds lo a rotation. F or a linear molecule a similar
motion corresponds 1 a bending of the bonds, and hence thi s molecule has an
additional normal vibrat ional mode (3N - 5 for a linear molecule vs. 3N - 6 for
a nonlinear one).
As will be seen later, lhere are many applications for which we need to know
which bands correspond to the fu ndamental vi brations.
6-5 EFFECTS GIVING RI SE TO ASSORPTION SANOS
Sulfur dioxide is predicted to have three normal modes fr om the 3N - 6 rule.
The spectral data (Table 3) show the presence of more tban three ba nds. The
three bands at 1361, 1151, and 519 cm - 1 are the fundam ntals and are referred
to as the v), VI ' and bands, res pectively (see Fig. 6- 5). The V symbolism is
used to label the various frequencies of fundamental vibrations and should not
be confused with the symbols v
o
, VI V
1
, etc., used to de ignate vari ous vi brational
levels of one mode in a molecule. By convent ion the highc t-frequency tot alIy
symmetric vibration is called VI ' the second highest totally symmetric vibration
V
1
, et c. When the symmetric ibrations have al! been assign d, the highest-
frequency asymmetric vibration is counted next, followed by the remaining
asymmetric vibrations in order of decreasing fr quency. An cxception is mad
to this rule for t he bending vibration of a linear molecule, which j labeled V
2
.
Another common convention involves labeling stretching vi brations v, bending
vibrations J, a nd out-of-plane b nding vibrati ons n. Subscripts, as, for asymmetric;
s, for symmetric; and d, for degenerate, are empl oyed with t hese symbols.
The VI mode in S02 is described as the symmetric stretch, v) as the asymmetric
stretch, and V
2
as the O-S-O hending mode. In general , the asymmetri c stretch
wil l occur at higher frequency t han t he symmetric slretch, and tretching mod s
occur at much higher frequencies than bending modes. There i a slight angl e
change in lhe stretching ibrations in order f r th molecule to retain it' center
of mas . The other absorpt ion freq uencies in Table 6-3 are assigned as indicated.
The overtone of VI occurs at a bo ul 2v
1
or 2305 cm - l . The bands al 1871 and
2499 cm - 1 a re refe rred to as combinaton bands. Ab orption of radiation of these
V
2 n
TABLE 6-3. Infrared
Spectrum of S02
\' (cm-
1
) Assillnmenl
519 v
2
606 VI - v
2
1151 v
1361 V
3
1871
"2 + v 3
2305 2v
2499 V + v
3
Jo.
O
O
/
O f c ~
V
+
6-5 EHecls Giving Rise lo Absorplion Bands 155
t
~ s ~
s
/s",
o o FIGURE 6-5 The three
~
O
/
0)1 .O
fundamental vibrations lor
k'
O
sullur dioxide (The
amplitudes are exaggerated
S
S
to i IIustrate the motion.)
"
O
/ 1"
O
.,.
O
/ ~
O
~ \
.. ':, ~
V
1
V
3
V2
energics occurs wit h the simul taneous excitation of both vibrational modes of
the combination. The 606 cm - 1 band is a difference band, which involves a
transition origi nati ng from t he state in which the v
2
mode is excited and changing
to that in which t he V I mode is exci ted. Note t hat all the bands in the spectrum
are account ed for by these assignments. Making the assignments is s ldom t his
simple; as wi ll be shown later, much other information, incl udi ng a nonnal
coordinate analysi s, is requi red to substanla te t hese assignments.
A more complicated ca e is the CO
2
molecule, for which four fundamentals
are predicted by t he 3N - S r uJe. A single band results fr om lhe two degenerate
vibrations V
2
of Fi g. 6, which correspond to bending modes at right angJes lo
each other. Laler we shall see how symmetry considerati ons aid in predicting
the number of degenerate bands lo be expecled. In more complex molecules some
of lhe fundamentals may be accidentall y degeneratc beca use two vi brat ion
fr equenciesj ust happen to be equal. This is not easily predicted, and the occurrence
of this phenomenon int roduces a serioll s compli cati on. The assignmenl of Ihe
flln damentals for CO z i more difficult lhan fo r S02 beca use many more bands
appear in lhe infrared and Raman spect ra. Bands at 2349, 1340, and 667 cm - 1
have been assigned to V}, VI ' and V
2
' respectivel y. The t ts of these assignments
have been descri bed in detail by Herzberg (see Additional References) and will
not be repeated here. In this example t he fundarn ntal s are the th ree rnost in tense
bands in the spect rurn. In sorne cases, there is only a srnalI di pole moment change
in a fundament al vibration, aod t11e corresponding absorpti on band is weak (see
the first selecti on rule).
The aboye discussion of the band at 1340 cm -1 has been sirnplified. ActuaJly,
it is an intense doublet with band maxima al 1286 and 1388 cm - 1. This splitting
is due lo a phenomenon known as Fermi resonance. The ov rtonc 2v
2
(2 x 667 = 1334 cm - 1) and lh fundamental VI should occur at a1most the sarne
t t
o- c- o
"j..
FIGURE 6-6 Carbon dioxide
fundamental vibrat ion modes.
O- c-o
+
VI V2 V3

156 Chapler 6 Vibration and Rotation Spectroscopy Infrared, Raman, and Mi crowave
frequency, The two vibrations interact by a typical quantum mechanical
resonance, and the frequency of one is raised while the frequency of the other is
lowered. The wave function describing these states corresponds to a mixing of
the wave functions of the two vibrational excited states (VI and 2v
2
) that arise
from the harmonic oscil/ator approximation. \Ve cannot say that one line
corresponds to VI and the other to 2v
2
, for both are mixtures of VI and 2v
2
. This
interaction also accounts for the high intensity of what, in the absence of
interaction, would have been a weak overtone (2v
2
). The intensity of the
fundamental is distributed between the two bands, for both bands consist partly
of the fundamental vibration.
The presence of Fermi resonance can sometimes be detected in more complex
molecules by examining deuterated molecules or by determining the spectrum
in various solvents. Since the Fermi resonance interaction requires that the
vibrations involved ha ve nearly the same frequency, the interaction wil! be affected
if one mode undergoes a frequency shift from auteration ol' a solvent effect while
the other mode does not. The two frequencies wi ll no longer be equivalent, and
the weak overtone will revert to a weak band or not be observcd in the spectrum.
O ther requirements for the Fermi resonance interaction will be in the
section on symmetry considerations.
6--6 NORMAL COOROINATE ANALYSES ANO BANO
ASSIGNMENTS
Degeneracy, vibration frequcncies outside the range of the instrument s, low
intensity fundamentals, overtoncs, combination bands, difference bands, and
Fermi resonance all complicate the a signment of fu ndamentals. T he problem
can sometimes be resolved for simple molecules by a technique kno wn as normal
coordinate ana/ysis. Normal coordinate analysis in volves solving the classical
mechanical problem of the vibrati ng molecule, assumi ng a pa rticul ar form of the
potential energy (usually the valence force fi eld), The details of this calculation
are beyond the scope of this text.(2,3) but it is informat ive to outline the problem
briefty so the reader can a ss the value and the limitations of the approach.
Furt hermore, severaJ importanl qualitative ideas will be developcd that we shall
use in subscquent di cussion. When we have fi ni hed, you will not know how to
do a normal coordinate analysis, but hopefully you will have a rough idea 01
what is invol ed.
Just as the electronic energy and electronic wave fu nctions of a molecule arc
rela ted by a secular determinant and secular equations (Chapter 3), the vi brati onal
energies, vibrational wave funcl ions, and force constants are related by a secular
determinant and a series of secular equations. The vibrat ional secular determinant
will be given herc as (for the derivation see referenL:cs 2 and 3):
F
I2
- (G-
I
)J2A .... F In --:- (G ILn)'
= 0
Here i.
th' G;.
is knO\\
modc' t
cOllnter
e ordin
L. Thr'
molccult
i cOlllrl'
ca n r
UI b n
bond an
comhUla
vlbration
fhc
n:(.:rencc: l .
Dlex
rum
the
Fted
vhile
amI
um.
1 the
S, lo\V
s, and
'oblem
!1ormal
lassieal
1 of lhe
ulatiol1
foblem
proach.
,ve shall
ho\V to
idea of
~ u l e are
ralional
1 secular
:rminant
EH; Normal Coordinate Analyses and Band Assignments 157
Here i, = 4rr
2
v
2
, where v is the vibrational frequency (note the resemblance of
this GJ, term to the energy term in a molecular orbital ca1culation); this quantity
is known, for one begins by making a tentalive assignment of al! the normal
modes to the ba nds in lhe spectrum. The basis sel for t his calcula lion (i.e .. lhe
counterpart of atomic orbit als in an m.o. caIculation) is [he set of internal
coordinates of the mo[ecule expressed in terms of 3N - 6 ato m displacements,
L. Three such coordinates. needed to descri be lhe normal modes for the wate r
molecule, are ill ustrated in Fi g. 6-7. The selection of these intem al ccordinales
is complicated in larger highly symmetric molecules beca use redundant coordinates
can result. Onc proceeds by el ecting an internal displacement vector for a change
in bond lcnglh for each bond in the molecule and then selecting indepelldclll
bond angles lO give the 3N - basis set. The normal mode is going to be some
combination of this basis sel of intern al di splacement coordinates, and the
vibrational wave funetion will teH us what this combination will be (again note
the resembla nce of this to an elcet ronic wave function for a molecule consisting
of lhe atomie orbit al bases set). In lhe secul ar determinant given aboye, F II is
the force constant for 'lretchi ng the O- H bond along L
II
, F21 is the fo rce
const ant for stretehing along L
22
, and Fa is related to the b nd along Lo. T he
off-diagonal element F2 1 in the vi brational secula r d terminant is called an
inreraclion{orce constant, and it indicates ho the lwo isolated sl retches interact
with one another. When. for example, L
22
is subjected to a unl di placemenl,
the bond along t
ll
wi U di tort lo minimi ze the potential energy of he strained
molecu le. F2 1 is roughly proporti onal to the displ acement of the bond along L
22
resulti ng fr om minimi zation of the energy of the molecule after di splacemenl
along L II ' Part of lhe interaction relales to h w Ihe bond strengt h along L
22
changes as the oxygen rehybridizes whcn Ihe bond along L 11 is st retched. f i) is
not necessarily identical to Pji'
The F-matrix el emcnts accounl for lhe potea ti a! energies of the vi bral ion.
The G-rnatrix el cments contain informati on about the kinetic 'nergy or the
molecule. The latter can be wri lten exactly for a molecule from fo rmulas given
by Wilson, Decius, and Cross(21 if we know the at om masses, the molecular bond
di stances. and Ihe bond angles.* This is a symmetric rnatrix. In practice, the: fo rce
constants are usually lhe only unknowns in the secula r determinant. and they
can be determined. (Now the problem differs from the format of lhe molecular
orbita l calculation.)
The secular determinanl giv n aboye can be wrilten in matrix notation as:
lf we multi ply by G we gel
IGF-Ei , I =O
5)
*1' l1c cV lualion of Ihe e-matri, ror a hcnt XY2-m olecuk has bcC' n workcd oul in detai l in
rcfcrence 18, S<:ct ion 1-11. The rcadcr is rdcrred to Ihis treat menl ror furtl1er details.
FIGURE 6-7 Internal
coordinates for the H
2
0
molecule.
158 Chapter 6 Vibration and Rotation Spectroscopy: Infrared, Raman, and Microwave
where E is the unit matrix. Furthermore, the G matrix has the property that the
),'s in the off-diagonal elements of the previous secular determinant have been
eliminated. The problem now is to solve
1 ... O
o
), = O
O
G"" F"I F""
where the G elements are all known, as are the ):s. There are in gen ral n values
of ), that satisfy this equation, and they are known. The d ifficulty with normal
coordinate a nalyses on most molecules is that there are more unknown force
constants than there are frequencies. F or the water molecule, the force constant
matrix is 3 x 3, and there are four un knowns* for the three frequencies. If one
deuterates the water molecule, new frequencies are obtained, but no new force
constants a re introduced. The
16
0,
17
0, and'
18
0 molecules could also be stud ied .
. The problem here is whether r not t he new equations we obtain in tTying to
get more simultaneous equations than force constants a re di ffe rent enough to
allow for a un ique, meaningful solution. (This is simi la r to the K -
1
vs. e problem
discussed in Chapter 4. Two parallel or nearly parallel equations do not solve
the problem, even though in the latter case a computer can pick a minimum.)
I n the simpler molecules, this is oft en not a pr oblem; but in more complex
molccules, t he analysis is not to be believed unless errors a re reported and some
statistical criteri on of the significa nce of the fit i presented. T his is readily
accomplished wit h a correlation matrix that indicates how extensively the
individual force constants are correlated. This problem is potentiall y so severe
that one should no! accept the results from a force co nstant analysis unless the
correlation ma trix is reported.
Suppose we were to d o a normal coordi na tc a nal ysis for Mn(CO)sX. We
would have 30 internal displacement coordinates (3 N - 6) a nd a 30 x 30 force
constant matrix, or many force conslants. Symmetry can red uce this mat ri x to
smaller blocks by requiring certain int eraction consta nt s to be zero (vide i/llra),
but there remain se eral a pproxi mations that must be introduced to solve the
problem. I n one analysis of t he problem, one could ass ume that lhe carbo nyl
stretches are so far removed in fr eq uency fro m any of t he ot hcr vibrations that
they can be treated separa tely.(4) This is eq ui val ent to claiming t ha t the
metal-carbon stretch does not in Au ence the c- o vibra tion and setting all
interaction constants of the e o stretches with a nything elsc equal to zero. Thi
leads to a 5 x 5 block for [he total secul ar detcrmina nt of force constants. Isot opi c
substitution is then cmployed to sol ve the problem. In a more l horough analysis,(5 )
the interaction con tants between M- e and e- o strelch coordinates that are
trans to each other ha ve beeo determi n d and foun d to be significant.
eott on a nd Kra ihanzel (4) have proposed a erude approximation for these
systems. They arbitraril y set any interaetion for ce cons ta nt F for carbonyl
trOflS
moieti s that are t rans lo one a not her equal to 2F
s
where F
Cls
correspond to
interaet ion conslants involving groups Ihat are cis. The numb" rs of unknowns
and freq uencies become comparable in many carbonyl compounds when this is
do ne. Jones (S ) has carried o ut a more rigorolls evaluation of t hi' problem and
The symmetry of the water molecule leads lo this.
In the
The firs
If
be 1 :< I
where ti
Rea r r n
01'
The resel
see why
diatomic
We
6-6 Normal Coordinate Analyses and Band Assignments 159
suggests that severe limitations be placed on systems for which the Cotton-
Kraihanzel approximations are invoked. Jt has been shown in the more complete
study that F
eis
is considerably larger than F
trons
' Another approach that is being
investigated to facilitate normal coordinate analyses involves transferring inter-
action force constants from a simple molecule, in which they are well known, to
larger, similar systems.
Let us next consider a simple system, which we assume to have been sol ved
for meaningful force constants. The force constant values can be substiluled into
the G and F matrices previously given, and the secular equations are now writtcn
by multiplying by a matrix of the basis set L, the internal displacements; i.e.,
IG F - E}'n I I L I = O (6-6)
Jn the case of water, F is 3 x 3, G is 3 x 3, E is 3 x 3 unit mal ri x, L is 3 x 1
(L, L
22
, and L
33
), and }' Il is the eigenvalue for which we wish to determine the
normal mode. The energics are now substituted one at a time. Ma t rix multiplicat ions
then yield the contribution of the basis set (i .e., the contribution of the individual
internal displacements) to the vibrational wave function for the normal mode
corresponding lO that frequency. This is done three times for the wate r molecule
with the three frequencies, leading to the wave functions for the three normal
modes.
For the water molecule, the wave functio ns for t he 3N - 6 vibrat ions are:
!J = Nt
o
+ N'(L + Ld N N'
!J2 = N(Ll + Lnl + N' L
o
1
!J3= - (L -Ld
2
Thc first two have Al symmetry, and the last has B1 symmetry.
Ir we had a diatomic molccule (e.g., HCl), al! of the abo ye matrices would
be 1 x 1 and we would have from equation (6- 6)
where the G matrix element is the reduced mass and F
1
is the only unknown.
Rcarranging, we scc that
F 2 2
-- = 4n v
I1HC
01'
rr::-:
(6-7)
v V ~
Th resemblance of thi s re ult to cquat ion (6- 3) is clear for AE = hv. No w we
see why equat ion (6- 3) can be used to gi e lhe force cons tant [or a bo nd in a
diatomic molecule but not in a more complex molecule. [n la rger, more complex
I
-c
160 Chapter 6 Vibration and Rotation Spectroscopy : Infrared, Raman , and Microwave
molecules, the observed frequency corresponds to a morecomplex vibration tha t
depends upon several bond force constants. The results ofa normal coordinate
anal ysis producetheforce constantsandindicateexact ly Iheform of each normal
mode in terms of the internal coordinates. For wat er. for example, the internal
coordinates in Fig.fr.7arecombined to produce normal modes that aresimilar
in form to those shown fo rS02in Fig. 6--5. This is expected becau e l he inlernal
displacement coordinates (which a re of the same form for SOz and HzO) can
fo rm the basis for producing a total representation by employing the symmetry
operations of the point group on t hem. Factoring the total representa tion
produces the symmct ry ofthe irreducible represen tat ions, which in thi s case are
the normalm des. For the water molecul , lhe total representa tion obla ined by
opera ting with the CZl' point group on the internal displacements shown in Fig.
6-7 is 3 1 3 1 (t he a ngle () is not changed by () l' or Cl ). Facloring the total
representation produces 2AI + Bl Next, projection o perators can be used on
this basis seljust as on a n a.o. basis set to produce
P(A I)L
ll
;;:; t
l
+ L
22
P(AI)Lo ;;:; Le 8)
P(B I)L
II
;;:; L II - L
22
T his problem nicely illust rates t he analogy bet ween t he symmetry aspects ofl he
mol ecular orbit a l problem and those of the vibrat ional pro blem.
T he inverse of the force consta nt matrix produces a mat rix of compliance
constant s(6)A di agonal complia nce consta n! is a measure of t he di splacement
that will take place in a coordinate as a result of a force imposed upon this
coordina te, ifthe othercoordina tes areall owed to adj ustto minimize t he energy.
There a re reported advantages to employing compl iance conslants io'tead of
force constants, and the reader is referred to the Iiterature fordet ail s,(6)
6-7 GROUP VIBRATIONS ANO THE LlMITATIONS OF
THIS IDEA
The idea that we can look at Ihe spectrum ofa complex molecule and assi gn
bands in Ihe spectrum to various functional groups in the mol ecule is callcd the
group vibration concept. This approach arose from the experi mental observation
thatmanyfuncti ona lgroupsabsorbina narrowregi onofthespectrumregardless
of the molecule Ihat conta ins th group. In the acetone molccule,* for example,
oneofthe normalmodes of ibral i n consists ofa e- ostretchingmolion wit h
negligiblemoti anoft he othera toms in themolecul e.Simila r/y,themet hy!groups
can be consi dered to undergo vi brati ons Ihat are independent ofthe moti on ' of
the ca rbonyl group. I n var ious mol ecules it is found Ihat carbonyl absorptions
d ue to the stretchi ng vibration occur in roughJy t he same spectra l region
1700cm- 1). As wil! be seen in the sect ion onapplicat ions, lhe posi ri on ofthc
band does vary slight ly (150 cm-
I
) because of the mass, inducti ve, ane!
conjugat iveeffectsofthe attached. Themethylgroup hasfi vecharacteri sl ic
*This molccule has analyzed by a normal coordinate Ireatment.

and S)
aroun<
ROO crr
vibrat i
more I
groups
Uofort
that 0\
possibl
cause
trelchl
assi gnn
spectru
solutes.
Th
incorrel
\ibrat ic
rclati\'
movc, t
harmon
Ihedlsc
\\i fl oc
(lf lh in
gmup,
when tl
combim
displa;
BI aS}rt
displ ac
illll.! ractl
nol mix
be lreab
m ewl
the 5 x
Wh
honds
lal
itc
lal
lal
lar
nal
:an
:try
ion
are
lb
rig.
olal
I on
6 Xl
Ir he
Ullce
'ffient
1 this
1crgy.
'ad of
assign
\ed the

,ardless

)11 with
groupS
tio ns of
Irptions
region
n uf the
ve, and
lctcristic
6-7 Group Vibrations and the Limitations of This Idea 161
absorption bands: two bands in the regio n from 3000 to 2860 (from the asymmetric
and symmetric stretch), one around 1470 to 1400 (the asymmetric bend), one
around 1380 to 1200 (the symmetric bend), and one in the region from 1200 to
800 cm -) (the rocking mode, in which the whole methyl group twists about the
C-C bond, undergoing a rocking-chair type of motion). The concept of group
vibrations involves dissecting the molecule into groups and assigning one or
more bands in the spectrum to the vibrations of each group. Many functiona l
groups in unknown compounds have been identified by using this assumption.
Unfortunately, in many complicated molecules there are many group vibrations
that overlap, and assignment of the bands in a spectrum beco mes difficult. It is
possible to perform experiments that help resolve this problem: deuteration wil!
cause a shift in vibrations involving hydrogen (e.g., C- H, O-H, or N-H
stretches and bends) by a factor of 1.3 to 1.4; characteristic shift s, which aid in
assignments, occur with certain donor functional groups (e.g. , C= O) when the
spectrum is examined in hydrogen-bonding solvcnts or in the presence of acidic
solu tes.
The limitations of the group vi bration concept should be emphasized so that
incorrect interpretat ions of infra red spectral data can be recogni zed. The group
vibration concept implies that t he vibrations of a particular functional group are
relatively independent of the rest of the molecule. If the center of mass is not to
move, this is impossible. AII of the nuclei in a molecule must undergo their
harmonic oscillations in a synchronous manncr in normal vibrations. In view of
the discussion in the previous section, we can see that the group vibration conccp
wil! be good when the normal mode wave function consists largely (80 to 90 %)
ofthe internal displacement in which only the group is involved, i.e. , the fun ctional
group vibration is the main internal dis placement coordinalc. This wi U occur
when the symmelry properties of lhe molecule are su eh as to restri et the
combination of the internal displacemcnts of the group with ol her int ernal
displacement coordinates; e.g., Lo in the water molecule cannot contribute lO the
Bl asymmetric stretch. When the vibrational mot ions invol vi ng the Iwo internal
displacement coordinates are very difrerent in energy, then the off-diagonal
interaction constants are smal!, t he two internal displacement coordinates are
not mixed extensively in the vibrat ional wave functions, and the vibrations can
be treated separately as group vibrations. Thi is equi valent to the assumption
made when we treated the ca rbonyl vibrations in M(C lsX separate!y to obtain
the 5 x 5 matrix.
When the atoms in a molecule are of similar mass and are connected by
bonds of comparable strength (e.g., al! single bonds as in BF)' NH)), al! the
normal modes will be mixt ures of severa! interna! displacement vectors. For
example, in BF3' NH
3
it would be impossible to assign a band to the B- N
strelching vibration beca use none ofthe normal modes correspond predominantly
to this sort of motion. When this occurs, the various group vi brations are said
to be coupled. Thi s term si mply describes a situat ion in which the very crude
group vibration conccpt is no! applicable to the descripti on of lhe normal mode
correspondi ng to a pa rticul ar absorption bando Thi s discussion shoul d be reread
if the reader cannot dis tinguish coupling from lhe phenomena of Fcrmi resonance
or combinalion bands.
The HCN molecule is interesting to conside r in the contexl of the aboye
discussion. The frequencies of a pure C- H and pure e- N stretch are si milar
in energy. The C- H and e- N group st retchi ng vibrat ions in lhe H- C- N
162 Chapler 6 Vibration and Rotation Spectroscopy . Infrared, Raman, and Microwave
Raman
Spectroscopy
molecule are coupled. The absorption band attributed to the C-H stretch actually
involves C-N motion to some extent and vice versa; Le. , l he observed frequencies
cannot be described as being apure C-H and apure C-N stretch. Evidence
to support this comes from deuteration studies, in which it is found that
deuteration affects the frequency of the band that might otherwise be assigned
to the C-N stretch. This absorption occurs at 2089 and 1906 cm -1 in the
molecules H-C-N and 0 - - N, respectiveJy. Equa tion (6- 3) would predict
that deuteration should have very lillle effect on the C-N frequency, for it has
little effect on the e -N reduced mass. The onl y way the freque ncy can be a ffected
is to have a coupling ofthe C-D stretch with the C-N stretch. Upon deuleration,
the C- H stretch at 3312 cm lis rcplaced by a C- O strctch at 2629 cm- l.
Si nce the C- D frequency is c\ oser to the C-N frequency than is t hat of C- H,
there is more ,-xtensive coupling in the deuterated compound. Because the
symmetries of the normal modes differ, the C- D bending vibration does not
couple wi th the " C-N stretch."
It wo uld be improper to draw conclusions concerning the strength of the
C- H bond from compa rison of the frequency for the C- H stretch in H- CN
with data for other C- H vi bra tions. The force constant s fo r the C- }-] bonds
can be calcuJated for the va rious comp unds by a normal coordinate ana lysis.
T hese values should be employed for such compa risons.
As anot her exampi of the difficulties encountered in lhe i nterpretation of
frequencies, consider the stretchi ng vibration for some carbonyl groups. Abso rp-
tion bands occur at 1928, 1827, a nd 1828 cm-[ in F
2
CO, Cl zCO, and Br2CO,
respectively,P) One might be tempted to conclude from the frequencies Ihat t he
high electronegal ivily of fiuor ne causes a pronolloced increase in the C- O fo rce
consta nt. However, a normal coordi nate analysi (7) shows that t he C- and
C- F vibrations are coupled and t hat t he c- o stretch also in volves considera ble
C- F motion. The frequency of ths normal mode is higher tha n would be expected
for an isol at ed c- o slretching vibrat i n wit h an equiva lent fo rce cons ta n!. T here
is a corresponding lower ing of the C- F st retchi ng freq uency. Since chlorine and
bromine are heavier, they make little contri bution to Ihe carbonyl stretch. The
normal coordinate anal ysis ind icates that the c- o stretching fo rce constants
are 12.85,1 2. 61, and 12. 83 miJLid ynes/ in F 2eO, Cl
2
eO, a nd Br 2CO, rcs pect ively.
A normal coordi nate analysi s and infrared st ll dies of 2C -, 13C_,
16
0 _,
18
0 _,
and H and D-sll bsti tuted ket ones conta ining an et hyl group a ltached to Lhe
carbonyl group indicate(8) that the band near 1750 cm - [ assigned to the C- O
slretch in these ketones corresponds to a normal mode t hat consis ts of about
75 % e- o and 25 % C- C st retching motions. These exam pl es should be kept
in mind whenever one is tempt ed to int erpret the frequencies of infra red ba nds
in t rms of eleclronic efTects. Force constants obtai ned from normal coo rd ina le
anal yses should be compared; frequencies read direct ly from spectra ' hould not
be. Unforlunately, reliable force constan ts are in limited supply,
6-8 INTRODUCTION
Raman spect roscopy is concerned with vibrational and rotat io n,al transitions,
and in t hi respect it is ' imilar to infrared spectroscopy. Since lhe 'elecli on rules
are different, t he informat ion obtained from the Raman spect rum often comple-
ments
in form
In
sample
inciden
can b
hol d r
m ust b-
r a e
decoml
minimi
a Ji nc
and 51
l he Kr
has eXI
bandpa
gho ts,
in rerer
Stokes
line

o
l ' -
on "
on rules
comple-
Laser
source
FIGURE 6-e The Raman
experiment (schematic) .
m ots that obtained from an infrared study and provides valuable structural
information.
In a Raman experiment, a monochromalic beam of lighl il lumina les Ihe
sample, and observa tions are made on Ihe sca tlered Jight at righl a ngle. to lhe
incident beam (Fig. 6-8). Monochromat ic light sources of differ nI freq uencies
can be employed; gas laser are comm nly u ed for t his purpose. Va rious samplc
holder configurati on are employed(9J ; the only requirement is tha t the detector
musl be al right angles to the source. This configuration is ill ust ra ted in Fig. 6.... 8
for a capillary cel\. Absorpt ion of the monochromat ic ligh t beam, leadi ng to
decomposi tion, can be a problem, as can fluorescence. These problcms are
minimized by choice of an appropriate gas laser(l OJ line: the He-Ne laser gives
l line al 6328 (red) ; t he Ar laser gives li nes at 4579. 4658, 476 , 4880, 491 5,
and 5145 A(blue-green) (the Ar + 4880 Aand 5145 Alines are usuall ti ed) ; a nd
lhe Kr laser givcs 5682 a nd 6471 lines. T he inlroduction of tu na bl e dye laser
has extended Ihe range of ti' abl v lengths even further. U'e of a narrow
bandpass fi lt er for each laser lin reduces effects from the largc number of laser
ghosts. A val uable discu si on of variOllS aspects of this experiment is contained
in reference 1 l .
Center of a
broad
Rayleigh
line
v !
u
FIGURE 6-9 Lines observed in a
Stokes Ant i-Stokes Raman spectrum (schemati c).
line line
<-
I
I I
vO-vv 11 VO+l1
v
Increasing v
164 Chapter 6 Vibration and Rotation Spectroscopy. Infrared, Raman, and Microwave
We should wonder how we obtain vibrational transitions when we employ
a visible or u.v. source. A quantum of the incident light of frequency V
O
and
energy hvocan collide with a molecule and be scattered with unchanged frequency.
This is referred to as Rayleigh scattering. The mechanism involves inducing a
dipole moment, D, in the molecule when it is in the field of the electric vector of
the radiation. The electrons in the molecule are forced into oscillations of the
same frequency as the radiation. This oscillating dipole radiates energy in all
directions and accounts for the Rayleigh scattering. Ir the photon is actually
absorbed in the process and re-emitted, this is fluorescence. The difrcrence between
scattering and fluorescence is thus a subtle one, having to do with the 1ifetime
of the species formed in the photon-molecule collision.
The scattering process jusl described corresponds to an elastic collision of
the molecule with the photon. Raman scattering involves an inelastic collision.
The molecule in its ground vibrational state accepts energy from lhe photon
being scattered, exciting the molecule into a higher vibrational state, while the
incident radiation now beco mes scattered wit h energy h(vO - vJ In the Raman
spectrum of the scattered li ght measured at right angles, we now detect a frequency
V
O
- vv' called the Stokes line, as shown in Fig. 9. The measured value of Vv is
identical to the infrared frequency that would excite this vibrational mode if it
were infrared-active.
A molecule in the vibrationally excited state v = i can collide with an incident
light quantum of frequency vo. The molecule can ret urn to the ground state by
giving its additional energy hv
v
to the photon. This photon, when scattered, wiIl
have a frequency V
O
+ Vv' The spectral line with this fregu ncy in the Raman
spectrum is referred to as an anti-Stokes li ne (see Fi g. 6-9). Because of the
Boltzmann distribution, there are fewer molecul es in t he v = 1 state than in v = O,
and the intensi ly of lhe anti-Stokes li ne is much lower than that of the Stokes lineo
80th Rayleigh and Raman scattering are relati vel y inefficient processes. Ooly
about 10-
3
of the intensit y of the incident xciting freq uency will appear as
Rayleigh scattering, and only about 10-
6
as Raman scattering. ~ a result, ery
intense sources are required in thi ' xperimcnt. Laser beams pro vide the required
intensity ~ 1 0 0 milliwalls to ~ 1 watt of power) and produce good spectra even
with very small samples.
6-9 RAMAN SELECTION RU LES
Th molecule interacts with electromagnetic radiation in the Raman experiment
via the oscillating induced dipole moment or, more accurately, the osci ll ating
molecula r polarizabil ity. The intensit y, 1, of the scatlered radiation, v
s
' is a function
of lhe polarizability, (Xii' of lile molecule which, for a randomly oriented solid, is
given by:
(6-9)
where lo is the iotensity of the incident radiaton and (Xij is an element of lhe
molecular polarizabi lly tensor. Molecul ar polarizability can be represented by
an ellipsoid; the change in polarizabil ity (as the CO
2
molecule, for example,
undcrgoes the symmetric stretch) can be schematicaIly iUustrated as io Fi g. 10.
syrr
stre
disl
con
POl
e l l l ~
RGl
displ
doull
x, (el
to\\'a
dipol
E lhe
Thc r
in th(
In mI
mol,
fiel d ~
D,.,ar
( ce F
malril
lhe fo
y
d
y.
a
of
he
atl
lIy
.en
me
unelion
solid, is
(6- 9)
6-9
symmetr ie
stretching -o . c I o- z ~ o _ e O- Z
displacements
(extended) (equilibrium)
corresponding
polarizability
ellipsoid
z
FIGURE 6-10 The ehange in pol ari zability lor the CO
2
moleeule lor various
displaeements 01 the atoms dur ing the symmetrie stretehing vibration. The
double-headed arrows in the ellipsoid ind ieale (a) Ihe z-axes 01 the ellipsoid, (b) Ihe
x, (e) the y, and (d) the xz.
When a molecule is placed in a static eleclric field, l he nllclei a r . attracted
toward the negative pole and lhe eleetrons toward the posi t i e pole, inducing a
dipole moment in t he molecule. If D repr S nts the ind uced di pole motu nt and
E the electrie fiel d, the polarizabi li ty !X is deft ned by the following quation :
D = :lE (6- 10)
The magnitude of this polarizabil ity depends upon lhe ori entali on of l he bonds
in the molecule wi th re pe 1 to the electric fi eld direeti on ; i.e. , it is ani sotropic.
rn most moleeules it is a tensor quant ity. The indueed dipole moment in the
moleeule wi U depend upon t he orienta tion of lhe m lecule with respeet to the
fi el d and, si nce lhe dipole momen! is a eetor. it wi lJ have t hree eomponents Dx.
Dy. and Dz. The polarizabili ty tenso r can be represented phy icall y as an ell ip oid
(see Fig. 10), and it has nine components thal can be d scrib d by a 3 x 3
malrix. The ind ueed dipole moment re related to the polarizabiJity tensor by
the foll owing eqllations :
Dx = cxxx Ex + cxx)"Ey + cxHE;
Dy = cX)' X E, + a ),J' Ev !XJ'= Ez (6- 11 )
D;: = cxzxEx + cxzyEy + IY.;zE,
Raman Selection Rules 165
---o e o- z
(compressed)
z
166 Chapter 6 Vibration and Rotat ion Spectroscopy : Infrared, Raman, and Microwave
These equations state that if we locate a molecule in an electric field so that the
ellipsoid axes point between the Cartesian axes, then the x-component of the
induced dipole moment will depend upon the magnitude of the electric field aJong
the y-axis beca use lhere is a polarizability component along xy that can interact
wit il Ey and make a conlr ibution to the change observed along x. The same is
true for the interaction of Ez with axz . Equations (6-11) can be written in matrix
form as
For an optical1y inactive molecule, the a tensor is symmetric and
If we choose a proper set ofaxes, we can carry ou t a transformation that
diagonalizes the tensor previously given. The new axes are called the principal
axes of the pola rizabil ity tensor wit h components ax,x " a y, y" and cxz ' z ' whose trace
is egual to that in the previous coordinate system.
Quanl um mechanically, the polarizabil ity of a mo1eculc by elect romagnetic
radiation al ong the di recl ion ij is given by
(6-12)
where m and n are the init ial and final tates of the molecule a nd e r presents
an excited state. Mi and Mj are electric dip le tran itio n moments along i and
j , whereas ve is the energy of the transition to e and V
o
and V
s
are the frequencies
of the incident and scattered radiat ion.
A previously mentioned, the select ion rules for Raman spectroscopy are
di ffer nt from those for illfrared. In order fo/' a vibration to be Raman-active, the
change in polarizability of the molecule \',Iith res pect to vibrational motion must not
be uro at the equilibriul/1 position of the normal vibration; i.e.,
~ a ) *O
(6-13)
er r e
where IX is t he pola rizabil ity and r represents the distance along the no rmal
coo rdinate. If lhe plOl of p lariza bi li ty, a, versus distance from t he equili brium
dist ance, re' al ong the nonnal coordi nate is that represenled by ig. 6--11(A), the
ibration wi ll b Rama n active. If the pl Ol i represenled by the curves 1 or 2 of
Fig. 6-- 11(B), Da/ /' will be zero al Or near th equilibrium distance, re' a nd t he
vibral ion will be Raman-inactive.
Small amplitudes of vibralion (as are normaJly encountered in a ibrat ion
mode) are indicated by the region on t he distance axis 0 0 each side of zero a nd
bet ween the dotted li nes . As can be seen from Fi g. 6--11, the vibration in (A)
FIGUR
hypoth
6-9 Raman Selechon Rules 167
Ing
acl
: is
:rix
Ihal
cipal
trace
:nclic
16- 12)
'esenls
! i and
lencies
'py are
ve,lhe
IIlsl 1101
(6-- 13)
normal
librium
the
or 201'
and the
'bration
and
in (A)
1 A I
I I
1
1
I
1
I I,
\1(
2
: I:
-----, -------
-- ---
, 1 :
,l '
I
I ! \1
1
I
1
I
I
I
1
+ +
distance r distance r
(A)
(B)
FIGURE 6-11 Polarizability as a lunction 01 distance lorsome
hypothetical molecules.
corresponds to an appreciable change in polarizability occurring in this regi on,
while that in (B) corresponds to practically no change. Hence, the Raman selcction
rule (6-13) is 01'ten stated : In order for a vibration to be Raman-active, there must
be a change in polarizability during the vibration.
The completely symmetric ,lretch ror CO
2
is represented in Fig. 6-10. T he
points labeled A and e in ig. 6- 11(A) corre pond to extreme stretchi ng of t he
bonds ror the symmetric stretch. A and e represent, respectively, more and less
polar izable t ructures than th quilibrium st ructure. A plot of IX versus r for the
symmetric slfetch is representcd by Fig. 6-11(A). T he change in polarizability for
the asyrn met ric stretch is represented by one of t he curves in Fig. 6-11( 8). As a
resLJlt, this vibration is Raman-inactive. Infrarcd aClivity is j ust the opposite of
Raman activity in this case. In general,for any molecule that possesses a center
uf symmetry, there will be no fu ndamental lines in common in the infrared and
Raman spectra. This is a very valuable generalization for st ruct ure d terrnination.
Ifthe same absorpt ion band is found in both the infra red and Raman spect ra
it is reasonably certain l hat the mol cul lacks a cenler of symmetry. It is possible
that in a molecule lacking a center of symmetry no identicallines appear because
of the low in tensity of one ofhe corresponding li nes in one of the spectra.
This discussion serves to iJJ ust rate quali tativel y the sclection ru les for Raman
spectroscopy. Itis oflen di fficult to tell by inspection the forrn of t he polarizabili ty
curve for a gi ven vibration. As a result, th is concept is more difficul t lO ut ili zc
qualitatively Ihan is Jle dipole momenl scJectio n rule in nrrared. In a later section
it will be shown how character tables and s mmet ry arguments can provide
information conceming the infrared and Raman activi ty of vi brati n . For now,
we summarize the aboye discus ion by stati ng that in order for a vibratio n to
be Raman active, lhe shape, size, or orientat ion of the elli psoid mu t change
during lhe vibration, as shown in Fig. 6-11(A).
168 Chapter 6 Vibralion and Rolali on Speclroscopy : Infrared, Raman , and Microwave
z
v
Oscillating induced
dipole
~ ~ ~ ~ ~ ~ _ ~
x
z
FIGURE 6-12 Raman scattering 01 yz plane-polarized radiation producing an
xz-polarized scattered wave when the polarizability is isotropic.
6-10 POLARIZEO ANO OEPOLARIZEO RAMAN LlNES
Valuable information can be obtai ned by studying lhe pol arized components of
a Raman line. In order to undersland how the Stokt:s lines can ha ve l pola riza tion,
we will first con idel" sorne scatt ring experi menls with poI, ri zed light. In F ig.
6- 12 t he interact ion of yz- polarized radi ati on wilh a molecule that has an isotropi c
polarizabilit y tensor is indicated. The oscillation induced in l he molecule wi ll be
in the ame plane as lhe electric fi dd a nd wilJ have a z-componcnt as shown by
the dou ble-headed arrow. 1f we observe emitted radiati on al ong the x-axis, il will
have to be xz polarized. Since ex is i otropic, the dir ction of the induced dipole
is unchanged as lhe molecule tumbles, and only xz scattered radiali on res ults. If
we had used xy-polari zed radiation as ur so urce, the osci llati ng induc d di poles
in a molccule with an isolropic polarizability would be oscillating parall el lo t he
x-axis. In Fi g. 6-13 the x-axis is perpendicular to the page, so t he xy-pl ane
polari zed radiat ion is also perpendi cular to the page. No componen! is d"lect d
z Oscillating induced di pole
v
x
FIGURE 6-13 Raman scatleri ng 01 xy-plan polarized radiation
produces no xz or yz components lor the scaltered wave when the
polarizabll ity is isotropi c.
v
6-10 Polarized and Depolarized Raman Lines 169
along x, for the molecular induced dipole moment oscillates parallel to x for aJl
orientations of the molecule.
As a result of the aboye discussion, it should now be c1ear that- even if our
so urce is non-polarized-the scattered radiation will be polarized if our molecuJe
is isotropic in ex, for there will be no xy-component.
The poJarizabiJity tensor is usually anisot ropic, as shown in Fig. 6-14.
Accordingly, the induced moment will not be coincident with the plane of the
electric field but will tend lO be oriented in the direction of greatest polarizabiJity.
The scattered light vibrates in the same plane as the induced dipoJe. As the
molecule tumbles, the orientation of the induced dipole moment relative to the
x-axis changes. Therefore, there are both xz and xy-components in the scattcrcd
beam giving rise to radiation thal is depolarized. Even if the incidcnt radiation
is polarized, an anisotropic polarizabiJi ty tensor will give rise to scattered radiat ion
that is depolarized. In the actual experiment, polarized radiation from a laser
source is employed and the polarization of the radiation scattered along the
x-axis is determined.
an
z
v
Nonpolarized radiation
x
FIGURE 6-14 Raman scattering 01 non-pol arized radiation Irom an
anisotropic polarizability tensor.
The aboye considerati on apply to l he Stokes lines, for which it is found
that a lotally symmelric vibration mode giues rise lO a polarized scatt eri.: d fine and
11G1 a vibration with lower symmetry is depolarized. This property can be used Co
("ollfirm whecher or not a vibralion has Al symmelry. Thus, by using an analyzer,
the scat tered Stokes radia tion traveli ng along lhe x-axis is resolved into two
pol arized components: radiation polarized in the y-dircct ion a nd that in the
z-direction. Radiation traveling along x and pol arized in the y-direction i rcfe rred
to as perpendicular and tha t component polarized in the z-direct ion is called
parallel. The depolarization ratio, p, i defined as the ratio of the intensi ty, 1, of
the perpendicular (y(J..)) to the parallel, z( ll), components of the Stokes hne :
l
yUl
p= (6- 14)
1:(1)
Tlzose Raman Zines for which p = 3/." are referred LO as depolarized Zines and
correspolld co uibrutions of the molecule that are not totully symmetric. T hose
Ra/llulI fines for which O< p < %are re{erred to as polarized Unes. 711.e vibrations
o{ rhe molecule must transform as A 1 in arder to be polari zed. The use of this
infonnati n in making band assignments will be made clearer after a discussion
of symmet ry considerations.
i
I
170 Chapler 6 Vibration and Rotation Spectroscopy: Infrared, Raman, and Microwave
6-11 RESONANCE RAMAN SPECTROSCOPY
As the laser exciting frequency in the Raman experiment approaches an allowed
electronic transition in the molecule being investigated, those normal modes that
are vibronically active in the electronic transition exhibit a pronounced enhance-
ment in their Raman intensities.(12) There are two applications of this fact. C ne
involves utilizing the intensity enhancement to study materials that can be obtained
only at low concentrations. T he second application involves the fact that only
those few vibrational modes near the si te of an electronic transition in a complex
molecule will be enhanced. Most examples of resonance Raman spectroscopy
involve the enhancement of totally symmetric modes and arise from intense
electronic transitions. There are recent examples in which vibronically allowed
electronic transitions enhance the Raman bands of modes that are not totally
symmetric, making them vibronically allowed.
It is possible for more than one electronic transition to be responsible for the
resonal1ce Raman effect, complicating the symmetry-based application just
discussed. By studying the intensity of t he resonance Raman bands as a fu nction
of the frequency of the exciting laser line, one can determine whether one electronic
transition (the so-called A-mechanism) or lwo (B-mechanism) are involved. The
intensily of a particular band is pr portional to the square of the frequency factor,
F. For the two mechanisms aboye, equations (6-15) and (6-16) have been proposed,
respect ively:
(6-15)
where ve is the frequency for the elect ronic transition, V
o
is the source frequenc
and V = with equal lO the frequency for t he vi brational transition; V
o
-
and
(6-16)
where Ve and V are the frequencies for the two electronic t ransitions involved and
s
lhe other terms are as defi ned for equation (6- 15). A large number of other
mechanisms and equations have recently been proposed.
An example of lhe enhanced intensity(13) from l he resonaoce Raman effect is
shown in Fi g. 6-15. In (A), a typical elect roll ic spectrum for a heme chromophore
is shown. In (B), parallel and perpendicul a r compon nts of l he resonance Raman
spectrum of a 5 x 10-
4
M solution of oxyhemogl obin are il lustrated. Without the
resoll ance enhancement associ ated with the 568 nm exciting wavelengtb, this
concentration of material would not have yielded a Raman pt:ctr um. The label
dp refers to a depolarizcd band (depolarization ratio of 3/
4
), P l O a pol arized band,
and ip to a band in which the depolarization ratio is grcater t han one (i.e., the
scalt red Iight is pola ri zed perpendicular to the polari zat ion of the incident light).
An ip band requires that the scattering tensor be antisymmetric (i. e" r:t.j = - r:t.
j
),
which is possible when V
o
a proaches V When the exciting li ne is far from an
electronic t ransition, the ralio cannot be larger than 3/
4
, The scattering tensor
elements discussed here a nd symbolizcd by "" are not to be confused wit h lhe
polarizability tensor elements discus ed earlier.
An assignment of lhe heme Raman spectrum has been made that is con istent
with the assigned electronic transiti ons. Tbe spectral features common to ma ny
dp
<D
f )
Jvl
(8)
FIGURE

Resonar
and the
perpend
is analY2
lo the inc
568.2 nm
Hb0
2
[F,
69, 2622
heme prc
symmetr:
In <li
inee [he
500 cm- '
o nly one
160
(6-15)
(6--16)
6-11 Resonance Raman Spectroscopy 171
Vi sible (a{3) resonance
30
(Al
I I
mM
o
X5
r-Soret-j
resonance
350 400 500 550 600
X(m/,,)
Hb0
2 :JI
Q

N
I
ip ip
N", ip
dp dp

ce
'"
Ip Ip I
dp dp
I 1 I 1
1
11
1600 1400 1300 1200 1100 1000 900 800 100 600
(BI
CM-I
FIGURE 6--15 (A) Ultraviolet (Soret) and visible (ex - (J)
chromophores in hemes. Spectrum 01 lerrocytochrome c. (B)
Resonance Raman spectra 01 oxyhemoglobin . Both the direction
and the polarization vector 01 the incident laser radiation are
perpendicular to the scattering direction. The scatlered radiation
is analyzed into components perpendicular (1.1. ) and parallel
to the incident polarization vector. The exciting wavelength was
nm (5682 A) lor Hb0
2
Concentrations are about 0.5 mM lor
Hb0
2
[From T. G. Spiro and T. C. Strekas, Proc. Nat!. Acad. Sci.,
69,2622 (1972) .]
heme protei n are discussed, as is the use of the depolariza lion rali os to infer local
ymmetry f lhe heme unit.(lJ)
In anolher application of this techn iq ue,(14) a resonance Rama n ana lysis of
oxyhemerythrin was carried out ti ing lhe oxygen --+ iron charge-transfer ba nd at
5000 to inten ify the O- O stretching vibrat ion . Two Raman frequencies we re
observed at 844 cm - l (p = 0.33) and at 500 cm - 1 (p = 0.4). When l80
z
is employed,
the bands shift to 798 cm - 1 and 478 cm - 1, respectively. The e bands do n t appear
in the deoxygenated protein. T he band al 844 cm - 1 has been assigned to lhe
O- O st retch anrl is no! coupled to lhe other vi brati onal morles in t he molecul e,
since the predicted frequency fo r isotopic sub Litulion (796 cm - 1) is o bserved . The
500 cm - 1 ba nd is a signed to an Fe-O- O stretching mode. The pectra indicate
only one type of O
2
complexo
l
172 Chapler6 Vibralion and Rolalion Speclroscopy: Infrared. Raman. and Microwave
r 11
th .
z co
We<
There
for a J
T
andt
l1loteel
Ihl:a
Simiar
anu B;
U .d n
(lrfn.:
101<11d
Symmetry
Aspects of
Molecular
Vibrations
F
F
F
.1
'S
F/"'l"'F
F
T
d
FIGURE&-16 Somepossible
structures for SF4
6-12 SIGNIFICANCE OF THENOMENClATURE USEDTO
DESCFURI= VARIOUS VI BRATIONS
In this section the conventions used to label the vibrations Al' Al' etc., will be
reviewed to refresh the reader's memory. Ifthe vibration is symmetric with r spect
to the highest-fold rotation axis, the vibration is designated by the letter A. Irit is
antisymmetric,theletterBis employed.E stands for adoublydegeneratevibration
and T for atripiydegeneratemode(F is commonlyused insteadofT in vibrational
spectroscopy).Thesubscripts9 andu refer to symmetrywith respect toan inversion
through a center of symmetry and are used only for molecules with a center of
symmetry. Ifa ibration is symmetric with respect to the horizontal plane of
symmetry, this is designated by', while " indicates antisymmetry with respect to
thisplane.Subscripts 1and2(asin Al and Al) indicatesymmetryandantisymmetry,
respective!y, toward a twofold axis that is perpendicular to the principal axis.
6-13 USE OF SYMMETRY CONSIDERATIONS TO
DETERMINE THENUMBER OF ACTIVE INFRARED
ANO RAMAN UNES
In this section we shall be concerned with c1assifying the 3N - 6 (or 3N - 5 for
alinearmolecule)vibrationsinamoleculeto[hevariousirreduciblerepresentations
in the pointgroup ofthe molecule. This informati o'n will then be used to indicate
thedegeneracyand numberofinfraredandRaman-act ive vibrati ons.Theprocedure
is best illustrated by considering the possible structures for SF4(C2,,, C3,;> and Id)
repre ented in Fig. 6- 16.
We first considerthe C1 11 struct ure.An x, y, z-coordinatesystem is constr ucted
for each atom and we proc ed to determine the lotal representation for this basis
set using the C
l
" character table reproduced in Table 6--4.
We know that when an atom is moved by a symrnetry operation, the
contribution to the totalrepresentati on will bezero;so we need only worry about
the x, y, and z coordi nales on atoms not mov d. FOf E, none of the atoms or
coordinates are moved,giving Xr( E) =15. Only the sulfur atom is no! mov d by
the e l operat ion, but the x and y coordinates ofthe sulfur each contribute -1
to thetotalrepresentationwhile thezcont ri bll tes +l.This leadsto X1'(C 2) = -l.
Sul fur and two oftheft uorine are not moved by reAection in the(Jxz pl ane,whilc
two ftuorine are moved.On the sll lfur atom this refl ecti on changes the sign 01' y
but leaves x and Z ull cha nged for a cont ribution of +1. The same is true for each
TABLE 6-4. C
l
" CharacterTablea
E el 1, -=) a ~ y : : )
1
-1
-1
1
- 1
1
- 1
1
- 1
-1
Z, 'Xx2,ay2, ::1. =2
R=,IXX )'
x.R)',0:;.<
y,
RxI1),=
For planarmolccules lhe x-axi si sperpendicular la lhe plane.
be
cet
,t is
ion
nal
5 fur
6-13 Use 01 Symmetry Consi derations to Determine the Number 01 Active Inlrared and Raman Lines 173
of the unshifted fluorines, leading to XT(av(xz)) = 3. Reflection through yz changes
Ihe x-coordinate to -1 for all three atoms not moved but does not change y or
z coordinates, leading lO Xr(a;yZ)) = 3. Summing up these results, we oblain:
Xl = 15 - 1 3 3
We can factor the tot al representation as follows:
fo r E
1
nA =-[[ '['15+1'1'(-[) + l J 3 + [. l 3J =5
4
A 1
n '=4 [1 ' 1' 15+ 1'1(-1) + 1'( -1)'3+ l'(-1)'3J =2
1
nB, = - [l' l 15 + J . (-1)' (- 1) + 1 (-1)' 3 + 11 3J = 4
4
1
11
8
' =-[1'1'15+ 1 ( - 1)(-1) + 1' 1'3 + l ( - 1) . 3J = 4
4
8 B
The resulls nA, = 5. nA, = 2, n , = 4, and n , = 4 repesenl the 3 V degrees offreedom
for a pentatomic elv structure.
To get Ihe tOla1 number of vibrations, the Ihre degrees of Iranslal ional freedom
and three of rotationa1 freedom must be e ubtracted (gi ing 3N - 6 fOf l nonlinea r
molecllle). Trall slation along the x-axis can be reprcsented by an arrow Iying along
th is axis, which, as seen from the e1 1' character lable, belongs to l he pecies B I'
Si miarl y, Iranslat ion along t he z and y axes Ira n rms according LO p cies A l
and Bl' Rotat ions along Ihe x, y, and z axes are represented by Ihe symbols R.
R).. and R: a nd belong to species A
2
, B
1
and B
2
respectively. These six degrees
of freedom (1 Al ' 1Al ' 2B l ' and 2B 2) a re sublracted from the represenLaLion of lhe
8 B
total degrees of freedom. prodll cing nA , = 4, nA, = J, n , = 2, and n , = 2, corre-
sponding lo Lhe nine vibration predicted from t he 3N - 6 rule.
W have now ca\culaled lhe p cies to whi ch lhe 3 . - 6 vibrati ons of SF4
belong if it has a e
21
Lr uclure. Four a re of pecie Al' one of Al' two of B
I
, a nd
two of 8
2
, The next j b is to determi ne which vibrations are infrar d active and
which are Raman active. For a fundament al transition to occur by ab'orpti on of
infrared electromagnet ic radiat ion, one of Ihe t hree integral
f1/1 1 ' 3:1/1 ,<' d (6-17)
must be non-zer or A l' The X, )\ and i op rators correspond LO Lh ri ' nt ation
of th eleclric field e lor relative to a molecul a r Carlesian co rdinate ystem. Thc
operalor i identi cal lo that di scussed in ele t ronic ab 'orpli on spectroscopy. Since
al! ground vibrali onaJ wave functions are Al (if oecessary, reread Chapler 4. Ihe
section on alomic aod mol clllar transit ions), Ihis amoun ts lo having l component
of Ibe t ransit ion dipole operator _x, ji, or zthat has tlle same symmetry as IPV ib<X '
whcrc lhe total vibrati onal exciled slate for a fu ndamental transition ha. lhe same
symmctry as Ihe nom1al mode excited. Accordingly, a fUlldamentallVill be infrared
174 Chapter 6 Vibration and Rotation Spectroscopy: Infrared , Raman, and Mi crowave
aclive if Ihe exciled normal mode belongs lO one of Ihe irreducible represenlalions
corresponding lO Ihe x , y, and z veclors, and will be inact ive if il does nol.
In order for a vibration to be Raman active, it is necessa ry that one of the
integrals of the type
(6--18)
be non-zero, i.e., the integrand A) . Here the operator P is one of the quadratic
functions ofthe x, y, and z-vec tors (i.e. , X 2, l, Z2, x y, yz, xz), simply or in combination
(i .e., Xl - l ). The symmetries of these functions are li sted in the character tabl
opposite their irred uci ble representati ons. Since these quantities are components
of the polarizability tensor, we find the foll owing rule stated: Afundamental transition
will be Raman acti ve if the corresponding normal mode belongs to the sarne irreducible
representat ions as one 01' more of the components of the polarzability tensor.
For the C
lv
structure of SF
4
, the Al' 8
2
, and B ) modes a re infrared active,
while A
2
is infrared inactive (neither x, y, nor z has Al symmetry). Eight infrared
bands a re expected: 4A) , 2B l ' and 2B2 ' Al! nine of (he fundamental vibratons are
Raman active, and the four Al modes will be polarized.
When we ca rry out the aboye procedure onthe J; structure for S F ~ we obla in
2
a total representaton XT = 15(E) 0(8 C3) 3(6CT
d
) - 1(6S
4
) - 1(3S
4
= 3C J Factor-
ing, we obtain:
1
n
l1
' = 24[1'1' 15+ 8' 1'0 +613
+ 6'1'( - 1) + 3 l (-I)J =1
1
n
A
'= - [I ' I' 15+ 8'1'0 + 6(-I) 3+ 6(-I)(-I)+31(-I)J = 0
24
1
n
E
= - [ 1 2 15 + 8 ( - 1) . O + 6 O . 3 + 6 O' ( - 1) + 3 2 ( -1)J =1
24
1
n
T
, = 24 [1 ' 3 15 + 8 O O + 6 (-1) ' 3 + 6 l (-1) + 3'(-I)'(-I)J = 1
1
N
r
, = - [l' 3 15 + 8 O O + 6 1 3 +6'(-1)'(-1)+3'(-1) (-I)J - 3
24
The J; charact r lable indicates Ihat the three lranslations are of species 'r;
and the threc rol alions of species TI' Sine TI and T
2
are tripl y degenera te, \Ve
need subtract only one of each from the total degr of freedom to remove Ihree
degrec of translation and thr of rotation. The total numb r of vibration bel ong
to species Al ' E, and 2T
2
gi ving rise to the nine modes predicted from the 3N - 6
rule. The si x T
2
ibrations (two lriply degenerate sets) are infrared acti ve and give
rise to two fundamental bands in the infrared spectrum. Al! modes are Raman
acti ve, gi ving ri e to four spectral bands corresponding to fu ndamentals. Of these,
Al is polarized. Jl an be shown simi larly that the e3" struclure of SF4 leads to
six infrared lin (lhree A l and lhre E) and six Raman lines (three A l and th ree
E), three of which are polarized (A 1)'
TABL
of SF
4
[ nfrare
mod
Raman
Polarizc
Q R.
Th
Ra man
elimina
conside
more r
tha! sincc
TABLE 6-
IR-Active
Vlbrallons
CHCI , (cm
260
364
66 7
760
1205
3033
6-13 Use of Symmetry Considerations to Determine the Number of Active Infrared and Raman Lines 175
TABLE 6-5. Summary 01 Active Modes Expected lor Various Conligurations
01 SF
4
the
e2 , T"
e
J
, . Found"
Infrared-active
modes 8(4AI' 2B
I
, 2B
2
) 2(2T
2
) 6(3A
I
,3E) S(or 7)
18)
Raman modes
Polarized modes
9(4A l ' Az. 2B
I
, 2Bz)
4(4A
I
)
4(A 1> E, 2T
2
)
I(A
l
)
6(3A
I
,3E)
3(3/11)
S(or 8)
I
=1
= 1
I)J = 1
I)J = 3
!c(ids lo
a R. E. Dodd, L. A. Woodward, and H. L Robcrt s, Trans. Farado)' SOC, 52, 1052 (1956).
The actual spectrum is round to contain five inrrared rundamentals, and five
Raman Iines, one or which is polarized. These results, summarized in Table 6--5,
eliminate the T, structure, leaving either e2, ' or e3u or the possible structures
consid red. This example demonstrates the point that although tlIere cannot be
more rundamental vibrations than aJlowed by a symmetry type, orten not al!
vibrations are detected. The p roblems in application or these concepts involve
separating overtones and combinati ons rrom the rundamentals ando as is often the
case, not finding sorne " active " rundamental vibrations because they have low
intensities.
Table 6--5 should be verified by the reader by using the character ta bles
contained in Appendix A and the procedure described aboye. By a detai lcd analysis
or he band contours and an assignment or the rreq uencies, il was conclllded that
the e2v tructure b st fits lhe observed spectrum. This structure was subsequently
confirmed by other physical mel hods.
The data avail a ble on CHCI ] and CDCJ ] are sum marized in Ta ble 6--6 and
\Vill be discllssed briefly beca use this exa mple ser es to review many or Ihe
principies discllssed. T he 3N - 6 rule pr dicts ni n\: normal vi brations. Jus t as
with lhe eJI' st ructure or SF4' the total representat ion show tha t these ninc
vibrations consist or three Al and three Especies or a total or six rundament al
rrcquencies. Al! si;.:. rundamentals wiIl be IR a nd Raman active, a nd the t hree Al
rundamentals \ViII give polari zed Rama n lines. T he observed bands that have
been assigned lO fu ndamental frequenei s a re summarized in Table 6--6. These
data indicate that the 3033, 667, a nd 364 cm -1 bands belong to Ihe totally
syrnmet ric vibrations (speeies Al)' for these bands a re Rama n pola rized. T hey
are labeled VI ' V
2
a nd v), re peeti vely. The other t hree bands are or speci es f.,
and the 1205,760, and 260 cm- bands are V
4
' V
s
, and "' res pecti vel y. Note
thal si nce the molecule does not ha ve a center of symmetry, t he IR and Raman
TABLE 6-6. Inlrared and Raman Fundamentals lor CHel .,
IR-Active Raman-Acllve
Vlbralions lor Vlbralions lor Raman Speclra
CHel ] (cm . ,) CHCI , (cm-
I
) 01 ceel ] (cm-
I
) Deslgnallon
260 262 262
1'6
364
667
760
366 (polarized)
668 (polariled)
761
367
651
738
v
J
l'
2
1'5
1205 1216 908
1'4
and three 3033 3019 (polarized) 2256 l'
I
I
i
l
I
'
176 Chapler 6 Vibration and Rotation Spectroscopy: Infrared, Raman, and Microwave
spectra have lines in common. The exact form of these fundamental vibrations
is ill u trated in Appendix C. The bands VI and are the C- H st retching and V
4
bending vibrations, respectively. Note how deuteration has a pronounced effect
on lhe 'e frequencies but almost no effect on the others. The vibrations at 3033
and 1205 cm -[ are almost pure - H modes. Snce the very light hydrogen or
deuterium ato m is moving, very little C- Cl motion is necessary to ret ain the
center of mass (to prevent net translation of the m0kcule).
The abo ye manipulations are quite simple and yet yield valuable information
about the slrucl ures of simple molecules. There are many applications of these
concepts. l t is strongly recommended that the reader carry out the exercises at
the end of this chapter.
Spectroscopists often use the V" symbolism in assigning vibrations. This can
be translated into the language of stretches, bends. and t is ts by referring to the
diagrams in Appendix C or in H rzberg (see Addi tional References) fo r an example
of a molecule with si milar symmetry and the 'ame number of atoms. The
irreducible representation of a given normal vi bration can be determined from
the dagrams by the procedure outlined in Chapter 2.
6-14 SYMMETRY REQUIREMENTS FOR COUPLlNG
COMBINATION BANOS, ANO FERMI RESONANCE
There are so me important symmet ry requirements regarding selection ru les for
overtone and combinaton bands. These can be demonst rated by considering
BF3' a D 3h molecule, as an example. T he D 3h char cter tabl e indicate lhat lhe
symmet ric stretch, VI' of species A l ' is infrared inactive (there is no dipole moment
change). The spe ies of the com bi naton band VI + V
3
(where V
3
is of species E' )
is given by lhe product of A' x E' = E' . The combi nation band i infrared act ive.
The V
2
vibration is of symmetry A / and is infrared active. The overtone 2v
2
is
of species A
2
" x A
2
" = Al ' , whi h is infrared inactive; 3v
2
is of species A
2
" and
is observed in the infrared spectrum. This behavior is strong support for the
initial structural assignment, lhat of aplanar molecule, and serves here as a nice
example to demonstrate the symmetry requirements for overtones and combi-
nation bands (recall lhe discllssion in Secr,ion 6-5).
In the case of Fermi resonance it is necessary that the states which are
participating have the same symmetry. or example, if 2v
2
is lo undergo Fermi
resonance with vI' one of the irreducible representations ror the direct product
2v
2
must be the same as for VI'
Coupling of group vibrations was mentioned earlier in this cha pter. In order
for cOll pling to occur, the vibrations must be of lhe same symmetry type. F or
cxample, in acetylene lhe symmetric C-H stretching vibration and the - C
stretching vibrat ions are of the same symmet ry typ and are highly coupled. The
observed decrease in the frequency of the symmetric C-H stretch upon
deuteration is smaJler than xpected, becallse of this coupling. Si nce the
asym metric C- H lretch and the "C- "stretch are of different symmetry. they
do not couple, and deuteration has the normal effect on the asymmet ric C-O
stretch (a decrease from 3287 to 2427 cm - I is observed).
6-'
PUl
infr
freq
infr,
1 cn
wide
valu
tab u
a ), pl
Iines
(1) TI
convc
(2) Th
order
mOme
rr
from I1
dist anc
Let w;
molucu
where .1
16.62 x I
E = /1\'.
energy:
The enCr
substit uti'
or
ons
and
O'eet
1033
n or
I the
ation
Ihcse
' es at
li s can
lo the
;ample
The
d from
rules for
lsidcring
that the
I moment
pecics E')
'cd acti ve.
Jne 2\'2 is
. A
2
" and
1ft for thc
as a nice
nd eombi-
whieh are
Fermi
!ct proJuct
ter. In order
:y type. For
.d the e-e
:ouplcd. The
tretch upon
z. Since the
they
metric e-O
6-15
6-15 MICROWAVE SPECTROSCOPY
Pure rotational transitions in a molecule can be induced by radiation in the far
inrrared and microwave regions or the spectrum. Ext remely good precision ror
rrequency determination is possible in the microwave region. Compared to the
infrared regio n or the spectrum, where measuremen ts are routinel y made to a bout
1 cm - 1, one can get resolution or about 10- 8 cm -1 in the mirowave region A
wide spectral range plus resolution and accuracy to 10- 8 cm -[ make this a very
valuabJe region ror finger prinl applications. A list or frequencies has bccn
tabulated(15,16) consisting of 1800 lines ror about 90 differcnt substances covering
a span of 200,000 MHz. * Only in lOor the cases reported were two or the 1800
lines c10ser than 0.25 M Hz.
There are two requirements that impose limitations on microwave studies.
(1) The spectrum must be obtained on the material in the gaseous state. For
conventional inst rumentation, a vapor pressure of at least 10-
3
torr is required.
(2) The molecule must have a permanent dipole moment in the ground state in
order to absorb microwave radiation, since rotation al one cannot create a dipole
moment in a molecule.
In addition to the fingerprint applicati on, other userul data can be obtained
[rom the microwave spectrum or a compound. Sorne or the most accurate bond
distance and bond angle data available have been obtained rrom these studies.
Let us first consi der a diat omic molecule. The rotational energy, E, ror a diatomic
molccule is given by the equati on:
E = hBJ(J + 1) (6-19)
where J is an integer the rotational quantum number; h is Planck's constant
(6.62 x 10-
27
erg sec); and B = h/87[2/ where / is t he momen t or inerl ia. Since
E = hv, we obtain the relationship for the rrequency, v, corresponding to this
energy:
v = BJ(J + 1) (6-20)
The energy or the transit ion rro m state J to J + 1 can be determined by
substitution in equation (6- 19), leading lo
I1E = 2Bh(J + 1)
or
= 2B(J + 1)
There is another selection rule (in addition to the dipole moment requirement)
ror microwave absorption, which st ates that I)"J = 1. Thererorc, lhe longesl
wavelength (lowest energy) absorption band in the speclrum will C' orrespond lO
A wave number of 1 mm-
1
is equivalcnt to a frequcncy of 299,800 MHz.
Microwave Spectroscopy 177
178 Chapter 6 Vibration and Rotat ion Spectr oscopy . Infrared, Raman, and Mi crowave
the transition from 1 = Oto 1 = 1, for which the freq uency of the absorbed energy
is:
2h
L1v = 2B = -- (6-21)
8n
2
1
L1v is measured and all other quantities in equation (6-21) are known except 1,
which can then be ca1culated.
AlI other lines in the spectrum will occur at shorter wavelengths and wi ll
be separated from each other by 2B [i. e., L1L1v = 2B(1 +2) - 2B(1 + L) = 2B,
where (1 +1) is the quantum number for the higher rotational state and J that
for the lower ; see Fig. 6- 17]. Once the moment of inertia is delermined, the
equilibrium intem uc1ear separation, "0' in the diatomic molecule can be ca1culated
with equation (6-22) :
(6-22)
where /1 is the reduced mass.
FIGURE 6-17 IIlustration 01 the O..... 1
and other rotational transit ions
(idealized).
0-1
In the aboye discussioos we have assumed a ri gi d rot or as a m del. This
means thal the atom positions in lhe molecule are not influcl1ced by the rot at iol1.
Because of lhe inftuence of centri fugal force 0 11 the mole ul e during the rotation,
there wi ll be a smaU amount of distorti on. As a result, the bond distance (and
J) will be larger for high val ues of 1, and the spacings betwecn the peaks will
decrea e slightl y as J increascs.
In a more complex molecule the moment f inertia i relaled to lhe bond
lengths and angl by a more complex relationshi p than (6- 22). A whole series
of simultaneous equations has to be solved to determine all the structural
parameters. lo order to g l enough experimenl l obs rvations to solve all these
equati ons, isotopic substitulion i employed. For pyridine, the mi crowave sp ctra
of six isotopically sub ti lut d compoll ods (pyr idine, 2-deuteropyri di ne, 3-
dellteropyri dine, 4-dclIteropyri dine, pyridine-2-
13
C, and pyri dine-3- t.> ) were
employed. For a more omplete discllssion of tbis problem, see Gordy mith,
and Trambarulo.(15)
By a detailed anal ysis of the microwa ve spect rum, ne can obtain information
about internal mot ioos in molecules. The torsional barrier frequency and energy
can be obtained. (l al
Double resonance Xp rimeots ha e also proved val uable for assigning peaks
and for determining relaxation ti me of tates. A gi ven transit ion i satu rated
wi th microwave power, producing a non-equilibrium distribution in th popu-
lations of the two levels inv lved. One then looks for an inc rease or decrease in
ot her transitions Ihat are thougbt to invol ve one of [hese levelsY 7b)
exr
rol.
upe
stre
fi ne
eva
nUCi
soli
Infol
B. In
6-11
6-17
0-1
6-17 Procedures 179
\ViII
2B,
that
the
uted
Accurate dipole moment measurements can be made from microwave
experiments. When an e\ectric field is applied to the sample being studied, the
rotational ne is split (the Stark effect). The magnitude of the splitting depends
upon the product of the dipole moment (to be evaluated) and the electric field
strength (which is known).
Much information is available from the Zeeman splitting of rotational
linesY 7c.d) The components of the magnetic susceptibility anisotropy can be
2
evaluated, as can the expectation value <r ) . As we shall see in the chapter on
nuclear quadrupole resonance, nqr, much the same information obtained on
solids by nqr can be obtained on gases by microwave spectroscopy.
6-16 ROTATIONAL RAMAN SPECTRA
Information equiva lcnt to that obtained in the microwave region can be obtained
from the rotational Raman spectrum, for which the permanent dipole selection
rule does not hold. As a result, very accurate data on homonuclear diatomic
molecules can be obtained from the rotational Raman spectrum. Experimentally,
the bands are detected as Stokes Iines with frequencies corresponding to rotat ional
transitions.
[n order for a molecule to exhibit a rotational Raman spectrum, Ihe
polarizability perpendicular to the axis of rotation must be anisotropic; i.e., (he
polarizability must be different in different directi ons in the plane perpendicular
to the axis. If the molecule has a threefold or higher axis of symmetry, the
polarizability will be the same in all directions and rot ational modes about this
axis will be Raman inactive. Other rotations in the mole ule may be Raman active.
For diatomic molecules the selection rule !J.J = 2 now applies :
!J.E = BI1(41' - 2) (6- 23)
and the frequency separation between the lines is 48 . If this separation is not at
least ~ O l cm- the lines cannot be resolved in t he Raman specl rum. The rest
of thc calculation is identical to that described previousl y. There has been onl y
limited application of this techr' :que lo more complex molecules.
6-17 PROCEDURES
a. In Infrared
The mosl common infrared equipment covcrs the wavelength region from 4000
lo 400 cm - 1 The grating resol ves polychromatic radiation into monochromatic
radiation so thal variati on in a b orption of a sample with changc in wavelength
ca n be studied. The resulting p ctrum i a plot of sample absorbancc or percent
transmission versu wavelength (see Fig. 6-26).
The readcr is rcfcrred to thc text by Na kamoto
l
181 and to rderence \\ for ex tensive compil a ti ons
of cxamplcs of infrarcd and Raman spcctroscopy, respcctivdy.
Applications of
Infrared and
Raman
Spectroscopy*
,
180 Chapter 6 Vibration and Rotation Spectroscopy. Infrared, Raman, and Microwave
Movable r:::::;:=::J Stationary
mirror
Source
L-

(A)
MIWV
I
, 'W/2 '- i+' , , , , ,
O
(8)
(C)
FIGURE 6-1 8 (A) Schematic
01 the FTIR technique. (8)
Radiation sensed atthe
detectorfor a continuously
moving mirror. (e) Inter-
ferrogram from a
polychromatic source.
The Fourier transform (FT rR) technique,')91 which will be discussed in more
detail in Chapter 7 on nmr, is now very common in infrared instrumentation(l91
The method greatly decreases the amount of time needed to accumulate a
spectrum. Thus, multiple scanning of the spectrum and computer storage of the
scans become feasible, greatly enhancing the signal- to-noise ratio. Furthermorc,
filtering is not required, eliminating the need for energy-wasting slits. Enhanced
resolution in a shorter time period is possible. A schematic illustration of the
method is shown in Fig. 6-18(A).
The monochromatic so urce is split into two components. One is SCI'I 't to a
stationary mirror traveling a distance r. The second component is sent to a mirror
av e
that moves, traveling a distance of r
2
The reflected components are
refocused at the detector. When = O, r) = r /"<,the beams reinforce. When
the mirror is moved so Ihat r
2
= " 2""e +//4, the radiation travels r/
ve
+),J2
().j4 going and coming back) and is 180
0
out of phase with the component that
traveled r
l
. The beams cancel. Irthe mirror is moved continuously, the intensity,
lb' of the radiation at the detector varies as shown in Fig. 6-18(8). Irthe mirror
is moved with a constanl velocity, V
M
, over a distance },/2, one cycle of a sine
wave is produced.
The frequency at the detector, VD' is relaled to the wavelcngth by
(6-24)
With a wavelength Xof 10 J1 (i.e. , a frequency of 1000 cm - 1) and a mirror v locity
of 0.5 mm/sec-
I
, a frequency of 50 Hz (cps) results. The low frequency signal
that results from the high frequency s urc i termed an interferogram. Poly-
chromatic radiation is employed in FTIR. Each component produces a wave
with a unique frequency. The summation of all such waves produces an
interferogram as shown in Fig. 6-18(C). All frequencies add only at /") = 1'2' T he
Fourier transform of the interferogram converts the time axis to a frequency axis
and gives al! the frequency components of the source along wi th their intensities,
Irthe beam passes through a sample before hitting the detector, sorne frequencies
will be absorbed and missing in the Fourier transformo The spect rum is obtained
by difference. A laser is used as a reference source to constantly cali brate lhe
frequency scale of the instrument.
Infrared spectra can be measured on gases, liquids, or solids. Liquids and
gases are generally studied by absorbance measurements. Certain wavelenglhs
are absorbed by the sample and the ot hers are transmittcd. The malerials used
to construct the cells must not absorb in the regions of interest. Special cells wit h
a long path length are nceded ror most gaseous samples.
Solutions are studied. The solvent absorption musl be subtracted
out. Differenl techniques are used depending on the instrumentation. Tn rcgions
where the solvent absorption is very large almost all of the radiation is absorbed
by the solvent and the sample and no sample absorptions can be detected in
these blank regi ons. The open regions for several common liquids used for solution
work are ilIu trated in Fig. 6-19.
Absorbance spectra of salid samples are often examined as mulIs. The mull
is prepared by first grindi ng the sample to a fine particle size and then adding
enough oi l or muLl ing agent to make a paste. The paste is examined as a thin
layer between sodium chloride (or other optical material) plates. The quality of
the spectrum obtained is very much dependent on the mu ll ing technique. When
Aceto
Acet Ol
BenZ81
ChlorQ
Diethyl
Dichlor
N, N- [
amidel
Dimeth

n - Hex
Paraffm
Poiy(ch
Pyridine
Carbond
Tetrachlc
CarbontE
Tetrahyd
Toluene
FIGURE
inciden!
(C) 20 JIl
he spec
, pect run
NU.l Or al
regioo e
The sam
th tism,
for anior
grindi ng
Trar
lransparc
surface a
contribut
presse ir
Refl
by tran 'n
specular
mirrorli k
surface. O
the incide.
a detect or
considered
'1
e
.
.,
rd
le
a
or
re
en
f.I2
6-17 Procedures 181
Wavelength [mi
3 4 5 6 7 8 9 10 12 1416 20 30
111111111111111 11 1 t ! l ll ll l! !" , !!!!!! I!! !!II I! !" !!! !!!!!!I I!! !!III !!!! !
Aeetone l b)
Aeetonitrile lb)
Benzene l b)
Chloroform (b)
Diethylether(e)
Diehloromethanelb)
N, N- Dimethylformie-
amide(e)
Dimethyl sulfoxide le)
Dioxane le)
n - Hexane (b)
Paraffin INujol) (b)
Poly (ehlorotrifluoroethane) (a)
Pyridine l b)
Carbondisulfide (a)
Tetraehloroethenelb)
Carbontetraehl oridela)
Tetrahydrofuran le)
Toluene (b)
-
3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600 400
Wavelength(em- JI
FIGURE 6-19 Reg ions i n whi ch various solvents transmit less th?n 20% 01 the
incident radi ation (indieated by solid bars) . (A) 200 ..m cell thickness; (B) 100 ..m;
(e) 20 pm. See relerences 18 and 19 lorother solvents.
the spectrum is examined, peaks from the mulling material will appear in the
spectrum and possibly mas k sample peaks. Iftwo spectra are obtained, one in
Nujol and one in hexachlorobutadiene, all wavelengths in the 5000 to 650 cm - I
regio n can be examined. Solid samples are sometimes examined as KBr discs.
The sample and KBr are intimately mixed, ground, and pressed into a clear di sc
that is mounted and examined directly. Care should be exercised in this procedure,
for anion exchange and other reactions may occur with the bromide ion during
grinding or pressing.
Transmission IR can be used(20) to study surfaces of solids that have
transparent windows in the infrared, e.g., oxides of silica and alumina. Hi gh
surface area materials should be used so that the speclra have an appreciable
cont ribution from the surface as opposed to the bul k. These sa mples can be
pressed into discs and inserted into the beam path.
Reftectance techniques( 21) can be applied to samples thal canno! be studied
by transmission. These methods can be classified into general categories -
specular and diffuse reftectance. Specular rcftcctance(22) is the front surface,
mirrorlike reftecti on off a smooth surface such as a metal foi l or si ngle crystal
surface. Diffuse reftectance is observed witb rough surfaces and powders. Since
the incident radiation i reftected diffusel y, it must be col1ected and refocused on
a detector. The reader is referred to reference 22 for the factors Ihal must be
considered in comparing absorption and reftect ion spectra.
l
l
182 Chapler 6 Vibration and Rotation Spectroscopy : Infrared, Raman , and Microwave
Source Pressue
Sample Microphone
illustration 01 the
photoacoust ic technique.
An additional technique, referred to as IR-External Reflection spectros-
copy,(221 involves studying films coated on highly re.flecting surfaces, e.g., gold.
Large angles of incidence enhance the sensiti vity of the technique. A polarization
dependence of the vibrational modes of the adsorbed molecule provides orientational
information about the adsorbed molecule when polari zed light is employed.
Photoacoustic Fourier transform spectroscopy (PAS)(2 J) provides an addi -
tional technique for obtaining the infrared spectrum of surface molecules.
Absorption of Iight energy by a confined gas heats it and increases its pressure.
If the Iight so urce is modulated there will be a modulation of the gas pressure.
Sound is generated at the frequency of the light modulation and can be detected
with a microphone. Modulated light absorbed by a solid heat its surface, whi ch
in turn conductively heats a boundary layer of air next to the surface as shown
in the Fig. 6-20. Sound is again generated, but the signal detected is reduced in
amplitude and delayed in phase because the heat must be conductively transmitted
to the surface. For solids, only the energy absorbed near the sample surface is
effective in heating the surface quickly enough to cont ribule to the photoacoustic
signa!. Thus, PAS is a true surface technique. In the FTIR/ PAS xperiment, each
wave number of light is modulated at a unique frequency aod this frequency
ioformation is preserved in the microphone signa!. Thus, PA detection is a sort
of thermal detection io which the light absorbed heats up the sample. PA spectra
are qualilatively and quantitatively similar to tran mssion speclra and are
commonly rali oed to a saturated reference (carbon black). Sample surface
morphology has a minor qual itative effect on tht: pectra. Depending on the
source employed. one can do PAS in the IR, near IR, u.v., or vi sible. Diffuse
reflectance infr ared Fourier transform spectroscopy (DRTFTS), is com-
pared(22.2 JI wi th PAS to enable one to choose the best method for the problem
al hand.
The spectrum obtained for a given sample depends upon the physical stale
of the sample. Gaseous samples usually exhibit rotational fine st rucl ure. This
fine structure is damped in solut ion spectra beca use collisions of molecules in
rhe condensed phase occur before a rotation is completed. In addi tion to lhe
difference in resolved fine st ructure, the number of absorption bands and the
frequencies of the vibrations vary in the di ffe rent states. As an ill usl ralion, lhe
fundamentals of S02 are reported in Table 6-7 for the different physi al slates.
Other effects not ill ustrated by (he data in Table 6-7 are ofteo encountered.
Often there are more bands in the liquid state than in the gaseous state of a
substance. The stronger intermolecular for ees that exist in (he solid and liquid
states compared with those in the gaseous state are (he cause of sli ght shift
TABlE 6-7. Frequencies (in cm-
1
) for S02
Fundamentals in Di fferent Physical States
Gas liquidO Solid
(assum
in freq
spect r
in the l
Bands
transl a
called 1
low \Va

ibrati o
the
contain:
the vibJ
intermo
As
th
IS preser
unit cell.
forbidde
vibratiOl
effecl of
As a si m
carbonat
ca/cite, w
ba nds (i n
(fR ) indi,
of CaCO
Ihal \' 1 Ix
th symm
re ults ca
As a resu
o bt ained
The !
hydrogc n-
IOtcrach 11
rrequency
and other
v
2
(a) 5;.8 525 528
Matr
v(a ) 1151 1144 1I44 have led te
v
3
(b) 1362 1336 1322
mediales a
1310
mat rix (e .g.
a Raman speC lrum.
lo 20 K).
by allowin
6-17 Procedu res 183
,-
1.
n
al
I-
s.
rc.
rc.
ted
ich
I in
tt ed
:e IS
Istic
:ach
~ n c y
sort
~ c l r
1 are
rfacc
n Ihe
i ffuse
cern-
:>blern
1 slale
:. This
ules in
lo Ihe
.nd Ihe
on. Ihe
I slates.
mlered.
lle of a
liquid
shifts
(assuming that there are no pronounced structural changes with change of phase)
in frequencies. Frequently, new bands below 300 cm - appear in the solid state
spectrum. The causes of these frequency shifts, band splittings, and new bands
in the condensed states are well understood(25) and will be discussed briefly he re.
Bands below 300 cm - 1 are often caused by falUce vibrations in solids, i.e.,
translational and torsional motions of the molecules in the lattice. These are
called phonon modes and are responsible for the infrared cutoff of NaCI cell s at
low wave numbers. Heavier atom alkali halides have phonon modes at lower
energies. These vibrations can form combination bands with the intramolecular
vibrations and cause prono unced frequency shifts in higher frequency regions of
Ihe spectrum. An additional complication arises if the unit cell of the crystal
contains more than one chemically equivalent molecule. When this is the case,
the vibrations in the individual molecules can couple with each other. This
intermolecular coupling can give rise to frequency shifts and band splitting.
As mentioned earlier, molecular symmetry is very important in determining
the infrared activity and degeneracy of a molecular vibration. When a molecule
is present in a crystal, the symmetry of the surroundings of the molecule in the
unit cell, the so-called sile symmetry, determines the selection ru les. Often bands
forbidden in the gaseous state or in solution appear in the solid, and degenerate
vibrations in the gaseous tate are split in the solid. The general probl em of the
effect of site symmetry on the selection rules has been treated theoret icatl y.l 26l
As a simple illustration of this effect, the infra red spectra of materials containing
carbonate ion will be considered. T he infrared and Raman spectra of CaCO ) in
calcite, where the carbonate ion is in a site of D) symmetry, contain the following
bands (in cm -1): VI> 1087 (R); V
2
, 879 (IR); \1 ) , 1432 (I R, R); \1
4
, 710 (IR, R). The
(IR) indicates infrared activity and the (R) Raman activity. The infrared spectra
of CaC ) in aragonit e, where the site symmetry for carbonate is es' differs in
that VI becomes infrared active and \1) and \1
4
each split into two bands. By using
the symmetry considerations previoll Iy discussed on the CO) 2 - ion, Ihe following
resu lts can be obtained:
VI "2
D)h
A '(R) A
2
" (/ R) E'(l R. R) E(lR, R)
D) A( R) A
2
UR) E(l R, R) E(J R, R)
es
A' (/ R, R) A"(J R, R) A'(I R, R) + A'(l R, R) A'(/ R, R) + A'(J R, R)
As a result of all these possible complications, the interpretation of spectra
obtained on soli ds is difficult.
The spectrum of a given solute often varies in different solvents. Jn
hydrogen-bonding solvents the shifts are, in part, due to specific solute-solvent
interactions that cause changes in the electron distribu!ion in the solute. The
frequency of the band is also dependen! upon the refractive index of the sol vent(2 7)
and other cffects.(28)
Mal rix isolation experiments combi ned with infrared ari d Raman st udies
have led lo interest ing developments. Unstable compound radicaIs, a nd inter-
mediates a re trapped in an inert or reactive solid matrix by co-condensing the
matrix (e.g., argo n) and the species to b studied at low temp ratures (often 4.2
lo 20 K). Ura nium, platinum, and palladium carbonyls have been prepared( 29a .b)
by alI owing controIl d diffusi on of CO into an a rgon mat rix of thc metal. The
are completely obscured, open rectangles partially obscured.
184 Chapter 6 Vibrat ion and Rotation Spectroscopy : Infrared, Raman, and Microwave
compounds Li02' Na0
2
, K02' Rb0
2
, and LiN
2
have also been made( 29c) and
investigated by infrared. The findings are consistent with e2u symmetry. Several
interesting species containing bound
2
,ca, and N 2 have been made(29d)
b. In Raman
Raman spectra are routinely run on gases, liquids, solutions, or pressed pellets.
Liquids can be purified for spectral studies by distillation into a sample cel]
Removal of dust is essential, since such contamination increases the background
near the exciti!lg lineo Turbid solutions are to be avoided. Water and 2 are
excellent Raman solvents because, in contrast to their behavior in the infrared,
they have good transparency in the Raman vibrational region. Figure 21
illustrates the cutoff region for various solvents in the Raman region. A complete
Raman spectrum can be obtained by using CS
2
, CHCI
3
, and C
2
Cl
4
. For colored
solutions, an exciting line should be used that is not absorbed. Fluorescence and
photolysis are problems when the sample absorbs the exciting line.
Solids are best investigated as pellets or mulls. The techniques for preparing
these are the same as those for infrared. If powders are examined, the larger the
crystals the better. For colored materials, rotating the sample during the
experiment prevents sample decomposition and permits one to obtain a good
spectrum. Surface scanning techniques are also helpful.( 9). Experimental aspects
are described in more detail in references lO and 11.
6-18 FINGERPRINTING
If an unknown is suspected to be a known compound, its spectrum can be
compared directl y with that of the known. The more bands the sample contains,
the more reliable the comparison.
The presence of water in a sample can be detected by its two characteristic
absorption bands in the 3600 to 3200 cm - 1 region and in the 1650 cm - 1 region.
CS
2
R
ir
CCI
4
R
ir
CHCI
3
R
ir
~
CH
2
CI
2
R
:
r
ir
C
2
CI
4
R
ir
HJCCN
R
~
ir
H
2
0
R
ir
2
R
ir
3000
1
d
- -CJ
e
O
=
e
ep o
-
-
o.
-
-
=
1
2000
WAVENUMBERS - cm-
1
_1=-
O
-

., ~
e
~

-
_.

O
-

-
-

-

e _.
-
- -
--
=
=
=
-
_1
1000
FIGURE 6--21 Solvent interference regions in the Raman region. Solid regions
If the w
300 m
addit io
clathrat{
h \Ved
ll1 an am'
constant
1650cm-
1
Stretching
4.
6-18 Fingerprinting 185
can be
If the water is present as lattice water, these two bands and one in the 600 to
300 cm - 1 region are observed. Tf t he water is coordinated to a metal ion, an
additional band in the 880 to 650 cm -[ region is often observed(18) In the
clathrate compound Ni(CNhNH 3' C6H6 . xH zO, the infrared spectrum(Z 3b) clearly
showed the presence of water, although it was not detected in a single crystal
x-ray study. In conncction with the earlier discussion on the effect of physical
state on the spectra of various substances, it is of interest to mention in passing
that the benzene is so located in the crystal lattice of this cIathrate that the
frequencies of the out-of-plane vibrations are increased over those in t he free
molecule, while the in-plane vibrations are not affected.
If the product of a reaction is suspected of being contaminated by starting
material, this can be confirmed by the prescnce of a band in the product due to
the starting material that is known to be absent in the pure product. Evcn if
spectra are not known, procedures ai med at purifica tion, e. g., recrystallization,
ma y be attempted. Changes in relative band intensities may then ind icate t hat
partial purification has been achieved. Consistent spectra on repeated purification
steps may be used as a check on completeness of purifi cation.
A more common application employs the group vibral ion concept to
ascertain the presence or absence of various functional groups in the molecule.
The following generalizations aid in this application :
1. Above 2500 cm - 1 nearly all fu ndamental vibrations invol ve a hydrogen
st retching mode. The O- H stretching vibration occurs around 3600 cm - 1.
Hydrogen bonding lowers the frequency and broadens the bando The N-H
stretch occurs in the 3300 to 3400 cm - 1 region. These ba nds often overIap lhe
O-H bands, but the N-H peaks are usually sharper. The N- H stretch in
ammonium and alkylammonium ions occurs at lower frequencies (2900 to 3200
cm -1). The C-H stretch occurs in the 2850 to 3000 cm - 1 region for an ali phatic
compound and in the 3000 to 3100 cm - 1 region for an aromatic compound.
Absorptions corresponding to S-H, P-H, and Si-H occur a round 2500, 2400,
and 2300 cm - 1, respectively.
2. The 2500 to 2000 cm -1 regio n involves the stretching vibraton for tripl
bonded molecules. The C-N group gves risc to a strong, sharp absorption that
occurs in the 2200 to 2300 cm - 1 region.
3. The 2000 to 1600 cm -1 regio n contains stretching vibrations for doubly
bonded molecules and bending vbrations ror the O-H, C-H, and N-H
groups. The carbonyl group in a ketone absorbs around 1700 cm -l . Conjugation
(
? )
in an amide RC-N(CH
3
h +--> RC=N(CH
3
h decreases the C-O force
constant and lowers the highly coupled (with C-N) carbonyl absorption to the
1650 cm -1 region. Hydrogen bonding lowers the carbonyl vibration frequency.
Stretchi ng vibrations from C=C and C=N occur in this region.
4. The region below 1600 cm - 1 is referred to as the fingerprint region for
many organic compounds. In this regio n significant di fferences occur in the
spectra of substances that are very much alike. This is the single bond region
and, as mentioned in the section on coupling, it is very common to get coupling
of individual single bonds that have similar force constants and connect similar
masses (e.g., C-O. C-C, and e -N stretches often couple). The absorption
111
186 Chapter 6 Vibration and Rotati on Spectroscopy : Intrared, Raman , and Microwave
BO
I f
6
(or,-;li
111
ca
(1101

" (CO)
" O)
SiO
" (NO)
'O NO
...
,,(PO)
I I I I
,g
PO
., (SO) I :-

c:
,,(s.o)
el>
Cl
" (CIO "(OCIO)
,.,
ao )(
'-
ffl
o era
la
lO " l O)
ex
c=::::;ft

AlX

ex
111
Si X
1-;5
1
-1
c:

.g
ti
GeX
t;I
lcI
8r
... -
.c
.;;

e
NX
"' 8, -1
..
'F---i
go
PX

o
ti
J:
AsX
rr

OX
-.==

I---'-I--l
SX
t-- f
1-11<-1
f--F-
FLQ--I
Sex
t- 1Ir-i
FIGURE 6-22(A) , (B). and
(e) Range 01 inlrared group
Irequencies lorsome
inorganic and organic
malerials,The symbol V
M
_
X
'
where M and Xare general
symbols lorIhe aloms
involved, corresponds lo a
slretching vibralion. The
symbols v" v
2
, ele, where
previously delined.The
symbol b corresponds lo an
in-plane bending vibralion (b
s
is a symmelric bend, b
d
is an
asymmelric bend). 1! lo an
oul-ol-plane bend, p lo
rocking and wagging
vibralions.
2400 2000 1500 JOOO 500 o
(A)
bands in this region for a given funct ional group occur at different frequencies
depending upon the skeleton ofthe molecule, beca use each vibrati on fl n involves
oscillation of a considerable numbcr of atoms of the molecular skeleton.
Many characteristic infrared group frequencies have been compiled to aid
in this application. Figure 6-22 shows several typical plots.
In the far regi on, it becomes very difficult to assign the observed spectrum
to group frequencies. Figure 6-23 1S a compilation that i!lustrates typical regions
in which absorption bands are found for molecules contai ning particular
functional groups.
6-1 9 SPECTRA OF GASES
The spectra of gases are often very much different fr om the spectra of mat rials
in the condensed phase or in solution. As can be seen in Fig. 6-20, a significant
difference is the presence of considerable fine structure in the gaseous spect rum,
The fine structure is due to a combination of vibrational and rot ational transitions.
For example, in a di atomic moJecuJe, there are not only transi ti ons correspondi ng
to the pure ibrat ional mode, V
o
, but also absorption corresponding to V
o
v,
c:
o
e
o
E
E
o
u
....
o
fIJ
11>
'8
E
11>
:>

u
o
:quencies
Iinvolves
In,
ed to aid
spectrum
alregions
particular
rmaterials
significant
spectrum,
transitions.
-responding
gto "o Vr
6-19 Spectra 01 Gases 187
lJl V3 lJ2
NCO-
H H
lJ
l
lJ
3
lJ
2
N - t----; t--i H
3
VI liS

NCS-
r--i H
en
VI liS
HH
e
N02- :1

1/2
e
o
uol+ HH H
vSv
l
E v
2
E
C10
2
- HH M
o
u lJs VI
C0
3
2
-
H H
'+--
liS VI o

N03- t-1 If
en
e I V
2
11.
Vs

' t-1 H H 83
3
-
o.
113

o

S03
2
-
.o
'"
112

M C103-
11
2
V. 1I3111
H H H Br03-
li S VI
11:2
11
10
3
- 1----1 H
Vs ,VI lJ.
"2
t--j H sol - i '" cu
'O
O l/s V.
VI

CI0
4
- H E
.,
"
liS lJz
lJ
l v..
P0
4
3
- t-=
!
H
!
ti

o 11,111 V.
e Mn04- H Hi
o
E
V
s
,11
1
11. v
t
o CrOi - H! l-'-f'I
a:
v. ,v VS,v1
SeOi- H :
z
t-r-t .2
'-
v 'f)
11.
2
e
Q)
H Mooi - IH
-
lJ
z
V, 11
1 4
'O
Asol'-
.:t 1
'O

lJ
l
V,
r. tt
a
W0
4
2
- O iH

M-CN
II(CS)
v(CN)
t--i
-
M-NCS"
., lJ(CO) lJ(MC)
'"
M-CO"
o
e I
M- NH3

.0><
(Fe, Hg M-NH
2

compex r '" oc. ,. ')'r' " '''.h'""') .""

'OE
., o M-N0
2
"
O1u
V (ONO) lJ(ONO) 8(ONO)
"2
H H I H "''0 M-ONO .0_
.,
lI(CO) lJ(CO) II(CO) 7r 8(OCO) v(MO)
E
r-f t--j HI HH f--l M-OCOz*
o
lJ NO)lI(NO) lJ(NO) 'TT' u
'O M-ON02
' H
..s 11(50) 6
4
(050) 8
d
(050)
*
).
I--i H
M-OSot
8(HOH pw(OH p,(OH2), P' (IOHz)
H
M-OH2
l
FIGURE 6-22 (continued)
4000 3000 2000 1500 1000 800 600
1 1 l. I 1 I
1-1
VC-o 8c-o '"c-o
I--i
1I0-
H -
H
vN- H 8N-H

vc.c vc_c II
C
-
H H
- C
VC!lN vC_N lIC-N
H H I
IIC-O IIC-O

liNO
1--1
( C- NOz.- ONz)
I/dCO:lV'
COr
HH
lIC-F lIC- ct
I---i f-----l
I/p_o
t--i
lJp_H
IIS-H
...
2000 1000 500 O
1 1 1 1 I 1 I
4000 3000 2000 1500 lOOO 800 600
(B)
1/ (cm-
I
)
(C)
,
I
FIGURE 6--23 Far infrared
vibrational frequency
correlation chart.
-1 -1
BOae 600e m 200 em
branched
Alkanes,
cYClo-heXIIt'IH
cydopentane$
21lkyl.pent.nes'___-i________-+________-t-.. _.....
cyclo-propanes----+--------+--------+----'.."""1
CF, _
-CCb
tfans p uche _

.CH.<:'________--I__--'__.,..___
CHC'----------t--------j---....--to
.c.c,----------+--------+-----'- -1____
..

At kenu.RCH == CRR I.ran.!: RCH=CHR
RRC ..CHl
RCH-CH= CH1
ci.
=CF1
=ccrl. ____ ___
.. ..

Al!enes -------------t--------+--------+---__='
Atkynes R C..cH _______ ..
alkylC-CH______+-______--+_______
C-e8r
e CI

Aromatics 1
1,2
1,3
1,_
1,2,4
1,3,5
1.2,3 ________+ ________+-________
1,2,3.4
_

1,2,3,5
l,2.4,5
1,2,3,4,5,6
1,2,3,4,5
Polyphenyls mono______--I________ -+______
.
mela
PO"
.F

C,
..Br .......-
.1
Heterocyclics ____l__------_t--------+-------+--
epoxy_

Nitro-
N;,,;,.. NHl Amines
N.H ____ ...
Esters ",celites
Amides
Acids
Ke"lones PhosphOrus afgano (RO),P
(RO).POH----+--------+----------1r--=--..,.
__---J--'___.f_______+_.
(RO)PO_
(RO,(PS)SM__-+_______ __
SI!i con OrpllO.!
M.ti\arg;Jr.o. VAI
,,,
'"
.
01)
..

ro<

Ox,ll"IO' ____
3Zi.d!1!_
PCl,_
PBr,_
PI.-
melllO.
mll....r
mri.ll,.
rrmllrl .
-SF, _
SO._
CIO._
PO._
s.a.__
C.o. __
MoQ._
Fl LIO. _
000.__
MoO. __
Wo._
00._
CIO,_
er{),_
IOI_
SO._
l iO,_
NbO._
F"t,o._
....0._
5,0,_
C,,o,_
SCH __
where 1',
contai n
there wil
transit ioJ
illustrat e.
is zero (i
R-brancr
The
equation
whereIIJ,
rotationc
6-19 Spectra of Gases 189
Sileon organo.SiH'__ __L-+-__....,___
SIC\

SiO
SiS

alkyl,SI
phenyiSi
phenyl .Ge--!--- -+----t-----t--"-
phenyl. Sn _ _ I_ _ _ -+___+_ _ _
phenyl .Pb _-!___-+___ -t-___ __
alkyl $n
lIlkylPb

Ferroc:.nte
Phltullocyaninti Ac:dylK:elonattS_
Oxalato
-P'-
InorSlInies CYltnldd... .
ClIrbQnyls _
11idtS___ _ f---_ _ _+- --
PC.._ ___ +-_ _ _ +-__ ___..--
pe r!_ ___ +-___-I-__---j___-+__
PI,
",cttlC, FIGURE 6-23 (conti nued)
mal al Sr,
mlUlr,
metal F
SO.
.SF'====:l===t===:;.
CIO. ____+_- --+----
PO._ _ _ _ +___+-___p __
S'O.____+-_ __I--__-+___ -+-__

MnO.----t-- -_If-----_+---+----I-
RuOo _ _ __+-___I--__-+___-+-___-t-_ _ _
Oill.____+_---_I_-----j- ---+---+---

W. ____+ ___
CIO.____

10,_
T;O.
Nbe,

5,0._ Mn,oJ...===t===t===t:::=- r
Cr'01'----+----f-----_+---_+----t-'-

800 600 400 200
WAVENUMBER IN cm-]
where V, represents the rotational frequency detected. Since any finite sampl e
contains many molecules, manydifferent rotati onalstates wiJl be populated and
there wiH be a whole series of lines corresponding to different v, values (i ,e"
transitions between many different rotational states). This phenomenon is
illustrated in Fig. 6-24.The Q-branch corresponds to the transition in which V,
is zero (i .e., a transition with no change in rotational quantum number), the
R-branch to V
o
+v" and the P-branch to va - v, .
ThefrequenciesofaH the bandsin Fig. 6-24canbeexpressed bythefoJlowing
equation:
wherem] has all integralvalues, incl udingzero, from +J to - J (where J is the
rotational quantum number)dependingon theselecti on rules. Whenm] =O,the
'
190 Chapter 6 Vibration and Rotation Spectroscopy : Infrared, Raman, and Mi crowave
Q branch
R branch P branch
transitions giving rise lo P, Q,
and R branches in a spectrum
01 a gas.
FIGURE6-24 Schematic 01 the
~ v
vibrational transition is one that occurs with no;change in rotational guantum
number. A Q-branch results. When m] is less than zero (J n + ---> J n transit ions),
lines in t he P-branch result, whereas lines in the R-branch correspond to m]
greater than zero.
A series of selection rules for the combination of vibration and rotation
transitions in various molecules is helpful in deducing structure:
1. Dlatomic Molecules. Most diatomic molecules do not possess a
Q-branch. Nitri c oxide (NO) is the only known cxample of a stable diatomic
molecule that has a Q-branch. The diatomic molecule must possess angular
momentum about the molecular axi s in order to have a Q-branch. (L states,
L = 0,have no Q-branch.)
2. LinearPolyatomicMol ecules. lf t hechangingdipolemomentfo ragiven
vi brational mode is parallel lO the principal rot ation axi s in the molecule, a
so-called paraUel band results, which has no Q-branch. The select ion rule for this
caseis I1J = 1;11) cannolbezero.Ifthedipolemomentchangeforthevi bra tion
has any vector component perpendicular to the princi pal axis, a perpendicular
band will result with a Q-branch, and I1J can be 0, 1. The asymrnetric C- O
stretch in CO
2
is a para llel band, while lhe C- O bending vibra tion i a
perpendicularbando Theutilizat ion ofthesecriteria in makingandsubstantiating
assi gnmentsofvibrat ions is apparent. If, in the spectrum ofa triat m c molecuJe,
any of t he infrared bands (v, v
2
, or v
3
) consists of a single P- and R-branch
wit hout any Q-branch (i.e. , a zero-gap separa tion), the molecule musl be linea r.
This type of evidence can be used t supporl li near st ructures for N
2
0 HCN,
andCOz . Therotationalspacingscanbeemployed,asdiscussed underthesection
on microwave spectroscopy, to evaluate lhe moment of inerti a. Note that even
thoughCO
2
doesnothavea permanentdipole(and henceis microwave inactive),
the rotational spacings can be obtai ned from the fine structure in the infrared
spect rum.
3. Non-linear Polyatomic Molecules. For the discussion of vi bration-
rotalion coupling in no n-linear polyatomic molecules it is necessary to define
the terms spherical, symmetric, and asymmelric lOp. Every non-li near molecule
hasthreefi nitemomentsofinertia.lnasphericaltop,e.g., CCI
4
alllhreemoments
areegua!. In a symmetri top,two ofthe three moments areequa!. Forexample,
of one selects the C
3
-axi ofCHJBr as the z-axis, then the moment of inerlia
along Ihe x-axis is equal lo that along lhe y-axi s. Any molecule wit h a t hreefold
orhigh r rotati on axis is a symmetric lopmoleculc (unless it is a spherical top).
In an asymmetric top, no two of lhe three moments are equal. Molecules with
no symmetry or t hose wit h on ly a twofold rotat ion axi s (H
2
0 , for example)are
asymmetric top molecules.
e
o
;
'"
E
c: '"
~
e
u'"
~
FIGURE
[From G
Spectro
permiss
For
moment
I\'ith po.
freguen
obtained
rot ation
a synl/ e
m lecul.
several ,
branches.
band ina
in Fig. 6-
11} =O. j
c:
.;
o
'"
'E
'"
e
~
Q
e
QI
u
;
Q.
FIGURE6-2
1340
6-19 Spectra of Gases 191
\ I
IIlJ
ton
vibration-
to define
mol
eculc
e
o
Ul
Ul
E
Ul
e
o

e
Q)
u

Q)
CL
1340 1320 1300 1280 1260
FIGURE 6-25 A parallel band lorCH
3
Br(symmetric top) .
(From G. M. Barrow, " Introduction to Molecular
Spectroscopy" . Copyright 1962 by McGraw-Hill , Inc. Used by
permission 01 McGraw-Hill Book Company.]
For symmetric top molecules, those vibrations having osciHating dipole
moments t hat are parallel to the principal axis produce a paraUel absorption band
with P-. Q-, and R-branches. The symmet ri c C- H slrelching and bending
frcquencies in CHJBr are examples of pa rall e! bands. The type of spectrum
obtained for a parallel band is ill ustrated in Fig. 6-25. Jn thi s example t he
rotational fi ne structure in the R-branch is not resol ved. The parallel band for
a symmet ric top molecule is similar to the per pendicula r band for a linear
molecule. For a perpendicula r absorption band in a symmetri c top molecule,
s veral Q-bands a re d tected, often \ ilh overlapping unresol ved P- and R-
branches. The C- 1 bending vibration in CH
3
Cl is an example of a perpendicula r
band in a symmet ric top molecule. A typical spectrum for t his case is illust rated
in Fig. 6-26. In a spherical IOp, the selecti on rule for a perpendicular band is
J = 0, 1. This information can be employed to support band assignments.
c:
o
.;
'E
'"
."
c:

Q
e
QI
u
...
QI
o..
Q Q
- --- iilcm-l) ----
FIGURE 6-26 Perpendicular bandcontainingtwoQbranches.
192 Chapter 6 Vibration and Rotat ion Spectroscopy : Infrared, Raman , and Mic rowave
FIGURE 6-27 Some possible
structures lar NSF
3
. N s N
111
F-S- F
1
N
111
S
1
F
/ 1"
F F F
/ I " F
F F
( Plana,)
C
2v
lt becomes very difficult in some cases to distinguish between symmetric
and asymmetric top molecules. As the symmetry of the asymmetric top becomes
lower, the task becomes easier. Considerable information can be obtained from
the band shape to support vibrational assignments. *
6-20 APPLlCATION OF RAMAN ANO INFRAREO
SELECTION RULES TO THE OETERMINATION OF
INORGANIC STRUCTURES
1. The structures in Fig. 6-27 represent so me of the possibilities thal should
be considered for a material with an empirical formula NSFj ' Table 6-8
summarizes the calculated number and symmetry of bands for these possible
structures. These results and the infrared activity of the bands should be
determined for practice, employing the procedure in the section on symmetry
considerations and the character tables in Appendix A.
The infrared spectrum has been reported. (30a) Six intense bands are found,
in agreement with the C
3v
structure but certainly not in conflict with other
possible structures. Some of the fundamentals may be of such low intensity lhat
they are not seen. However, it was found that four of the bands (VI ' Vz, V
3
, 1' 5)
have P-, Q-, and R-branches. This is good evidence that the molecule being
investigated is a symmetric top molecule and supports a structure. The C
3 v
spectral data are contained in Table 6-9, where they are compared with data
reported for POF3.(30b) The forms of the vibrations are diagrammed in Appendix
C (see the discussion of the ZXY3-molecule). These data, combined with an nmr
study, have been employed to support the C
3 v
structure F
3
S-N. Polarized
Raman studies were not ca rried out. These would not add a great deal of structural
information bu t would help confirm the assignments. The A J bands should be
polarized and the E bands depolarized.
The FJN-S structure has not been eliminated by these data. The frequencies
of the observed bands provide information to favor the F 3SN structure. The
See Herzberg (in Addilional References), pp. 380-390, for an explanation of the phenomena
just discussed. Many applications of these principies are di scussed in this reference.
s- sI
freq ucn
ntainec
equatio
would ni
6-20 Application 01 Raman and Inlrared Selection Rules to the Determination 01 Inorganic Structures 193
TABLE 6-8. Calculated Number 01 Bands lorVarious
Structures 01 NSF3
c
2
,.
(C2-axis Is the 7.-8Jlls)
C" . C.
3A 1 (IR active) 4A 1 (lRactive) 7A' (1 Ractive)
38I (IR active) 2A" (IR active)
3E (IRactive) 2B
2
(IR active)
S- N stretch is the only fundamental vibration that could be expected at a
freqllency of1515 cm- J. [A very rOllgh approximati onfor this frequency can be
obtained by employing the C C force constant and the S a nd N masses in
equation (6--3).J The NFstretching vi brations in NF3occur at 1031 cm- J and
would notbeexpe tedto beas highas 1515cm- 1 in F3N- S.TheF3 N structll re
receives further supp rt from micr wave and mass spectroscopic studies. The
lowmomentofinertiacalcul ated from thernicrowavestlldiescannotbeexp1ai ned
lInless the sulfur atom is at the center ofmass.
2. The same approach as that olltlined above was employed to prove t hat
perchlorylfluoride, CI0
3
F has a e
3u
structure ins tead of02ClOF.(30C)
3. An appreciati on for sorne of the difficultie encountered in ma king
spectral assignments ca n be obtained from an a rticl by Wilson and HlInt (la)
on the reassignment ofthe spectrum ofS02F2 ' Oft en a sel ofband ass ignments
may appear self-consistent, but the e assignment may not be a unjque sel. The
cffect of isotopic subs tit uti on on spectral shifts can be employed to provide
additional SlIpport for the assignments rnade. A Raman study has also been
reported.(3Jb)
4. The infrared and Raman spectra have been interpreted to indicate a
plana rstructurefor N
2
0
4
.(3JC) St ructures correspondingto the pla na r D
2h
mod 1
and the staggered D2d configuration were considered. Snce the infrared and
Raman spectra have no tines in comrnon it is proposed that t he rnoleculc has a
center ofsymmetry. A rigorous assignmentofthe bandscould not be made with
the available data.
5. Thespectral datafor B2H6support the bridged hydrogenstructure.<32a)
Theent irespectrumisanalyzed,assignmentsaremade,andconc1usionsregarding
the structure are drawn from the rotational fine structure of sorne of the
perpendicular bands.
6. An infrared and Raman study<32b) sllpports a planar T-shaped e
2u
structure for CIF3' Too ma ny fundamentals were observed for either a D 3h or
e3" slructure. Sorne oft he bands had po, Q-, and R-branches, while others had
only P- and R-branches. Si nce all fundamentals for a tetraatomic e
3u
rnolecule
(e.y., PF3) have po, Q-, and R- branches, this structure is eliminated.
7. The infrared and Raman spectra of B
2
(0 H
3
)4 have been interpreted
lo indicate(32c) aplanar arrangement for the boron and oxygen atoms. Many
bands were found in the spectrum. Assignments were made that are consstent
with aplanar e
2h
molecule. More fundamentals were found t han would be
predicted from a D2d mode!. The infrared and Raman spectra do not ha ve a
coincidence of any ofthe vibrations asigned to B- B or B- O modes; but, as
would be expectedfor theproposed struct ure, theCH
3
and o- evibrat ons are
found in both the infrared and Raman. Good agreement is fou nd for t he bands
TABLE 6-9. Fundamental
Vibration Frequencies for
NSF3 and OPF3
NSF,
1515 1415
775 873
521 473
811 990
429 485
342 345
I 12.0
194 Chapter6 Vibration and Rotation Spectroscopy : Infrared. Raman. and Microwave
Bond Strength
Frequency Shift
Relations
FIGURE 6-28 Inlrared
speclra 01 pehnol and a
hydrogen-bonded phenol.
assigned to the O-C and -CH} modes in this molecule and in the B(OCH
3
h
molecule, ilJ ustrating the applicability of the group frequency concept. The aboye
assignments indicate aplanar structure, but since the interpretation is very much
dependent on the correctness of the assignments, they should be confirmed by
isotopic substitution. The band assignments made are con istent with those
caleulated fr om a normal coordinate anal ysis assuming a C
2h
mode\.
One final advantage of combining Raman studies with infrared will be
mentioned. Oft en, in the infrared spectra, it is difficult to distinguish combination
bands or overtones from fundamentals. This is us ually not a problem in the
Raman, for the fundamentals are much more intense. An extensive review of the
inorganic applications of Raman spectroscopy( ll) should be consulted for other
applications of this technique.
There are many example ' in the li terat ure of attempts to infer the bond trength
for coordination of a Lewis acid to Lewis base fr om the magnitude of the infrared
shift of sorne acid (or base) functi onal group upon coordination. Usually a
relationship between these two quantities is tacitl y assnmed, and the infrared
shift interpreted as though it were a bond strength in terms of the electronic
st ructures of the acid and base. This approach is to be discouraged for the
probl em is too complex to permit su eh an assumption.
The systems that have been most thor ughly studied are the hydrogen
bonding ones. In general, hyd rogen bondi ng( 33) to an X- H molccule resul ts in
a decrease in th frequency and a broadening of the absorption band that is
a igned to the X-H stretching vi bration. The speclra of free phenol, A (where
X = C
6
H
s
O - ), and a hydrogen-bonded phenol, B, are indicated in ig. 6- 28.
Thc magnitude of ' V
OH
' the frequency shift upon for mabon of al: 1 complex
wi th a base, is rel ated l O - !lB for the formation of t he 1:1adduct meas ured in
a poorl y solvating solvent, for a large series of di fferent bases as shown(3 4) in
Fig. 6-29. Different aleohols req uire di fferen t li nes, as illustrated by the separate
A Free phenol In CCI
4
B Phenol plus donar in CCI
4
A______
B
A
~
3600 3500 3400 3300 3200
10.0
w
....
O
:e
8.0
"-
....
~
(J
x:
6.0
~
4.0
2.0
0.0
FIGURE E
Irnes are
p-t-bulylp
(6 ) The
represen1
N.N-di me!
~ v plol01
solid line
dotted li.
varied. O
various a
-.1H(kc<
-.1H(kcf
-.1H(kcc
-.1H(kCl
The authc
donors (j.
a nd !lI'OH
for a gi ve
the base \
6-20 Application 01 Raman and Inlrared Selection Rules to t he Determination 01 Inorgan ic Structures 195
12.0
10.0
w
...J
O
::E
......
8.0
...J
<
O

6.0
:i
<l
I
4.0
2.0
0.0
100 200 300 400 500 600 700 800 900
FIGURE 6-29 Constant-acid.constant-base Irequency shift-enthalpy relations. Sol id
lines are constant-acid lines. The phenol line al so contai ns values lor
p-t-butylphenol (+) , phenol ( O), p-ch lorophenol ( O ), and m-trifluoromethylphenol
(6) The acid butanol is represented by and (CF3)2CHOH by .... The number 1
represents all points on the pyridine con stant-base line ; 2, ethyl acetate ; and 4,
N,N-dimethylace:amide. (The pyrid i ne-(CF
3
h CHOH v is estimated Irom the v vs .
v plot 01 thi s acid and phenol.)
solid lines in this figure. The solid lines are referred to as constant-acid li nes. The
dotted lines represent data in which the base is held constant and the acid is
varied. Over this range of enthalpies, a linear constant-acid equation exists for
various aleohol s:
mol e -
1
) = (0.0105 0.0007) + 3.0(0.2)(phenols) (6- 25a)
mole-
1
) = (0.0115 0.0008) + 3.6(0.03)[(CF
3
h CHOH]
(6-25b)
- mol e - 1) = (0.0106 0.0005) V
OH
+ 1.65(10.09)(t-butanol) (6-25c)
mole -
1
) = (0.0123 0.0006) + 1.8(0.1)(pyrrol e(34)) (6-25d)
The authors(34-38) cauti on aga inst the use of this rel al ions hlp for a new c1ass of
do nors (i.e ., a functional group not yet tudi ed) ithout fi r t eval uating -
and for at least one system involving thi functional group. The enthalpy
for a given acid has be n shoWQ lo be related to two differ nt properties(35) of
the ba via the llowing relation:
(6-26)
l
l
l
196 Chapter 6 Vibrati on and Rot ation Spectroscopy : Infrared. Raman. and Mi crowave
where EA and E
B
are roughly relat ed to the tendency of the acid and base to
undergo electrostahc interaction and CA and C
B
to their tendency to undergo
covalent interactiol'l. Parameters for many difierent acids and bases have been
report ed. When the range ofC
8
/ E
8
is between L5 and 6.0, the enthalpy-frequency
shift correlati ons hold to within 0.3 kcal mole - l . For sulfur d nors, where this
ratio is the plots of Fig. 6-29 do not hold.(36) Unless tlv
OH
should ha ve the
same functional dependence on E8 and C
B
as - !'lH does, there will have to be
a limitation on the C/E ratio of the base that can be used. Furthermore, there
is an experimental point at which tlH and tlv
OH
are both equal to zero.
Accordingly, l he li ne wil l have to curve; this curvature is predi cted by theory( 3
7
)
The theoret ical treatment also predicts curvature on the high frequency end of
lhe curve. A a result, extrapolation of lhe curve in either direction is dangerous.
The analysis(37) indicates that frequency shifts can be employed instead of force
constants because the high-energy O-H stretching vibration is far enough
removed in energy from other vibrations that t he band assigned to it is a nearly
pure O- H stretching vibration.
In view of the considerable effort involved in an enthal py measuremen t (often
one or two days of work), this relat ionship is a welcome one for a cerlaining the
strength of the hydrogen bond. However, much confusion has been generated
by the inappropriate use of this relation. Inappropriate solvent selection, and
enthalpies that are a compo ite of t hings other than the si mple 1 : 1 adduct
formation reaetion (e.g., two di fferent donor tes in the same molecule(38)), should
be avoided.
Additional correlati ons of this sort involving different types of aeids, and
others involving some spect roscopic change in the base upon coordination, woul d
be most useful. However, they cannot be naively ass umed but must be tesled
against measured enthalpies and the Jimitations sought. In a study of the Lewi s
acid chloroform,(39) it was found that the ent halpy of adduct forma ti on did not
correlate with the observed frequency shift.
6-21 CHANGES IN THE SPECTRA OF DONOR
MOLECULES UPON COORDINATION
The infrared spectrum of N,N-dimethylacetamide in the solvent CCI
4
has an
absorption band at 1662 cm - 1 that is due to a highly coupled carbonyl absorption.
The low freq uency compared to acetone (1715 cm - 1) is attributed to a resonance
interaction with the lone par on the nitrogen (see Fig. 6-30). Upon complexation
with several Lewis acids, a decrease in the frequency of this band is observed(40)
This decrease has been attributed to the effect of oxygen coordination to the
aeid. Oxygen coordination could have several effects upon the vibration :
FIGURE6-30 Resonance structures lar
N,N-dimethylacetamide.
1.
coordi n
for the
a highe
2.
a bond
3.
force ce
cau 'es
coordin
higb -fre
oxygen
nit roge!
frequen
Th
to Fe
J

in these
T his ca
chrornil
Pd(NH:
expecte(
C-N fI
De
tion an
phorarn
A deerei
is obser'
manyrn
in lhe pi
IS an in
frequenc
The
indicate
ligand ir
in lhe ca
The

in terest.
to rr ba(
thoughl
coordim
analysis
is expe 1
shi ft aris
due to a
aLion.
14B
mIO the
for the d
The
bands in
n
:y
IS
1e
;>e
Je
ro.
~ )
of
IUS.
Irce
ll gh
arly
Iften
~ t h e
ated
and
lduct
lOuld
1, and
.... ould
lested
Lcwis
,id not
has an
6-21 Changes in the Spectra 01 Donor Molecules upon Coordination 197
1. Since the oxygen atom has to move against the atom to which it is
coordinated, an increase in frequency should result. In effect this is to say that
for the system X-O= ~ the C-O and X-O vibrations couple, producing
a higher-energy carbonyl absorption.
2. A change in oxygen hybridization could increase (or decrease) the C- O
(J bond strength and increase (or decrease) the force constant of the C-O bond.
3. The most important effect in this case involved decreasing the carbonyl
force constant by draining n electro n density out of the carbonyl group. T his
causes the observed decrease in the carbonyl frequency and indicates oxygen
coordination. The absence of any absorption in the carbonyl region on the
high-freq uency side of the uncomplexed carbonyl band is further support for only
oxygen coordination. If there were nitrogen coordination in the complexes, the
nitrogen lone pair would be involved, resulting in a decreased C- vibration
frequency and a higher-energy carbonyl absorption.
The decrease in the carbonyl stretching frequency of urea upon complexation
to Fe3+, Cr3+, Zn
2
+, or Cu
2
. is interpreted as indicating oxygen coordination
in these complexes(41
J
The explanation is similar to that described for the amides.
This concJusion is supported by x-ray studies on the structure of the iron and
chromium complexes.(42
1
Nitrogen coordination is observed in the compounds
Pd(NH2CONH2)2Cl 2 and Pt(NH2CONH2)2Cl2' and the spectra show the
expected increase in the C-O stretching frequency as well as a decrease in the
C-N frequency.
Decreases in the P-O stretching frequencies indicative of oxygen coordina-
tion are observed when triphenylphosphine oxide(43J and hexamethylphos-
phoramide, OP[N(CH
3
)2J3 ,(44) are coordinated to metal ions, phenol, or iodine.
A decrease in the S-O stretching frequency, indicative of oxygcn coordination,
is observed when dimethyl sulfoxide or tetramethylene sulfoxide is complcxed to
many metal ions, iodine, and phenol(451 The S-O stretching frequency increases
in the palladium complex of dimethyl sulfoxide, compared to free sulfoxide. This
is an indication of sulfur coordination in this complex. The N-O stretching
frequency of pyridine N-oxide is decreased upon complexation.(46)
The infrared spectra of sorne ethylenediaminetetraacetic acid complexes
indicate that this ligand behaves as a tetradentate, pentadentate, or hexadentate
Iigand in various complexes. The interpretation is based upon absorption bands
in the carbonyl region corresponding to free and complexed carbonyl groups.(47
1
The change in C-N stretching frequency of nitriles(48) and metal cyanides(49
1
resulting from their interaction with Lewis acids has attracted considerable
interest. When such compounds are coordinated to Lewis acids that are not able
to n back-bond, the C N stretching frequency increases. This was originally
thought to be due to the coupling effect described aboye in the discussion of the
coordination of amides. A combined molecular orbital and normal coordinate
analysis of acetonitrile and sorne of its adducts(48) indicates that a slght increase
is expected from this effect but that the principal contribution to the observed
shift arises from an increase in the C N force constant. This increase is mainly
due to an increase in the C-N sigma bond strength from nitrogen rehybridiz-
ation.(481 In those systems where there is extensive n back-bonding from the acid
into the n* orbitals of the nitrile group, the decreased pi bond energy accounts
ror the decreased freq uency.
There have been many papers(50-52
1
on the assignment of the absorption
bands in simple ammine complexes. T he spectra have been analyzed in terms of
:
198 Chapter 6 Vibration and Rotation Spectroscopy : Infrared, Raman, and Microwave
a single M-NH
3
group, i.e., a local C
3
" structure. In the sodium chloride range,
absorption is usually found in four regions near 3300, 1600, 1300, and 825 cm -
l
These have been assigned to N-H stretching, N H
3
degenerate deformation,
NH
3
symmetric deformation, and -NH
3
rockng, respectively. Deuteration
studies( 51) support these assignments. lt was concluded that no metal-nitrogen
vibrations in these transition metal ion complexes occur in the sodium chloride
regon. The frequencies of the bands are dependent upon the metal ion, the type
of crystal lattice, and the anion.(5 2) The anion effect is attributed to hydrogen
bondi ng. References by Chatt el al.( 52 ) are highly recommended readings for more
detai ls on this su bject.
Infrared spectroscopy has been very valuable(5 3-55) in determining whether
the thiocyanate ion, NCS -, is bonded in a metal compl x via t he nitrogen atom
or the sulfur atom. Since both modes of bonding have been detected, the an ion
is said to be ambidentate. The CN stretch generally occurs at a lower frequency
i!1 the N-bonded isomer than in the S-bonded one. The vibration assigned to
"C- S" is a better guide, occurring in the 780 to 760 cm - 1 region for
nitrogen-coordinated complexes and in the 690 to 720 cm - 1 region for sulfur-
bonded ones. The "NCS bend " is also diagnostic occurring in Ihe 450 to 440
cm - I region for the N-bonded isomer and in t he 400 to 440 cm - 1 region for
the S-bonded isomer. The observed intensity differences for t he different isomers
are also diagnosticoThe reader is referred t !i terature reviews( 56.57) for many
examples of ambidentate coordination by this ani on.
lt should be pointed out that solid materiaLs can be oblained that contain
noncoordinated donor molecules trapped in the crystal lattice. By virtue of lhe
lattice environment, changes in the spectrum of the donor can occur in t hese
instances wilhout coordination. lt is thus not pos ible to prove coordinati on by
a frequency shift in the infrared spect rum of [he donor taken on a mull of a solido
This problem can be resolved if the soli d ca n be put in soluti on a nd the spectrum
compared wit h that of the donor in tlli s solvent.
Caution should also be exercised in drawing concl usi n regarding the
strength of the interaction between a donor and a Lewis acid (including metal
ions) from the magnitude of the frequency shift of the donor. Usually, t his
relationship has not been adequately demonstrated with reli able, easily int rpreted
enthalpy data. There will very probably be cases in which good correlati ons a re
obtained, bu t no general st atements can be made at present.
Excellent discussions of the important role 11fr red spectroscopy has played
in elucidating l he st ruct ure of many transiti on metal complexes are avai la ble.(l81
The spectra of metal carbonyls, met a l acetylacetona tes, cyanide, thiocyanate, a nd
several other types of complexes are discussed.
6- 22 CHANGE IN SPECTRA ACCOMPANYING CHANGE
IN SYMMETRY UPON COORDINATION
Some of the most useful appli ca tion' of infrared spe froscopy in the a rea of
coordinaton and organomet aUic cherrustry occur when the symmet ry of a ligand
is changed upon compl xat ion. For example, t he symmetry change accompanying
t he binding of small molecules (e.g., N
z
, O
2
, a nd H
2
) to transiti on metal ons
has a dramat c infl uence on t he infra red spectra of these ma teri al s. When azide
IOn IS al
N
2
, is (
Raman
line apf
N-N s
the sam
Th<
tha! lh
enter o
vi brati o
inactive
lower fr
0 -0 1;
Wh
a rise in
21 1 cm
deuterat,
the char
hydrogel
Evi(
[rom inl
e ordina
of Ihe o,
Byd
represenl
A
2
"(JR).
The ban4
(iR) A ~ 1
vibrat ion
infrared
6-10.
The
N-D as)
B for plal
and 1280
correspor
appears.
one can r,
coordina!
in e
2
; y
roode of (
TABLE6-
for Vari o
ge,
I
:m,
Ion
~ n
ide
ype
gen
lore
l her
tom
nion
ency
Id to
for
IIlfur-
440
mfor
mers
many
ntain
ofthe
these
:lon Y
asolid.
ectrum
ng the
~ metal
lly, this
=rpreted
ons are
6-22 Change in Spectra Accompanying Change in Symmetry upon Coordination 199
ion is added to Ru(NH
3
)s(H 20)3 +, a product containing coordinated dinitrogen,
N
2
, is obtained.(S8) The stretching vibration of free N
2
is infrared inactive but
Raman active, with a band at 2331 cm-
I
In Ru(NH
3
)sN/+, a sharp intense
line appears(S9) at 2130 cm-
I
in the infrared spectrum that is attributed to the
N-N stretching vibration. In IrN
2
CI[P(C
6
H
s
hJ2 and HCoN
2
[P(C
6
H
s
hJ3 ,(60)
the same vibration gives rise to bands at 2095 cm - I and 2088 cm - 1, respectively.
The complex Ir OCl [P(C
6
H
s
hJ2 picks up O
2
and binds it in such a way
that the O-O bond axis is perpendicular to a line drawn from iridium to the
center of theO-O bond. An infrared band assigned(6 1) to the O-O stretching
vibration in the complex occurs at 857 cm - l. This corresponds to an infrared
inactive stretch in free O
2
, which does have a Raman band at 1555 cm-
l
T he
lower frequency in the complex is attributed to electron transfer making the
O-O bond peroxide-like.
When H
2
is added to IrCOCl[ P(C
6
H
s
hJ2' two new sharp absorption bands
arise in the infrared at 2190 and 2100 cm-l. The infr ared bands at 2160 and
2101 cm-
I
in IrH
2
CO[ P(C
6
H
s
h ] are shifted to 1620 and 1548 cm -
I
in the
deuterated analogue.'62) The agreement of these shifts with those predi cted from
the change in redl!lced mass indicates that these vibrations are mainly metal-
hyd rogen modes.
Evidence to support coordination of the nitrate ion can also be obtained
from infrared studies(63,6
4
1 because of the symmetry change accompanying
M
/ 0
O
coordination. Free nitrate ion has D3h symmetry, but upon coordi nation of one
"
O-N or
M/ " N-O
" O/
of the oxygens, the symmetTy is lowered to C
21J
or to es as shown in F ig. 6-3 1. "O
By determi ni ng the total representat on and the symmetries of the irred ucible C
s
C
2 v
representations comprisi ng the 3N - 6 vibrations in D 3 11 NaNO) , one finds A 1'( R),
FIGURE 6--31 C
s
and C
2v
A
2
"(IR), 2E'(R}(IR), The Raman and infrared activity is indicated in parent heses.
structures af coordinated
The bands in D 3h NaN0
3
are assigned as VI 1068 cm -
1
(R)A ', \1
2
831 cm-
I
nitrate.
(I R) A;, v
3
1400 cm - 1 (R)( IR)E', and v
4
710 cm - (R)(IR)E
f
The forms of these
vibrations are shown in Appendix B. I n C
2v
and C. syrnmetr , A becomes
infrared active and each of l he E
f
modes splits into two bands, as shown in Table
6-10.
The E' asymmetric stretch in the nitrate ion is splil into a high-frequency
N- O asymmelri c sl retch and a lower-frequency symmetric stretch (see Appendix
B for pl anar XY3 and ZXY2 molecules) upon coordination. These occur at 1460
and 1280 cm - (20 cm - 1), respectively. An additi onal NO stretching frequency,
corresponding roughl to lhe inacti ve symrnetric st retch in nit rate ion, al ' o
appears. Thus, in the absence of complicati ons from site symmet ry problems,
one can readily tell from the infrared spcctrum whether or not the nitrate ion is
coordinatcd. The magnitude of Ihe splitting of the E' mode is g nerall y greater
in e2" symmel ry lhan in C
s
' and this criterion ha ' been used lo upport this
mode of coordination.
TABLE 6-10. Correlation Chart Connecti ng the Vi brati onl Mode Symmet ri es
tar Various Kinds of N0
3
- Coordinati on
Al R) A
2
"(I R) f(IR. R) E'(IR, R)
A(IR, R)
A
I
'(IR, R)
B(IR R)
A"(I R, R)
AI (l R, R) + Bz{IR. R)
Af(lR, R) + A'(IR. R)
A(l R, R) + B
2
(1R, R)
A'(IR. R) + A'(lR, R)
200 Chapter 6 Vibration and Rotation Spectroscopy : Infrared, Raman, and Microwave
The sulfate ion is another good example to demonstrate the effect of change
in symmetry on spectra. The sulfate ion (7;1symmetry) has two infrared band
in the sodium chloride region : one assigned to V
3
at 1104 cm -1 and one to \14-
at 613 cm - 1. (See Appendi x C for the forms of these vibrations.) In the complex
[ Co(NH
3
)sOS0 3JBr the coordinated sulfate group has lower symmetry, C
3v
' Si
bands now appear at 970 (VI)' 438 (vzl, 1032 to 1044 and 1117 to 1143 (from v
3
) ,
and 645 and 604 cm - 1 (from V4)' In a bridged sulfate group the symmelry is
lowered to C
2 v
and even more bands appear. For a bridged gro up the v
3
band
of SO/- is split into three peaks and the V
4
band into three pcaks.(6
5
1Infrared
spectroscopy is thus a very effective tool for determining the nature of the bonding
of sulfate ion in complexes.
The infrared spectra of various materials containing perchlorate ion have
been interpreted(661 to indicate lhe existence of coordinated perchlorate. As aboye,
the change in symmetry brought about by coordination increases the number of
bands in the spectrum. References to similar st udies on other anions are contained
in the text by Nakamoto.(
18
1
In another appl icat ion of this general idea, it was proposed that lhe
five-coordinate addit ion compound, (CH3hSnCl' (CH3)2 S0, had a structure in
which the three methyl groups were in the equatorial positio ns because the
symmetric Sn- C st retch present in (CH3hSnCl di sappea red in the addition
compound(67) Tn (CH
3
hSnCI the asymmetric and symmetric stretches occur al
545 cm -1 and 514 cm - 1, respectively'<68) In the adduct a single Sn- vibration
due to lhe asymmetric n-C stretch is detected at 551 cm - 1. This is expecled
for the isomer with three methyl groups in l he equatorial positi on because a
small dipole moment change is associated wit h the symmetric strctch in this
isomer. For all other possible structures thal can be writ ten, al least two Sn-C
vibrations should be observed. There is al so a pronounced decrease in lhe
frequency of the Sn-Cl stretching mode in the addition compound.
Infrared spectroscopy has be n used to excellent adva ntage in a study of the
inftuence of pressure on molecular structural transformations. Several sysl ems
were found to change reversibly with pressure. Changes in t he infrared spectrum
accompanying high spin-Iow spin interconversi ons oftransition metal ion ystems
with pressure are also reported(69)
A very elegant illustration of the consequences of symmetry change on the
infr ared spectrum involves the metal carbonyl compounds of general formula
M(CO)sX and the 13C-substituted derivatives
PO
) Our main interest is the high
wavenumber region associated mainly with the carbonyl stretching vibrations.
This, coupled with t he fact that the C O stretch and the M-C st retch are
widely separated in energy, enables us to use as a crude basis set for the vi brali onal
problem the five C-O bond displacement vectors shown in Fig. 6-32A. The
operations of t he C
41
' point group for lhe all -
12
C- O compound produce the
result 2A 1 (one radial and one axial), B 1 (radi al), and E (radial). Three are infrared
activ and four a re Raman active. The forms of these vibrations are illustraled
in Fig. 6-32B.
Thc infrared spectrum of Mo( O)sBr is shown in Fig. 6-33. The band labeled
a is assigned to A 1 (radi al), e lo El' and 9 to A 1 (axial). The assignment of e to
El is confirmed by studying( 7
1
1 derivatives in which Br is replaced by an
asymmetric group that lowers tbe symmetry from C
4v
' This results in splitting
of this band into two peaks separated by 3 to 12 cm - 1 in various derivatives.
The otber bands and shoulders in the spectrum have been assigned to 13C
o'"
~
A,I
FIGUR
modes
derival
Conse(
13eo.
Fi
m()lecu
cont rib
'
e
s
IS
fl d
ed
ng

of
6-22 Change in Spectra Accompanying Change in Symmetry upon Coordination 201
X

M

e
1
o
(A)
X X X X X
A, (radial) A, (axial) 8 ,
*-t-***
E
(B)
FIGURE 6-32 (A) CO basis set lor carbonyl stretches. (B) The resulting normal
modes.
deriva ti ves, for there is 1.1 % 13e in naturally occurri ng carbon compounds.
Consequently, 1.1 % of the molecules have an axial Deo and 4.4 % have a radial
Deo. There will be very few molecules wi th two 13e groups in them.
Fi rst, we shall consider the consequences of having an axial Deo in the
molecule. The symmetry is still C
4 V
' a nd the B 1 and E modes (which ha ve no
contribution from the axial group) will be unaffected by lhe mass change. The
lwo Al modes having the same symmetry will mix, so isotopic substit ution could
affect both; but it will have a major effect on Al (axi al). The band h (at
1958 cm - 1) in the spectrum is assigned to A1 (axi al), for il is roughly what can
be expected for the change in 9 from the mass change.
(b) (e)
al Id e f 9 h ab d h
100
I
rf
N

,
100
80 80
60 60
40 40
11
r\V
hl
1
r
..
1;
20 20
O o
11
FIGURE 6-33 (A) High resolution inlrared spectrum of Mo(CO)sBr in the 2200 to
1900 cm - ' region . (B) Spectrum after three hours 01 exchange wi th '3CO.
.
l
'
202 Chapter6 Vibration and Rotation Spectroscopy : Infrared. Raman . and Mi crowave
x x x x x
f*-t-*f
A"
FIGURE 6-34 Infrared allowed vibrations in M(CO)4('3CO)X with 13CO in the radial
position.
FormoJeculesin whicha 13COis locatedin theradial position,thesymmetry
is lowered to C
s
, leading to the possible vibrations (the solid circle indicates
l3CO) illustrated in Fig. 6-34. Only the A" will rigorously be unallected by the
mass change, and it resembJes the E mode in the all_
12
O molecule. AII of the
other four modes ca n mix and could be shifted by di stributing the mass effect
over all four modes. This would shift the vibrations to lower frequencies than
those in the all 12CO molecule. Band f is assigned as al1 A' mode in the radial
13 O monosubstit uted molecules that is largely A' . Band d is either a radial Al
mode of the axially substituted molecule or the highest A' ofthe C
s
molecule.
Thefo rmer assignment would involve an intensity that is about 1% of the Al
in the aH 12eo molecule; since the intensity is foun d to be abou! 10%, it is
ass igned to an A' mode in the C
s
molecule. A normal coordinate analysis(4) has
been ca rried out to substantiate these assignments. An important part of this
work is t he assignment of a particular band to radi a] ligands and another to
axial ligands. When l3CO is added, the change in intensit y of these bands can
be followed and the relative rates ofaxial versus radial substit ution determined.
Jones et al.
s
have ca rried out a normal coordinate anal y, is on systems of
[his type, employing a large number ofisotopes. They conclude that the n-bond
orders on these systems obtained by using the Cotton-Kraihanzel(4) approxi-
mations must be viewed wit h suspicion. The m re complete analysis indicates
thatas the for mal positive cha rge on the central at om increases in forming
M( O)s Br from M(CO)6' the O'-bonding increases and t he cxtent of n back-
bonding decreases.(S) This study(5 ) provides a good reference lo illust rate the
informat ion that can be reliably obtained [rom a normal coordinate analysis.
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(19
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~
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elTect
than
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al Al
lecule.
he Al
~ it is
;(4) has
of this
ther to
Ids can
mined.
tems of
x-bond
IPPro
x1
-
ndicates
forming
x back-
rate the
alysis.
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'
204 Chapter6 Vibration and Rotation Spectroscopy: Infrared, Raman, and Microwave
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49. D. F.Shriver and 1. Posner,1. Amer. Chem. Soc. ,88, 1672 (1966).
50. M. G. Miles el al., Inorg. Chem., 7, 1721 (1 968), and references therein.
51. S, Mizushi ma, t Nakagawa, and1. V. Quagli ano,1. Chem. Phys., 23, 1367 (1955); G.
Barrow, R.Krueger. and F. Basolo,1. l norg. Nucl. Chem.. 2,340(1956).
52. J.Chatt, L. A. Dunca n'on,and L. M.Venanzi,1. Chem,Soc" 1955,4461; /956;2712.
53. 1. Lewis, R. S, Nyholm, and P. W. Smith, J. Chem. Soc., /96/ , 4590.
54. A, Sabatini and I. Bertini, Inorg. Chem. ,4, 959 (1965).
55. N.1. DeSlefano and 1.. L. Burmeister, Inorg. Chem., /0, 998 (1971).
56. J, L Burmeister, Coord. Chem. Rev., 3, 225 (1968).
57. A. H, Norbury and A.I. P.Si nha, Quart. Rev. Chem. Soc.. 24, 69 (1970).
58. A. D. AlIen and C. V. Senolf. Chem. Comm., 621 (1965) ; A.D. Allen, el al., J. Amer.
Chem.Soc. ,89,5595 (1967); A. O,AlIen and F.Botlomley, Accls. Chem. Res., /,360
(1968).
59. 1. P.Coliman and Y. Ka ng, J . Amer. Chem. Soc. ,88, 3459 (1966).
60. 1. Yamamoloet al. , Chem. Comm., 79 (1967); BulI. Chem,Soc,Japan,40, 700(1967).
61. P. B. Chock and J Hal pern. J. Amer. Chem. Soc.,88,351 ( 1966).
62. L. Vaska, Chem. Comm. 614 (1960).
6 . B.
C.
64. 1. R
65. K. r
Ll
66. B. J
67. '
68. H. ~
Edg
69. 1. R.
70. If [
71. 1. B.
A. In 1I
Introduc
N n.Ce
~
L. H. 101
W. G. F
Vlb,
LAW
G. Barr
AdvatJCe
G.Her/b
G. Herzb
Prim
E. B. WiI!
ork
D. Slecle.
B. Rcfer
L. H.10nl
M.DaviCl
1963.
.Nak.lm
4t hel
K. akan
Day.
strucl
A. Fi nch t
Nt:\\
L. J. Bell a!
1975.
L. 1Bellan
1974
58).
8).
,3/4,
cncCS
1971) ;
963).
972).
Drago
n. Soc.,
alional
therein.
n.
. Amcr.
/,360
(1967).
63. B. M. Gatehouse, S. E. Livingston, and R. S. Nyholm, J.Chem. Soc., /957,4222 ; e
c. Addison and B. M. Gatehouse, J. Chem. Soc., /960,613.
64. 1. R. Ferraro, J. Inorg. ucl . Chem. , /0, 319 (I959).
65. K. akamotoet al., 1. Amer. Chem.Soc., 79,4904(1957) ;e G. Barraclough and M.
L. Tobe, 1. Chem. Sec., /96/ , 1993.
66. B.J. Ha thaway and A. E. Underhill, J. Chem. Soc. , /96/, 3091.
67. .A. Matwiyoffand R. S.Drago. Inorg. Chem., 3, 337 (1964).
68. H. Kriegsman a nd S. Pischtschan, Z.Anorg. AII gem. Chem., 308, 212 (1961); W. F.
Edgell and e H.Ward,J. Mol. Spectr., 8,343 (1962).
69. 1. R. Ferraro and G. J. Long, Accts. Chcm. Re ., 8, 171 (I975).
70. H. D. Kaesz et al. , 1. Amer. Chcm. Soc.,89, 2844 (1967).
71. 1. B. Wilford and F. G. A. Stone, Inorg. hcm., 4, 389 (1965).
A. In the area ofinfrared, highly recommcnded refercnccs dealing with theory are:
Introductory
. B. Colthup, L. H. Daly, and S. E. Wi herl cy, " Introduction to Infrared a nd Ra man
Spectroscopy," 3rd ed., Academic Pres , ew York, 1990.
L. H.Jones, "l norganic Vibrational Spectroscopy. " Vol. 1, M. Dckker, ew York, 1971.
W. G. Fately et al., "lnfrared and Raman Se1ection Rul es or Mol ecular and Latti ce
Vi brations :The Corrclation Method," Wiley-Intersciencc, New York, 1972.
L. A. Woodward, "Int roduction to t he Theory of Molecular Vibrations and Vibrational
Spectroscopy," Oxford Universily Press, New York, J972.
G. Barrow, Ulntroduction to Molecular Spectroscopy," McGraw- Hi ll , ew York, 1962.
Advanced
G. Herzberg," Spectra of Diatomic Moleculcs," 2nd ed., Van ostrand, Princcton, 1950.
G. Herzberg, "Infrared and Raman Spectra of Polyatomjc Molecules" Van ostrand,
Princeton, 1945.
E. B.Wilson, J. e Decius, and P e Cross,.,Molecular Vibrations," McGraw- Hill, New
York, 1955.
D. Steele, "Theory of Vibrational Spectroscopy," W. B. Saunders, Phil adelphia, 1971.
B. References dealing with applications are:
L. H.Jones,"Inorganic Vibrationa l Spectroscopy," Vol. 1, M. Dek ker, New York, 1971.
M. Davies, ed., "Infrared Spectroscopy and Molecular Structure," Elsevier, Amsterdam,
1963.
K. Nakamoto,"Infraredand RamanSpectraofInorga nicandCoordinationCompound s,"
4th ed., Wiley, New York, 1986.
K. Nakanishi and P. H.Solomon," I nfrared Absorption Spectroscopy" 2nd ed. , Holden-
Day, San Franci sco, 1977. his reference contains many examples of involving
structure determination oforganic compounds from infrared spect ra.
A. Finch et al. , "Chemical Applications ofFar 1nfrared Spectroscopy," Academic Press,
New York, 1970.
L. 1. Bcllamy,"The Infrared Spectra ofComplex Molecules," 3rd ed., Wiley, ew York,
1975.
L. J Bellamy,"Advancesin Infrared GroupF requencies," Halsted Press, ~ w York, 1968.
ADDITIONAL
REFERENCES
206 Chapter 6
EXERCISES
Vibration and Rotation Spectroscopy: Infrared, Raman, and Microwave
1. R. Ferraro, "Low Frequeney Vibrations of Inorganie C ordination Compounds,"
Pl enum Press, New York, 1971.
" Praeti ealFourierTransformInfraredSpeetroseopy,"eds. J. R. Ferraroand K.Kri shman,
Academie p,ess, San Diego, 1990.
Compllallons
"SadtlerSt andardSpcetra,"SadtlerResea reh Laboratories,Phil adelphia, Pa.(Aeolleetion
ofspeetra for use in identifieation,determination ofthe purit y ofeompou nds, etc.)
Raman Spectroscopy
H. A. Szymanski ,ed.," RamanSpeetroscopy," Plenum Press,NewYork,1967;Vol. 2,1970.
A.Anderson, ed., "The Raman ElTeet," Vols. 1and 2, M. Dekker, New York, 197J.
M.C. Tobin,"Laser RamanSpcct roscopy," Wiley, ew York,1971; Vol. 35 in "Chemi cal
Analysis," P.1. Elving and I. M. Kolthoff,ed.
R.S.Tobias,J.Chem.Edue., 44,2, 70 (1967).
J.A. Koningstein,"IntroduetiontolheTheoryofthe Raman lTeel," D.Reide!,Do rdrecht ,
1972.
D. A. Long," Raman Spectroscopy," MeGraw-Hill , New York, 1977.
J.M.Stencel, " Raman Spectroscopy for Catalysis," Van ost rand Rei nhold, ew York,
1990.
A. T. Tu,"Raman Spectroseopy in Biology " Wiley, New York , 1982.
C. B. Moore,ed., "Chemieal and Bioehemieal J\pplieations of Lasers," Aeademic Press,
Ncw York, 1974.
\. Considcrthee
3
.. st ructureof - SFJ' (a) Showthatthe total represent atio nis E =15;
2eJ =O;30'" =3. (b) Indicat ethe proeedurc thal shows that t he irreducible repr en-
tati ons 4A , IA
2
and 5E re ult from this total represe ntation. (e) Show that
4A +lA
2
+5E equals E =15 ; 2e
3
=O; 3a
u
=3. (d) Indicale the speei es for the
allowed :(e) infrared,(l) Raman,and(g) Raman-polarized banos. (h) How many bands'
would be seen for(e),(l), and (g),ass uming all allowed funda menlal s are observed?
2. ConsiderXeF
4
as ha vingD..h symmet ry. Using lheproeedure in exereise 1,show that
the total number of vibrati ons is indicated by A,g +B9 +8
2
" +A
2
" +B
2u
+2E".
Also indicate the speeie for the allowed (a) infrared, (b) Raman, and (e) Ra man-
pol arized bands. (d) Huw many bands would be seen for (a), (b), and (e),assumingall
allowed fundamen tals are observed ?
3. Consi der the molecule trans- 2F2'
a. To which point group does it elong?
b. How many fundamental vibrations are expected?
C. To whal irreducible rcpresent ations do these belong?
d. What is the difference bet ween the A" and B" vibrations?
e. Whi ch vibralions are infrared active and which are Raman active?
f. How many polarized lines areexpeeted ?
4.
a.
b.
5. a.
b.
a.
b.
7. S
sI
recht,
York,
Prcss,
Exercises 207
g. How many lines are coincident in the infrared and Raman? Does thi sagree with
the center of symmetry rule ?
h. To which species do lhe following vibrations belong? N-N stretch. symmctric
N-Fstretch, and asymmetric N-Fstretch.
i. Can the N- stretch and N-Fstretch couple?
4. lndicate to which irreducible reprcscntati ons lhe vibrations belongand indicalc how
many active IR,aclive Raman,and polarized Raman lines are expected for:
b. A linear N
1
F2 molecule (D" 1,)
5. a. Why is cis- 2 2 in the point group e
2
" instead of D
21
,?
b. What symmctry element is missing from the pyramidal structurc of SF
4
that IS
required for D
4
/o (i.e" which oneelerncnt would give rise to all mi ssi ng opl:rations)?
6. The infrared peetrum ofgaseous HCIconsists ofa series oflines spaced 20.68 cm- 1
apart. (Recall that wavenumbers must be converteli to frequen cy lO cmploy lhe
equations gi ven in this text.)
a. Calculatc the momenl ofinerti a ofHC!.
b. Calculate the equilibrium internuclear separation.
7. uppose that valence considera tions enahlcd one to conclude that the foll owing
structures were possible for lhe hypothetical molccul c X2Y2 :
y
y-X-X-y
Theinfraredspectrumofthegashasseveral bandslVith P-, Q- , and R-bra nches.Which
tructures are eliminated?
8. An X- H fund amental vibration in lhe linear molecule A-X- H is found lo occur
at 3025cm- l At what frcqucncy is the X - D vibration expected? ltis found lha t
theX- Dvibration is lowered by only about halftlleexpected amount,and the A- X
stretching frequency is affected by deuteration, Explain. Would you expect the
A-X-H bending fr equcncy to be affecled by deuleral ion? Why?
9. HolV many normal modes of ibrali on does a planar SCIJ molecule hay ?Rder lo
ppendix C and illustrale lhese modes, Indicale which areinfrared ina ti ve. onrtrtn
these conclusions by employmg symmetry consideralion to delermine lh numberof
acti ve infr, r d and raman lines. Indicale the Raman pOlarizecf and depolarizcd lines
and the pa ralleland perpendicular vibrations.
10. h following assignments are reporled for the spectrum ofGeH
4
: 2114. T
2
; 2106,
Al;931 ,E; 819. 7 ~ Label these using Ihe v" s mbolism. (E modes are numbercd after
singly degenerat csymmel ric and asyrnmetric vi brali ons,and T modes ar numbered
afler E modes.)Refer to Appendix elo illust ratethe form fo rcachoflhe.e vibrations
and label th m as bends or stretches.
208 Chapter 6 Vibration and Rotation Spectroscopy : Infrared, Raman , and Mi crowave
11. Refer to the normal modes fo r aplanar ZXY2-molecule (Appendix e). Verify thc
assignmentofv
s
asBl andv
6
asB1 byuseof thecharactcrtablcs. Explaintheprocedure.
12. a. Indicate theinfraredandRamanactivities for themodesofthetrigo nal bipyramidal
XYs-molecule (Appendix Cl.
b Docs this molecLile possess a center ofsymmetry')
13. The spectrum of Co( H
3
),,(CI0
4
lJ has absorpLon bands at 3320, 3240, 1630, 1352,
and 803 cm l For purposes ofassi gnment ofthe ammonia vibrations,the molecule
H]31
ca nbe treatedasa e3u-molecule, .Refer to AppendixC for adi agram
[
of the e modes; utilizing the material in this chapter and Chapter 4, assign these
modes. Use the V
n
symbolism to label the bands and also describe them as bends.
tretches., etc.
14. What changes would you expect to see in the infrared spectrum of H3 O CH] if
a. coordination occurred on oxygL:n ?
b. coordination occurrL:d 011 slIlfur?
15. In which case would the spectrum ofcoordi nated [(CH,hNJ3PO be mast likel y to
resemble the spect rum ofthe free Ijgand:
a. Oxygen coordination?
b. t rogen coordinat ion?
Why?
16. Usingavalueofk =4.5 X 10
5
dynescm-1forthec-ebondstretchingforceconstanl.
calculate the wavenumber(cm- 1l for lhe C-Cstretching vibration.
/CH
2
- H
2
17. he compound HgCI
2
' O '::-0could be a linear polymer with di oxanc
CHz- CH2
in the chair form ora monomerwith bi dentale dioxaneinthe boat form.Howcould
infrared and Raman be used to di stinguish bet ween these possibilities'l
18. Which complex would have more - O vibrations: (NH)l5CoNO/" or
(NH))sC ON0
2
+?
19. What diflerences (number ofbands and frequencies) are xpected between the ( -O
absorptions 01' the following:
20. Given the NH3 molecu]e below, determine the total representation for lh vi brations
and () 's(8
2
notshown).Use projectionoperat ors lodeterminethevibrational
wave Cunctions.
Exercises 209
r
H)
Z'
HI ../9,
~ H
21. Consider the tetrahedral anion BCl
4
-.
9. How many bands do you expcct io the infrared spectrum?
b. How many bands do you expect in the Raman speclrum?
c. How many Raman-polarized bands do you expect?
d. How many S- CI stretches do you expect in the IR ?
to
22. Thc hyd rogen booding Lewis acid CHCI) has a C-Hstretching freq uency that is
lowered upon deuteration.
a. What is responsible for the theorcticalfactor of 1.4?
b. What could be responsible if the observed factor were le. s than 1.4?
c. When the compound is dissolved in the Lewis base NEt
J
, the C-H st retching
frequency is lowered. Rati onalizc the 10wcring.
d. Ifone examin s the C- O shift upon add uct fo rmat ion with Et)N, the percentage
lowering is smaller than that in (b). Rati onali ze this finding.
23. he compound (CHJhSnCIexhibits two infraredactive Sn-C l retchesat 545 cm-
and 514cm 1 The1 Rspcctrum 00 the five-coordinate add uct B (CH)hSnCI (where
Bis a base) shows a single Sn-Cstret ching band around 550 cm-
1
9. onsider a tetrahcdral struclurcfor (CH)hSnCI and predict the numberofSn-C
stretches expected.
b. Assume a tri gonal bipyramidal structure for the adcl uct with the methyl groups
Iying in a pl ane. How many Sn-C stretching bands are expected?
c. How do you explain the actual spectru m?
24. 3 . How many infra red-active nor mal modes con taining Sn-CI stretching would be
expccted for t hc six-coordinate species cis-SnC1
4
X
2
?
b. Describe bricfty the selecti on rules for Raman speclrosocopy and for infrared
sp ctroscopy.
210 Chapter 6 Vibration and Rotation Spectroscopy : Infrared , Raman, and Mi crowave
25. Iron pentacarbonyl, Fe(COJs, possesses D
3
. symmetry.
a. Determinelhe numberand irreducible representationsortheIR-activeand ;::aman-
active rundamentals lo be expected for this compound.
b. the number orTR-active carbonyl stretching bands to be expected.
26. Consider the following IR data, taken from NakamolO's book
l 18J
:
K
3
[ Mn(CN)J
2125 cm- 1
K
4
[Mn(CN)GJ 2060 cm-
I
Ks[ Mn(C )J 2048 cm-
I
Oiscllss lhis trend in CNstretchingfrequeneies in terms ofbonding in thecomplexcs,
and the relationship this hason force eonslants and frequencies. What do you predict
for lhe Mn-C force constanls in this series')
27. Use ofIR and Raman speetroscopy is valuablc in determining the stereochemi stryof
metal carbonyl complexes and va rious substituled metal carbonyls. C=Ostrelehes
areoftenanalyzcdseparatelyfrom lherestor the molcculc(explain whyIhisassumption
is oris not valid).
a. For Cr(COJ
and Cr( CO)s L (lreat L as a point ligand), work out lhe symmetry
of the 1 R- and Raman-allowed CO st relches.
b. Do the same as in (a) for Mo(CO)4DTH (DTH is lhe bidenlale ligand
CH
3
SCH
2
CH
2
SCI-I
J
), and for tral1,I-Mo(CO)4[P(OC
6
H
s
) J]2' Do your findings
explain the IR spectra below? (Hint: remember asumplions impl ieit in lhe
analysis.) [ peelra reported by M. Y. Darensbourg and D. 1. J,
Chem, Ed,47, 33 (1970),J
2000 1900cm-
1
2000 1900 cm-
1
w w
(J (J
z z
80 80
:!
g
i

60 60 :::&
Z '" Z
'"
< <
40 40
a:: a::

20 20
Nuclear Magnetic
Resonance
7
Spectroscopy-
Elementary Aspects
In this chapt r, lhe principIes neces ary for an el ementary appreciati on of nuclear
Introduction(1,2,3)
magnetic re onance(I - 3) (nmr) will be present d. The Teader mas teri ng this
chaptcr wi ll have a minimum kno Iedge of those principies required for spectral
interpretat ion of the r sults from slow passage as well as Fourier tra nsform
experimen ts. Chapter 8 expands upon several of thc important concepts in-
troduced hefe and illustr tes several ot her types of applications of nmr. Varyi ng
appreciati ons of t his ubject a n be obtained by complete reading of Chapter 7
rnctry
and se lected readi ngs from hapter 8.
Protons and neutrons both have a spin qll anturn nu n ber of 1/
2
and,
ligand depend ing on h w these part icles pair up in the nucl liS, the resultan! nucleu
may or may not have a net non-zeTO nuclear spin qll antum number, 1. If the
spins of all the particles are pai red, there will be n net spi n and the nucl ear spin .
quantum number I will be zeTO. This type of nucleus is said to have zero spin
and is reprcsenlt:d in Fig. 7-I (A). When 1 is '/2' !here is one net unpaired spin and
lhis unpaired spin imparts a nuclear magnel ic moment, JI to the Iluc/ells. T he
di tribu!ion of positi ve eharge in l nucl us of this typ i phcrica l. Thc propert ies
for 1 = 1/
2
are repre' nled symbolically in Fig. 7-1(B) as a pinniog sphere (vide
infra). When 1 1, the nucleus has pi n associated with it and the nuclea r charge
dist ri bution is non- phcri cal: see Fig. 7- 1( ). The nucleus is said to possess an
electric quadrupole moment eQ, where e is the unit of electrostatic charge and
1= o, )l = O I = } )l te O, eO = O 1 ) 1, )l te O, eO >0 I 1, )l te O, eO < O
(A) (B) (e)
(D)
FIGURE 7- 1 Vari ous representations 01 nuclei . 211
212 Chapter 7 Nuclear Magnelic Resonance Speclroscopy-Elemenlary Aspecls
Qis a measure of the devialion of lhe nuclear charge distribulion from sph ri cal
symmetry. For a spherical nucleus, eQ is zero. A positive value of Q indicates
that charge is oriented aJong the direction of the principal axis (Fig. 7-1 (C)),
while a negative value of Q indicates charge accumulation perpendicular to the
principal axis (Fig. 7-1(D)).
Nuclei with even numbers of both prolons and neutrons al! belong to the
type represenled in Fig. 7-1(A). Typical examples nelude
16
0 , 12e , and 32S. The
values for 1, /.1, and eQ for many other nuclei have been tabula ted,< l. 2. 3) and are
more easily looked up than figured out. Atable summarizing these properties is
included inside the front cover.
Nuclear magnetic resonance speclroscopy is often concerned wilh nuclei
wit h 1 = 1/
2
, examples ofwhich include lH, 13C. 31p a nd 19F. Spectra also result
from nuclei for which 1;:: 1, but cannol be obtained on nuelei wilh 1 = O.
Unpaired nuclear spin leads to a nuclear magnetic momenl. The allowed
orientalions of lhe nuclear magnelic moment vector in a magnelic field are
indicated by lhe nuclear spin angular momentum quantum numher, mI ' This
quanlum number takes on values 1, 1 -1, ... ,( -1 + 1), -1. When 1 = I/
Z
'
mI = 1/
2
corresponding to alignments of the magnetic moment with and op-
posed to the field. When 1 = 1, mI has values of 1, O, and - 1, corresponding,
respectively, to alignments with, perpendicular to, and opposed to the fi el d. In
the absence of a magnetic field, al! orientat ions of the nuclear momenl are
degenerale. In the presence of a n external fiel d, however, this degeneracy wil! be
removed. For a nuc!eus with 1 = 1/
2
, the mI = + 1/
2
state will b lower in energy
and the _1/ 2 slate higher, as indicated in Fig. 7-2. The energy d ifference belween
the two slales, a l magnetic fi el d strengths commonly employed, corresponds to
radio frequency radialion; il is lhis transition lhat occurs in t he nmr experiment.
m, = -'2
1
E
N
e
m
'= +'2
1
, =-'2
1
m
r
R
G
m, = +tl
t:.E
Y
No applied Applled
field magnetic field
FIGURE 7-2 Splitting 01 the m = '/
2
states in a magnetic
lield.
vcctc
the a
p is
the a
sho\\
angu
dime
Asso(
whict
w h r ~
chara
ratio
nlOm(
A nuc
If a b
the aI
{/ is tI
and (rJ
The il
( n the
Thc IT
it to I
equati
field j
Classical
Description of
the NMR
Experiment-The
Bloch Equations
7- 1 SOME DEFINITIONS
We begin our classical description of nmr by reviewing sorne of the background
physics of magnetism and defini ng a few terms necessary to understand nmr. l t
is very important to appreciate what is meant by angular momentum. Ci rcula l ing
charges have angular momentum associated with them. P lanar angul a r mo-
mentum, p(ep) is given by p(ep ) = r x mv where r , shown in F ig. 7- 3 is the position
en
with ti
lO Ne
1
lorque
7-2
7-2 Behavior 01 a Bar Magnet in a Magnetic Field 213
vector of the particle e; v its linear momentum vector; m is the mass; and r.p is G
ical
theangularchangethatsignifies an angularmomentum.Theangularmomentum
ates
:C)),
the
the
The
I are
les IS
.uclei
'esult
owed
:t are
This
= 1/2'
d op-
lding,
:Id. In
11 are
,..ill be
:nergy
:tween
nds to
Ilent.
und
mo-
position
p is perpendicular to the plane of the circulating change, and the direction of
the angularmomentum vector is given by the right-hand rule. For the situation
shown in Fig. 7-3, the vector points into the page.
The nucleus is a more complicated three-dimensional problem. The total
angular momentum 01 a nucleus is given by J, but it is convenient to define a
dimensionless angular momentum operator by
or = l/t (7-1)
Associated with the angular momentum IS a classical magnetic momenl, ~ N
which can be taken as parallel to J, so:
(7-2)
where y, the magnetogyric (sometimes caJled gyromagnetic) ratio is a constant
characteristicofthe nucJeus. From equati on (7- 2), we see that the magnetogyric
ratio represents the ratio ofthenuclear magnetic moment to the nuclearangular
momentum.
7-2 BEHAVIOR OF A BAR MAGNET
IN A MAGNETIC FIELD
Anucleuswitha'magneticmomentcan be treatedasthough it wereabarmagnet.
Ir a barmagnet were placed in a magneti c!leld, the magnet would prec ss about
the applied field,Ho,as shown for a spinning nuclear mom nt in Fig.7 . Here
nis the angle that the magnetic moment vector makes wi th the applied field,
anu w, the Larmorfrequency, is thefrequency ofthenuclear moment precession.
Thc instantaneous motion of the nuclear moment (indicated by the arrowhead
011 lhe dashed circle) is tangential to the circle and perpendicular to Ji and Ho.
The magnetic field is exertinga force or torqueon the nuclear moment, causing
it to precess about the applied field. For use later, we would like to write an
cquation to describe the precession ofa magnet in a magnetic field. The applied
neld Ho exerts atorquet on Ji which is given by the cross producl :
(7-3)
The right-hand rule teUs you that the mamen! is precessing dockwise in Fig. 7-4,
wilh lhe lorque andinslantaneous molionperpendicular lo ii and Ho. According
to Newton's law, force is equal to the time deri vat ive of the momentum,so the
torque is the time derivative ofthe angular momentum.
d _
t = - (tl)
de
r
e-
FIGURE 7-3 Circulaling
charge giving rise lo planar
angular momenlum.
,
... ~ - -
'.
---
Nuclear
:-> moment
FIGURE 7-4 Precession 01
a nuclear moment in an
applied lield 01 strenglh Ho.
1
!
l

x
214 Chapler7 Nuclear Magneti c Resonance Spectroscopy-Elementary Aspects
z
->-_/
J?------y
FIGURE 1-5 The rotating
trame u, v, z in a Cartesian
coordinate system x,
y, z.
With the equationji= fli . the equatonfarprecesson of the moments gi ven
by:
4i
)l d(fli) ~
=)Ir
dt dt
or
(7-4)
dji. ~
- = ji= - 'Hax ji
dt
(Thedot isan abbreviation for Ihe time derivative ofsorne properly, in this case
ji; the minus sign arises because we have changed lhe order for taking the
cross product.) Thus, w, the precession frequency or the Larmor frequency, is
given by:
(7-5)
whcre thesign of)l determinesthe sense ofthe preeession. According to equation
(7-5), thefre quency oI the precession depends upon thf.' appli ed}l e/d strength and
the magnetogyric ratio ofthe I1lldelt s. The energy ofthissystem s yi ven by the da(
product of jiand Ha.
;; = - ji . 110= - [i [[ Holcos O (7-6)
7-3 ROTATING AXIS SYSTEMS
There is one more mathematical construct that greatly aids Ihe analysis of the
nmrexperiment,and this is lhe idea ofa rotating coordi nal syslem or rotating
Irwne. In Fig. 7-5, a et ofX - , y-, and z-coordinates i ill uslrated.The rotating
fra me is described by he rotali ng axes 1I ami e, which rot ate al 'ome fr equency
w in lhe xy-plane. The z-axis is common to bot h coordinalc sy'tems. 11' t hc
rotati ngframe rotatesalsomcrrcqucncyless Ihan the Larmorfr eqll ency,it would
appearloanobse rveron lheu,vframe thatlhe prccessionalfrequcncy hasslowed,
which would corrcspond to a wcakening of lhe appli ed field. Labeling this
apparent ly weaker fleld as H
eff
, our precessing moment is described in the
rot ating frame by
(7- 7)
where IHoff l< IHol.H
efr
is seen to be a function ofW , and if W is raSler than
the pr cessional fre quency ofthemomen t,(u. it wi ll appearas thollgh lhe z-fi el d
has changed direction.Theelrecti e !leld. l1.rr ,can be wrillen as:
(7- 8)
whe
;r. e
W h ~
l fra
and,
7-4
he
Concl
infor
cnscn
blllk
l/ el I/i
Inan
be IOj
aligi1lT
eqllati
If
tbeS Y ~
eqllilib
where R
per lInit
from eq
at3001<
(3 x 10
Thl
w have
changin
invol vcs
nuclei in
a magne
the fi eld
from me
/.\ {ji /)(;'11
(7- 4)
(7--5)
ation
{/l1d
the dot
(7- 6)
in thc
(7- 7)
lhan
:-fiel d
(7- 8)
7-4 Magnetization Vectors and Relaxation 215
wheree is a unit vector along lhe z-axis. The lime dependence orlhe moment,
z
Ji , can be rewritten as
( (J I)_ ] _
J.l = - y
[
\ Ha - y ez x J.l
(7-9)
Whcn (JI = (J) = yH
o
, then 1/-/<lTI = Oand jiappears to be stationary. Thus, in
a rrame rolatingwilh lhe Larmor rrequency,we haveeliminatcd limedependency
and, in so doing, greatly simpli flcd the problem.
7-4 MAGNETlZATION VECTORS ANO RELAXATION
The concepts in this section are vital to an understanding ornmr. Of these, the
concept or relaxation wil l be developed in stages as the nccessary background
inrormation is covered. For practical purposcs it is necessary to consider an
ensemble or la rge number ormoments because the nmrcxperiment is done with
bulk samples. The moments in lhe sample add vectorially to give a
11ft magnetizatioll, M .
M= Lji (7-10)
In an ensemble orspins in a field, those orientations aligncd wit h the field will
be lower in energy and preferred. However, thermal energies o ppose total
alignment ; experimentall y, onl y a small net magnetizat ion is observed. The
cquation ror the motion orprecession orMis si milar to that ror ji,i.e.,
(7-11)
Irwe place a sample in a magnetic field at constant temperature and allow
the systcm to come to equilibrium, the resulting system is said to t eat thermal
equilibrium. At thermal equilibrium, the magnetiaticJfl. :"Vl
o
, is given by
11
2
N
IMol= f(l +I)Ho
(7-12)
where k is the130l tzmann constantand N o is the number ormagnetic mome nts
per unit volume(i.e., the numberorspins per unit volume).This equation results
rrom equation (7- 6)and the assumption ora Boltzmann distribut ion. For 1-1
2
0
at300 Kand Ho = 10,000 ga ll ss(1 tesla) the valueorMo is about3 x 10-
6
gauss
(3 x 10- 10 T).
T hc deseription orthe magneti/'.ation is not yet complete ror,atequili brium,
we have a dynamic situat ion in whieh any one gven nuclear moment is rapi dly
changingitsorientationwit h respect tothefield. Themechanism ror reorient a tion
involves t ime-dependent fields that arise rrom the molecula r moton ofmagnetic
nuclei in the sample. Suppose, as in Fig. 7-6. that nucleus B, a n llc!eus tha t has
a magnetic moment, passed by nucleus A, whose nuclear moment is opposed to
the field. The spin orA eould be oriented wit h the field via the fluctuating ficld
rrom moving B. In t he proces. t he tra nsl ational o r rota tional energy or the

A
'\
7
B
FIGURE 7--6 Relaxation
mechanisms.
l
,
7-5
216 Chapter 7 Nuclear Magnetic Resonance Spectroscopy-Elementary Aspects
t
M u-----t) )
(A) (8) (e) (O) (E) (F)
FIGURE 1-7 The decay 01 the Mu-component and growth 01 the
Mz-component when a lield in the u-direction is turned off and one in the
z-direction is turned on.
molecule containing B would be increased, since A gives up energy on going to
a more stable orientation aligned with the field. This process is referred to as
spin-lattice relaxation. Nueleus B is the lattice ; it can be a magnetic nueleus in
the sameoranothersamplemoleculeorin thesolvent. These nuelei do not ha ve
to be hydrogens and may even be unpaired electrons in the sa me or other
molecules. The fluctuating field from motion ofthe magnetic nueleus must have
the same frequency as that of the nmr transition in order for this relaxation
process to occur. However, moving magnetic nuelei have a wide distributi on of
frequency components, and the required one is always present.
Another process can al so occurwhen the two nuelei interact, whereby
nueleus B,withmI = 1/
2
goes tothehigher-energymI = - 1/
2
statewhile nueleus
A changes from - 1/
2
to + 1/
2
T here is no net cha nge in spin from thi s process,
and it is referred to as a.spin-spin relaxation mechanism.
Togain moreinsight int o t he natureof processes, let us examine
the decay in magnetization as a function of time. Consider an experiment in
which we have our magnetization aligned along the u axis as in Fig. 7-7(A). We
then switch on a field aligned wi th the z-axis ; Mu diminishcs and M, grows,
generally at different rates. In Fig. 7-7(E), for example, the u-component has
completel y decayed, but the z-component has not yet reached equilibrium, for
it gets larger in Fig. 7-7(F).Thegrowth and decay are first-order processes, and
Bloch proposed the foJlowing equation for the three-dimensionalcase(i.e., u-, v-,
and z-magnetizations are involved and the field is located along the z-axis):
. M
M = _ _ u
M
v
= (7-13)
" T
2
(7-14)
and
where 1/ T
2
and l / TI are first-order rate constants, Mo is the equilibrium value
of the z-magnetization, and u- and v-components va nish at equilibrium. In
general, it is found that 1/ T
2
> l / TI ' Instead of rate constants, l / T, it is more
usual to refer to their reciprocals (i. e., the T' s), which are lifetimes or relaxation
times. Since TI refers to the z-component, it is called the longitudinal relaxation
time, while T
2
is called the transverse relaxation time. Thespin-Iattice mechanism
contributes to TI' and t he spin-spin mechanism is one ofseveral contributions
to T
2
.
Befor
adva
lion(
10 a r
(7-6f
wher
nuele
lhe I
wheft
In eq
and (
neld
the1/
betw
0[1 n
in Fi
[he e
The t
quan
lI1em
and
into
or th
or ;-tl
-
.c. 1F
Ig lo
O as
J S in
have
lther
have
alion
Cln of
ereby
Icleus
DceSS,
ImIDe
mI in
,j. We
ro\Vs,
1I has
m, for
, and
7-5 THE NMR TRANSITION
Before proceeding wilh our classical descriplion of the nmr experiment, it is
advantageous to introduce a few concepts from the quantum mechanical descrip-
tion of the experimenl. When the bare nucleus (no electrons around il) is placed
in a magnetic field, Ho' Ihe field and the nuclear moment inleract [see equation
(7-6)J as descri bed by the Hamiltonian for the system
(7-15)
where, as shown in equation (7-2), /iN = ytil with lhe N subscript denoting a
nuclear momenl. When it is obvious that we are referring to a nuclear moment,
the N subscripl will be dropped. Combining equations (7-2)* and (7-15) yields
(7-16)
where YN is constant for a given nuclells, gN is the nuclear 9 factor and:
,
'-
fJN = eh/ 2mc (7- 17)
-
In eq lIation (7- 17), m is the mass of the proton, e is the charge of l he proton,
and e is the speed of lighl.
The expectation values of the operator [ ~ where z is selected as lhe applied
field direction, are given by mI where mI = 1, 1 - 1, ... , - I. The deg neracy of
Ihe mI states that existed in the absence of the field is removed by the interaction
belween lhe field Ho and the nuclear magnetic moment flN' The quantized
orientations of these nuclear moments relative to an applied fiel d Ho a re shown
in Fig. 7- 8 for 1 = 1/
2
and 1 = 1. Since the eigenvalues of the operator I ~ are mI '
the eigenvalues of El (i .e., the energy levels) are gi ven by equalion (7- 18).
(7-1 8)
The energy as a function of Ihe field is illustrated for 1 = L/
2
in Fig. 7-9. The
quantity gN is positive for a proton, as is fJN' so the posilive mI value is lowesl
in encrgy. The nuclear wave functions are abbrevialed as IIX) and 113) for lhe + 1/
2
and _1/2 states, respectively. By inserting values of mI = + 1/
2
and mI = _1/2
into equation (7-18), we find that the energy difference, !lE, between these sta les
or the energy of the transition hv for a nucleus of spin 1/
2
is given by gNfJNHo
or yhH
o
.
(7- 18a)
We loca te the field Ho al ong (he z-axis a nd, since H
y
a nd Hx are zero, only Hol, is non-zero;
.e. , Hxl" and H)J" are zero because Hx and H
y
are zero.
7-5 The NMR Transition 217
+.1.
2
1
2
(A)
+1
f----+ Q
-1
(B)
FIGURE 7-8 Ouantized
orientation 01 mi lor (A)
1= '1
2
and (B) 1= 1.
218 Chapter 7 Nuclear Magnetic Resonance Spectroscopy- Elementary Aspects
1
mI =-"2
E
N
E
FIGURE 7-9 The lield dependence 01
the energies 01 mi = 1/
2
,
R--
G
Y
mI = +.1
2
o -H inc, ->
'Sincc mI = + 1
/ 2
is lo er in cnergy than mI = - 1/
2
, ther will be a slighl
excess populalion of the lo energy tate al room lemp rat ure, a described by
the Bol tzmann di lribution expression in equat ion (7- 19):
(7- 19)
For a prolon. !lE is 10.
3
cm 1 in a I T field, and k T 200 cm-
l
, At ro )m
temperalu re, lhere is a ratio of 1.0000066 (+1/
2
) spi n t one (_1/
2
), The
probabili ly of a nuclear moment being in the + 1/
2
statc is (1/ 2{1 + and
that of it bei ng in t he - 1/
2
statc is C/l) (1 + (recall ur discussi n of
equation (7- 12)),
The cnergy separat ion corre, pond n J to hv ccurs in lhe radi o-frequency
region of Ihe p;cl rum at lhe magnclic fi Id strenglhs usua ll y em loyed in lhe
experi menl. ne appl i a ci rcul a rl polarized radio fn.:quency (d.) fleld at righ t
angle lO Ho (vide infra), and lhe magnelic component of thi electromagneti
fi el d.H1.pr vides atorquel{ flipth moment from f11
I
= + 1/
2 tO
_1 /
2
, causi ng
lran il ions lo occur.
7-6 THE BlOCH EQUATIONS
In order to undersland many of the applications of nrnr, il is ar)' to
appreciate the change in magneliLal i n of lhe system wit h lime as lhe H 1 field
i ap plied, This result i provid d by the Bloch equaton. [ncorp rat ng equations
(7- 13) and (7-14), descri bing rel axati on pr es es. jnlo equation (7- [ l ) hich
de. cribes the precession of lhe magn tizati on, and converting to the rota ti ng
fra me gi es lhe Bloch equalio n:
(7-20)

torquc rrom
rcla \ 31illn effecls
dl:
" dd
a slight
bed by
(7- 19)
rolating
(7- 20)
In the presence or H and in lhe rotating rrame, equation (7-8)- which describes
Herrin Ihe rotating fram - b comes:
(7- 21)
where the rra me is rOlaling with the rrequen cy (J) corresponding to t he rrequency
or the H fieJd. the oscill ating fiel J at ri ght angles to Ho. Equation (7- 20) is a
vect or equation in thc rot ating rra me that can b st be written in terms or lhe
componenl S or M, which are M". M,,, anJ M: .
The l hree compon nI or lhe Bloch equalion are:
(7-22)
(7- 2 )
. dM.
M_= -- = roH M,. + (M
o
- Mz)/ T
I
(7- 24)
- dt
In these equations, OJo is lhc Larmor frequency, which equals ~ H o , and lhe
11 , u rderence rrame is rotal ing al angular v locit y w.
Experimenlally, e monilor Ihe magnelizalion in lhe ,<,y-planeo rererred lo
as the lra nsv rse componenl. Usi ng a pha c-sen. iti ve delector. we monitor the
component or magnetiza ti on ind uc d alo ng lh l/-axis. In a slo opas ag or
.t ady-sl'te xperiment, on ly a u-componen l or magnetizat ion cxi ts; but b cause
or a 90 phase lag associated \ ith lhe el ctro nic detecti on system, a component
90' lit or phase with 11 is measured. Slow-passage or steady-stale cond itions
require H lO be weak (or Ihe order or milligauss) compared lo /J o (which is of
lhe order or kilogauss). Then. accordi ng to equal i n (7- 21), the !-c mp ne nl
domina les unless W is close lo W
o
so lhat lhe fu t term (Hu = wo/'/ ) becomes
sITIaJ!. (Note that (V I is lhe rrequeney oft h d . field and l/O / the Larmor frequency
of prec ssion aboul H ; .e. , (!J i= ' H
I
.) When W is clo e lo the Larmor
fr quency, wo . lhen H
eff
i tipp"d toward the u-axis. Since Ho is b ing changed
si wl y, lhe nc l cffecl is lO change H
dr
lowl y. The individual moments con tinue
lo pre ss about Horr as a consequencc or Ihe torque, whieh is perpendi ular t
H.rf As a result, :Vi remains parallcl t H
eff
and a u-component reslI1Is. Figure
7 lO represenls lhe ti ppi ng or M LO remain ali gned with H. rr as we pass through
resonance. The HI fi eld is al ong lhe u-axis. \t is also an a ltern at ing fi eld with
the rrequency or the rOla li ng rrame. A static field will not tip lh magnetizalion
celar signi ficantly becau e . is '0 sl11 al!.
Relaxat ion proce s. TI' try to preserve Ihe orient ation along the Sl rong
: fl eld, a' hown by lh arrow labelcd T in Fig. 7- 10. Undcr steady-stale
7--6 The Bl och Equat ions 219
Ne/
M."'-'"
,
"

, ,
magneli:tallon
'--"'-----_u
~ M ,
(M, Is Ihe ne/ z componen/
o( Ihe magna/izalion and
nol a precflsslng magnelic
momenl)
FIGURE 7- 10 Effect 01 H, on
the nel magnet ization 01 an
Ho lield .
I
220 Chapler 7 Nuclear Magnetic Resonance Spectroscopy-Elementary Aspects
conditions, al! time derivatives are zero, so equations (7-22), (7-23), and (7-24)
are all equal to ze ro and can be solved to produce:
(7-25)
(7-26)
(7- 27)
7-7 THE NMR EXPERIMENT
Equations (7- 25) to (7-27) describe the magnet ization of our sample in the
so-called slow passage experiment, which is schematica Jly illustrated in Fig. 7- 11.
In this method, one appli s a strong homogeneous magnet ic field. causi ng the
nuclei to precess. Radiation of energy comparable to tlE is then imposed with
a radio frequency transmitter, producing H l ' When the applied fr quency from
the radio transmitter is equal to the La rmor frequency, the two are said to be
in resonance, and a u,v-component is induced whi ch ca n be detected. T his is
lhe condit ion in (7- 21) when Ho wJ,'. Q uant um mechanically, this is equiv-
al ent to sorne nudei being excited from the low energy state (mi = + 1/
2
) lO Ihe
high encrgy slate (mI = - 1/
2
; sec Fig. 7-9) by a bsorpti on of energy from the rJ
source at a frequency equal to the Larmor frequency. Since tlE = hv and w = 21[1' ,
tlE i proportional to the Larmor frequency, w. ncrgy will be extracted from
t he rJ source only when t his resonance condit ion (w = 2n\' ) is ful fill d. Wit h an
electronic detector (see Fi g. 7-11), one can o bscrv the frequency at which a
u,v-component is induced or at which the loss of energ from the transmi tter
occurs, allowing the resonance freq uency to be measured.
It is possible to match the Larmor frequency and the applied radio freq uency
either by holding the field strength constant (and hence w constant) and scanning
Solenoid
(B)
FIGURE 7-11 Schematic diagram ef a simple nmr spectremeter.
ti va
trer
Ilxed
tren
ans
di rec
and
is im
and (
l o 7-
f f he
lhe pr
w ule
for an a
7-7 The NMR Experiment 221
4)
~ 5
26)
27)
the
- 1 J.
, the
with
[rom
o be
lis is
lI UlV-
o the
~ e r.f.
o 271\' .
from
ll h an
lieh a
mittcr
lucncy
mning
a variable applied radio frequency until matching occurs or by varying Ihe field
strength until w becomes equallo a fixed applied frequency. lo the latter method,
fix ed frcquency probes (source and detector coils) are employed and the field
strength at wh,ich resonance occurs is measured. T wo experimental configura-
tions are used in this experiment. In Fig. 7-11(A) the H o field direction (z-
direction) is perpendicular to the sample tube, while in Fig, 7-11( B) the Ho ficId
and the sample are coaxial. There are sorne applications in which th is difference
is important (vide infra),
Wc can now see why the relaxation processes discussed in equati ons (7-13)
and (7- 14) had to be added to our complete equation ((7-20), which led to (7-25)
to (7- 27) for the slow passage experiment) for the behavior of the magnetization,
If the populations of nucIei in the ground and excited states were equal, then
the probabi lity that the nucIeus would emit energy under the resonance condition
would equal the probability that the nucJeus would absorb energy (i.e., transitions
m(+l/z) ...... m(_l / z) would be as probable as m(_l /z ) -. m(+l/z)' No ne!
change would then be detected by the radio-frequency pro be. As mentioned
earlier, in a strong magnetic field there wiJl be a slight excess of nucIei aligned
with the field (lower energy sta te) and consequently a net absorption of energy
results, In the absence o[ relaxation, energy is absorbed from lhe d, ignal until
the population in the lower state equals Ihat in the higher state, Thi s equili brium
position is attained asymptQtically. loitiall y absorption might be detected but
this absorption would gradually di sappear as the populations of ground and
exeitcd states beca me equal. When this occurs, the sample is said to be satu rated.
Without saturation, the relaxation mechanisms all ow nuclei lo returo to the
lower energy state without emitting radiation. As a result there is always an
excess of nucIei in the lower energy state, and a continuous absorption of energy
from the Lf. source by the sample can occur.
The nmr experiment has significance to the chemist beca use nuclei exist in
atoms linked by bonds into molecules. The energy of the nucIear resooancc (i,e"
the field strength required to attain a Larmor frequency equal to the fixed
frequency) is dependent upon the electronic environment about the nucIeus. The
electrons shield the nucIeus, so that the magnitude of the field seen at the nucIeus,
H/I" is different from the applied field, Ho:
(7-28)
where (J, the shielding constanl, is a dimensionless quantity that represents the
shielding of the nucIeus by the electrons. The value of the shielding constant
depends on several Cactors, which will be discussed in detail later.
In a slow sweep of Ho, the various magnetizations of the different nuclei
are sampled individually, beca use the nucleus is shielded or deshielded causing
H,v to differ. For a molecule with two different kinds of hydrogen atoms this will
Jead to a spectrum Iike that shown in Fig. 7- 12.
One other point is worth making here, The differences in the magnetogyric
ratios oC different kinds of nucIei are much larger than the effects fr om (J , so there
is no trouble distinguishing signals from the different kinds of nuclei in a sample'
e.g., 19F and IH are never confused. The frequency ranges are so vastly separated
that different instrumentation is required to study different kinds of nucIei . In
Table 7- 1, the resonance conditions (hv = gNf3NHo) for various nucIei are given
for an applied field of 10,000 gauss.
I
e
a.
O
ti)
.D
<l:
>-

(j)
e
w
lhe
the
prC!
the
abo
so t
tow
lipp
worH
pr e
wou
FIGURE 7-12 A low resolution nmr spectrum 01 a sample containing
two different kinds 01 protons.
v. ou
way
IS nc
The frequencies in Table 7-1 a re in MHz (10
6
Hertz or 10
6
e/s), and
the
the variation in the proton resonances of typical organic compounds from
fune
di'ferent shielding constants is only 600 Hz at 10 kil ogauss. In sorne paramag-
netie eomplexes, shifts of the order of magnitude of 840,000Hz have been
observed; but even these could not be eonfused with a fluorine resonance. The
relative sensitivities ofsome nuclei in [he nmrexperi ment arealso listed in Ta ble
Thi
7-1, with a more complete compilation given in Table 8-2.
all m
The most common nmr experiment invol ves the pulse method. We shall
We
di seuss Ihis ex perimenl in more detai l later but now briefly consider it in the
sel e
context ofequat ion (7-21). Suppose that a single trong H I pulse i imposcd
(e .g., H I 100 gauss Ho- w Jy for all of the protons). Referri ng to the
decu
calle,
equation for ".rr.
r OUI
Lore
H
-
efr =I-l c
-
" +
(
Ho - y
W
1Je z tram
prop
Dmr
TABLE 7- 1. Important Nuclei in NMR
NMR
Frequency
In 10
Relallve"
Senslllvily Magnetlc
b
Isotope
Abundance
(%)
Kllogauss
Fleld
d
(constant
Ho)
Momenl
(,,)
Spln
r
(1)
l B
2H (D)
JOB
99.9844%
0.0156
18.83
42.577
6.536
4.575
l.0000
0.0096
0.0199
2.7927
0.8574
1.8006
1.
.2
1
3
llB
13C
14N
IsN
19F
29Si
31p
J
17
S
n
[19Sn
81.17
1.108
99.635
0.365
100.
4.70
100.
7.67
8.68
13.660
10. 705
3.076
4.315
40.055
8.460
17.235
15.77
15.87
0.165
0.0159
0.0010
0.0010
0.834
0.0785
0.0664
0.0453
0.0518
2.6880
0.7022
0.4036
-0.2830
2.6273
- 0.5548
1.1305
-0.9949
- 10409
3/
2
1/
2
1
1/
2
1'
/ J
1/
2
1/
2
1/
2
1/
2
FIGUI
in ma
a For equal numbers of nuclci , wherc 1H equals one.
b In mulliples of the nuclear magneton, eh/4rrMc.
, In multiples of h/2rr.
,1 MHz.
dislribl
and
Thc
able
shall
7-7
the local Ho will vary slightly from nudeus to nucleus, but HI is so large that
the term H le" is completcly dominant, and H.
ff
is almost the same for all nuclei
present. Al! nucJei are sampled si multancously. Since H1 is direct d al ong 11 and
the net magnetization along z, t he cross product requires that M bcgin to precess
about u. The pulse time is short, compa red to the time for one full precession,
so the magnetizati on does not have time to precess around u, but merely tips
toward v. Accordingly, the v-component is measured in this experimenl as Mis
tipped I ward v. Most experiment are now being done by Fourier tra nsform
procedures. Ir a strong pulse were employed for a very long t ime, the nuclei
would preces ' a round Herr as in the slow passage experi ment ; a u-component
would arise and v would disappear. Pulse experiments a re not usually done this
way. When a strong pulse is employed for a short eno ugh duration* that there
is no time for any rclaxation to occur du ring Ihe pulse (t p ::::; 10 microseconds),
the Bl och eq uations predict the following expression for the v-component , as a
function of time, t:
(7- 29)
Thi s expression results from the Fourier transform of equati n (7-23), which
allows conversion from rhe frequ ncy domain (7- 23) to the lime domain (7-29).
We shall d iscuss this topic in mor detail later. The quantity dM"fdt cannot be
set equal to zero in this experi ment. The v-compon nt of the magnet iza tion
decays with time according to equation (7-29), as shown in Fig. 7-13. This is
called a free induction decay curve and it can be analyzed by computer (via
Fourier transformation, vide infra) to give a frequency spectrum inden t ica l lO the
Lorenlzian slow passagc result. A compa rison of Ihe slow pussage and Fourier
transform experiments is provided in able 7-2. We shall cover fu ndamental
l)ropertics of nmr in this chapter t hat are independent of the way in which the
mr experiment is carried out, i.e., slow passage or Fouri er tra nsformo
Time
FIGURE 7- 13 Free induction decay curve; a plot 01 the change
in magnetization 01 the sample with time.
In Cha pter 8, we shaIl provide an equi valen! description of this experiment in lerms of the
distribution of frequencies that make up the squarc wave produced from this pulsing.
The NMR Experiment 223
'
224 Chapter 7 Nuclear Magnetic Resonance Spectroscopy-ElementaryAspects
The Quantum
Mechanical
Description of
the NMR
Experiment
TABLE 7-2. A Comparison 01 the Fourier Translorm and the Slow-Passage
Experiment (100 MHz) in Terms 01 the Equation
yHcffa = (I'H
o
- wl)e. +,,,Hle
u
Experimenl
OrderofMagnllude
ofFrequeocl es lo
sec-,(Hz)
Ha and w, yHa - W b )IH
l
Whal Happens? Whal Is Measured?
slow
passage
10
(at resonance)
10 precess about
Hcrr many times as
we sweep through
resonance, so Mlips
toward u.
Fourier
tra nsform
(FT)
10
4
1 0
6
(and hence
precess aboul Hcrr
i ofa revolution
or less during the
pulse time, so M
tips toward v.
Multipl ying by )' put sH<[r in unit offrequency (Hz).
h If you are accustomed to thinking in terms of part s per mill ion, nOle that 10
4
/10" = lOO x 10-
6
=
100 ppm.
7-8 PROPERTIES OF
Now, to gain valuable insight, let us reexamine this whole problem using a
quantum mechanical instead of a cJassicaJ mecha nical a pp roach. Quantum
mechanicsshowsusthatfor f = 1/
2
, therearetwoallowedorient a t ions ofthespi n
angular momentum vector in a magnetic field (Fig. 7- 8) and will also indicate
the necessary requirement s to induce transitions between these energy states by
an appropriate perturbation, i.e. , the application ofan oscillati ng magnelic field
withenergiescorrespondingto d.radiation.Thenecessarydirection for thisfield
can be determined from a consideration of the spin angular momentum oper-
ators.
The P operator has eigenvalues f(l +1) (as in an atom, where t he orbital
angular momentum operatorUIj = t(l +1)fi21j). Any one ofthe components of
[ (e.g., [z) commutes with P, so we can specify eigenvalues of both P and l. .
The eigenvalues of[ zare given by f , (I - 1), ...- f (like m values in an atom,
where thez-component ofangular momentum, Lz, is given by Lzlj = mfilj with
mI = 1, ...,O). f n general, if two operators commute, then there exist simultaneous
eigenfunctions of both operators for which eigenvatues can be specified.
Tt is a simple matter to determine whether two operators commute. Ifthey
do, then by our earlierdefinition ofcommutation (Cha pter 2)
Theaboyedifferenceis abbreviated by thesymbol [p,[J.Similarequations can
be written for[,and [y, i.e.,
Ho\
Ei ge
eige
W
spm
Thu
oper
oper
l he I
foll o
func
ical
com
An

Con:
alter
term

H=:
for '
simi l
7- 9
7-9 Transition Probabi li ties 225
However, i
z
does not commute with i , or i
y
, e.g.,
Eigenvalues tor (2 exist, and if we decide to specify eigenval ues for i " then
eigenvalues for and y do not exist.
Average values (Chapter 3) could be calculaled for the ix and f,. operators.
We shall make these concepts more specific by applying thesc operators to the
spin wave functions 'Y. and f3 for / = 1/ 2 nuclei and showing the results:
iza = (+ t/
2
)a
(7-30)
i
z
f3 = (-1 / 2)f3
i , f3 = ( - 12):>:
(7- 31)
yf3 = (-1/2)ia
Thus, the i
z
operator yields eigenvalues, since operation on a gives back a and
operation on f3 gives f3. The ix and iy operators do not yield eigenvai ues, since
operation on ti produces f3 and operation on f3 yields 0: . The average value for
the property f, or iy is given by an equation of lhe sort JI/I *OPVf drl S 1/12 dr. T he
following relations hold for a and f3 (as Ihey do for orthonormal electronic wave
functions) :
and f af3 de = O
As mentioned in Chapter 3, the integrals encountered in quantul1l mecha n-
ical descripti ons of systems are written employing lhe bra and leet notation for
convenience. Recall that the symbol < I is referred to as abra and I ) as a ket.
An integral of the form S(I/I* Op I/I)dr is written as <I/II Opll/l ) , whereas an
integral of the form S1/1 1*1/12 de is writt n as <1/1 I I 1/12 )'
7- 9 TRANSITION PROB ABILlTIES
Con ider the effect of the H 1 field in the quantum mechanical descri pt ion. Ir lhe
alternating field is written in t rms of an amplitude H/ , we get a perl urbing
term in the Hamiltonian of the form of eq llation (7-32):
Rpert = -yhHxOi
x
cos w t (7-32)
Recall from eq llation (7- 16) that R for a nllclellS in a z-field was
f = - yflJ-J
o
( = -gNf3
N
H
o
i
c
, so now the perturbation is of a similar form but
ror an x-fi eld that is al ternating.
The equalion describing the probability of a transition in the nmr, P, is
similar to lha! in u.v. and IR, and is given by
(7-33)
I
(
where g(w) is a general hne shape functi on, which is an empirical function that
descri bes how the ab orplion vari e near resonance. To a pply cqualion (7- 33),
\Ve need to evaluate ma lrix elem nI of the fo rm (q>cx IT, 1q and delcrmine
whet her t hey are zero or non-zero.
The olut ion is best accompli hed by const ructing a malrix thal summarize
all of the integra ls lhat must be eva lualed lO describe the system in a magnelic
fi eld wit h and wi t hout H l ' Rows and col umns are constructed, which are headed
by l he basis sel. In t rus case, we have one nuclells wilh a and f3 nuclear spin
wave funct ions leading lO:
f3
(a lR + Rpcrtl,:x ) ( alH + Rpcrt lf3)
f3
( f3 IH + Rpertl .:x ) (fJlfI + Hpcrllfi)
By Ihis procedure, we have considered all possible ma tri x clement a nd also have
lh m in llch a form that if E were subtracled from t he diagonal elcments we
would hay the ecular determinanl, which can be sol ved t give the energie ' of
these 'lates in an applied field (Ha + H ). * The resul ting energies eo uJd then be
ll sed in Ihe ecular e uations (produced by matrix multiplicati on of the secul ar
dClerminant wilh a matrix of lhe basis sel) to give the wa e functions in lhe lield.
(Nolice lhe analogy of this lo our handling of Ihe secular delerminant and
equation in the se ti on on Hckel calculalions in Chapter 3.)
We begin by evaluating the elemenls in t he secul ar determi nanl when the
applied fi Id is Ha (with a z-component only), i. e., lhe Zeeman expcriment. Since
there is n x- r y-field component (only 2), Ihefe a re no or fv opcrators and
al! matrix element of Ihe form ( 1 f, 1) 01' (1 i ),I) are zero. The off- diagonal
elemenls, (al f:l fi) and ($I fzla) are also zero beca use f:I f3 ) = _ 1/
2
f3, and
( alf3 ) and (f3I e< ) are zero. The only non-zero matrix elements are (Xli. la) and
(f31 f. If3 ) , with lhe former eorresponding lO stabiJizaton, +1/
2
(i.e., /2 ( a la), and
Ihe latter to destabilization, - 1/
2
, With no off-di agonal elcmenls, the eigenvaJues
are obtained direetly and the basis se! is nol mixcd, so lhe lwo wave funclol1s
are a and f3. When these are substituted into equation (7-33) for (p and q>cx, lhe
matrix elernent is zero wit h f. and Ihe lransition is not allowed, (al f3 ) = O.
Next, we shall consider whal happen when an H 1 ficld along lhe x-axis
is add d to the Zeeman experi menl deserib d aboye. We must now worry
about malrix elemenls involving f . The diagonal elernents (alf..lcx) are zero
[(al f,la) = 1/2(al f3) = OJ obut lhe oA'-diagonal elements (Xlf<l fi ) a re non-zero.
inee the H I field i small compared 10 Ha (.:-component), lhese off-diagonal
malrix clemenlS arc so small a to have a negligIble effecl 011 Ihe energies (lhe
effect of f" on the diagonal is the same as in the Zeeman experiment ). However,
lhe small off-diagonal matrix e1emcnts are impor tant beeause lhey provide a
mechanism for inducing tTanstions from C( lo f3 because tlle new \Vave fun ct iolls
f ar the system wilh H 1 present (i.e. , obtai ned afler diagonalizing OUT matri: ) mix
a liu t!! f3 character nto {h!! a-Zeeman st a/ e {l/uf a li ll te a i/l to (he fJ- Zeeman sta te.
The new wave funeton for the cc-Zeeman stale now is q> = l - a
2
1!X) + alf3 ),
Rccallthat (t/I\R\t/I) = E(t/I It/I). for an onhonormal basi s sel, (t/I.I'p..) eq uals I when 11 = 1/1
but equals zero when n # m. Thus. E appears onl y on lhe diagonal or l he encrgy determinanl.
.... h
fun,
Iran
torq
Ih
len
alo
equ
flll
(ran.
vi'
7-9 Transition Probabili ti es 227
where a 1, and a si milar change occurs in lhe fJ slale. When the e new wave
functi ons q are substituted into equalion (7- 33), P is non-z r , mak ing Ihe
transil ion allowed. This corresponds lo the da . ical picture of H 1 exerling a
torque to gi ve a transverse componenl lo Ihe magnetization. Thus, w see thal
Ihe probabilil y, P, of a Iransition occurring dcp nds upon the off- diagonal mal rix
elemenls in lhe a,fi ba is being non-zero, so thal cquat ion (7- 33) is non-zero.
Nexl, onsider what would happen if the rJ. perturbi ng 6eld H 1 was placed
along the z-axis. The off-diagonal matrix elemen! would again be zero, s
eqllalion (7- 33) becomes
p = = O
This w uld corrcspond lo a slig.ht reinfo rcemenl of Ho, but would not allow
Iran ilions. Thi x rci e sho s thal H 1 cannot be coli ncar wil h Ho to gel an
Ilmr Ira n. ilion. (In lhe cJassical model, Ihere has lO be a perpendicul ar componen!
fol' Hi to exerl a torque.)
Finally, consider the case in which I = 1. Malrix el ements <m' l f( lm) vani -h
uIlles //l ' = m 1. Conscquently, for I = 1, lhe allowed tra nsitions are between
adjacenl leveIs with 11m = 1, giving tuo = I1E = ),111-/
0
,
[n ummary. si mply placing a amplt: in a magnelic fi eld, H o' remo es Ihe
degeneracy of lhe mI slates. Now, a radio-fr queney . ou re i ne ded to provide
/I' to ind uce lhe Iransition. Absorpli on of en rgy occur provided lhat lh
magn tic vector of the o cillati ng eleclromagl1 lic fiel d, H l' ha a component
p ' rp ndicular lO Ihe leady fi Id. 110 . of lhe magn et. Olherwise (i .e., if H 1 is
paral1 el to Ho), the o 'cil1ati ng fi eld simply modulales Ihe applied fiel d, slighlly
changing lhe energy levels ofthe pin sy lcm, but no energy absorption occurs.
h inOucnce of relaxalion effect , on nmr line shapes leads to ome ery
imporlanl appl ical ions of nmr pl.ctroscopy. Accordingly. il is worthwhile to
summarize and cxtend our und,x tanding of lhe e phenomena. We begin wilh
a di sCLl s ion of relaxa ti on proce e and their etfect on the shape' of the
re onance lineo The lifelim of a given spin tate inAuences lhe spectral line widlh
via Ihe Uncertainl y Principie, which is given in equatloll (7- 34) :
(7- 34)
Since E = Ir l' and [ = T
2
the lifetime oC lhe exci led slale, the range of
trequencies i' given by v 1/ T
2
The quantity 1/ T
1
as employed here lumps
log ther all of the fa tors inftucncing thc line wi dth (i .e. al! th relaxal ion
pr een: ) and i' ' imply one-half Ihe widlh of the speclral li ne a! half-height.
Wh n the only conl ribu li on to T
z
is from spin-latt ice eft cts, then T
2
= TI' Mo t
molecllle conla in magnetic nuclei: in the spin-Iattice mecha ni m a local ft ucluat-
ing fie ld arising from the motion of magnet ic nuclei in lhe laltice couples lhe
energy 01' lhe nuclear spi n lo other degrees of freedom in the sample. e.g.,
Iranslational or rotalional energy. The lattice rcfers lO olher aloms in lhe
molecule or olher molecule , including lh .ol vent. F r liquids, TI values are
usual1y belween 10 -
2
and 10
2
seconds bul approa h values of 10-
4
.cconds ir
Relaxation
Effects and
Mechanisms
228 Chapter 7 Nuclear Magnetic Res onance Spectroscopy- Elementary Aspects
FI GURE 7-14 The same
nmr transition occurring in a
bulk sample in an
inhomogeneous field .
certain paramagnetic ions are present. The extent of spin-lattice relaxation
depends upon (1) the magnitude of the local field and (2) the rate of fluctuation.
Pa ramagnetic ions have much more intense magnetic fields associated with them
and are very efficient at causing relaxation. The water proton signal in a O. l-M
solution of Mn(H 20)6 2+ is so extensively broadened by efficient relaxation from
Mn
z
+ that a proton signal cannot be detected in the nmr spectrum. As mentioned
before, the spin-Iattice process can be described by a firsl order rate constant
(l / TI ) for the decay of the z-component of the magnetization, say, after the field
is turned off, and is refe rrcd to as longitudinal relaxation.
Nexl. we shall discuss some processes that affect the xy-components of the
magnet izalion and are referred to as transverse relaxation processes. The spin-
lattice cffect di scussed aboye always contri butes to randomizat ion of the xy-
component; therefore,
where J/ T
z
' incl udes all effecls other Ihan the spin-lattice mechanism. When the
dominant rel axation mechanism is spin-lattice for bOlh longit udinal and trans-
verse processes, .e., l T! = I/ T
2
, then 1T
2
' is igno red. The quan tity we used in
the Bloch equations is and not 1f T
2
'. I n solution, t hese Ol her effecls,
are small for a proton compared lO l T , so ( I/ T
2
) = (l T!). T he other effects
include field inhomogeneity, spin-spin exchange, and the interaction between
nuclear moments. We sha!l discuss these in detail , beginning with field in-
homogeneity.
When the ficld is not homogeneous, protons of the same type in di ffe rent
parts of the sample experience different fields and give rise to a distribution of
frequencies, as shown in Fig. 7- 14. This causes a broad bando The effect of
inhomogeneity can be minimized by spinning the sample.
Interaction between nuclear moments is al so incl uded in T
z
'. When a
neighboring magnetic nucleus stays in a given relati ve posit ion fo r a long time,
as in solids or viscous liq uids, the local field felt by the proton has a z ero frequenc y
contribution; i.e. , it is not a fluctuating field as in the T proc ss fr om the fi eld
of the neighboring magnetic dipoles. A given type of proton could have neighbors
with, for instance, a + + - + - combination of nuclear moments in one
molecule, + - + - - in another, and so forth. Variability in the static field
experienced by difl'crent protons of the same type causes broadening just like
field inhomogeneity did. To give you some appreciation for the magnitude of
this effect, a proton, for example, creates a field of about 10 gauss when it is 1 A
away. This could cause a broadening of 10
5
Hz. As a result of this cffect, extremely
broad lines are observed when the nmr spectra of solids are taken. This effect is
averaged to zero in non-viscous solutions by molecular rotation.
The process of spin-s pi n exchange contributes to TI but not to T, for it
does not influence the z-component of the magneti zation. In this process, a
nucleus in an excited state transfers its energy to a nucleus in the ground sta te.
The excited nucleus returns to the ground state in the process and simultaneously
converts the ground state nucleus to lhe excited state. No net change in the
z-component results, but Ihe u- and v-components a re randomized.
In common praclice, l T
z
' is never reaJly used. Either 1T
2
= l T (wilh J/T
2
'
nc!
fro
em
em
res
Th,
hei
haJ

Thl
Ihe
i!lu
7-10 Measuring the Chemical Shift 229
negligibJe) or we just di scuss I / T
2
. In a typical nmr spectrum, I / T
2
is obtained
rrom the line shape (as will be shown) and it either equals l / TI or it does not.
As menti oned earlier, the true rorm or a broadened line is described
empirically by a shape runcti on g(w), which describes how the a bsorpti on or
energy varies near resonance acco rding to equation (7-33). Since magnetic
resonance lines in soluti on have a Lorentzian fine shape
(7- 35)
The width or the band between the points where absorption is half its maximum
X}'-
height is 2{f 2 in units or radians sec-
I
. In units or hert z, the rull ba ndwidth at
balf hei ght is given by l /nT
2
.
7-10 MEASURING THE CHEMICAL SHIFT
The shielding constant, equation (7-28), makes nmr or nterest to a chemi st. In
the typical nmr spectrum, the magneti c field s pl otted versus absorption as
ilJustrated by the low res olution spectrum or et hanol shown in Fig. 7- 15. T he
-Increasing field strength (constant frequency)-..-
-Increasing frequency (constant field)--
- Increasing shielding--
FIGURE 7-15 Low resolution proton nmr spectrum 01 C
2
H
s
OH.
least shielded proton (smallest 0") on the electronegative oxygen a t om interacts
with the field at lowest applied field strength. The a reas under the peaks are in
direct proportion to the numbers or equivalent hydrogens, 1: 2: 3, on the
hydroxyl, methylene, and methyl groups. Note that the separaton or absorption
peaks rrom - e H) and - CH
2
- hydrogens n this spectrum is much grea ter
than tha t in the inrrared spectrum.
We wish to calibrate the horizontal axis or Fig. 7- 15 so t hat the field strength
(or so me runction or it) at whi ch the protons absorb energy rrom the rado
frequency probe can be recordcd. Equalion (7-28) could be cmployed, but
accurate measurement of HN and Ha is difficult. Instead, a referencl: materi al is
employed, and the difference betw n the fic\d strength at wh ich t he sample
nucleus a bsorbs and that at which the nucleus in the reference compound absorb
is measured.
The re[erence compound is added to the samplc (vide nIra), so it must be
unreactive. Furt hermore, it is convenient if its resonance is in a region that does
not overlap other resonances in the molecules typically studied. Tet ramethylsi-
lane, TMS, has both prop cties a nd is a very common refcrence ma terial [or
non-aqueous solvents. In view of the limitcd sol ubility of TMS in water, satts of
the anion (CH
3
), Si D
2
CD
2
C0
2
- are commonly used. The position of its
resonance is sel at zero on the chart paper.
The magnetic field differences indicated by Ihe peaks in Fig. 7-15 are ver y
smal1, and it is difficult to construct a magnet that do not dri ft on this scale.
Accordingty, most instruments pick a resonance and electronically adj ust the
field circuit to ma intai n or lock this peak at a con tant position. This can be
accomplished by having some materi al in a sealed capillary in the sample lube
or in the insl rument to lock on, or el se by picking a resonance in the spectrllm
of lhe solution bei ng studied for the purpose. The former procedurc is descri bed
as an externallock and the lalter as an internallock. The internal lock produces
more accurate results. Temperature and bul k magnetic susceptibil it y clli cts are
minimized. The field is being locked on a resonance that ha all of the advantages
of an internal standard (vide infra). In a typical xperiment employi ng a n inl ernal
lock, Ihe 2H signal of a deutera ted sol nt is utili zed via a separate lran ' mi tter-
receiver system.
With TMS at zero, il is possible to measure the di fferences in peak ma xima,
~ . Although the field is being varied in the slow passage experiment, the abscissa
and hence the differences in peak positions are calibrat ed in a frequcncy unit of
cycles per second referred to as hertz (Hz). Tbis should cause no confusion.
for frequency and fi eld strength are related by equation (7- 5):
w = }'H
According to eq uation (7-28), Ihe shicl ding of the various n uclei, (J Ha,
depends upon the field strength, Ha. If a fixed frequency probe of 60 MHz is
employed, the field utili zed will be different than if a JOO- M Hz probe is empl oyed.
As shown in Fig. 7-16, the peak separations are 10j6 as large at 100 MHz as at
60 MHz
100 MHz A. /\.
--'
370
- - - - - - - - - - - - - ~
258 122 o
222 155
' ~ - - - - - - - - - - - - -
t'> , Hz (H increasing--)
FIGURE 7-16 The nmr speclrum of CH
3
CH
2
0H al 60 Mhz and al 100 MHz.
60
wh
us,'d i ~
he
is
,Ie
bs
be
les
SI-
ror
of
its
ery
lile.
he
be
be
Ulll
bed
h:es
are
.Iges
mal
tter-
ima,
:issa
lit 01'
sion,
aHo,
Hz is
oyed.
,\:-. at
o
7-10 Measuring Ihe C'hemical 8hift 231
60 MHz.Toovercome this problem and to obtain values for the peak posili ons,
which are independen t offi eld st rength, the chemical shrt, O, is defined as
0= -- (7- 36)
fIxedfrequencyoftheprobe,V
o
Since the probe frequency ofva is in unit ofmegahertz(MHz). and /j, has units
of hert z, lhe fraction is multi plied by the factor 10
6
to give convenient numbers
for Oin units ofparts per miliion, ppm. The chemical shift,O, isindep ndent of
the probe freq uenc employed.
If the sample nuclei are deshielded relative to the reference peak, /j, i
posi tive* byconvention. When Si( H
3
)4 is employedas a standard,most proton
i5 values are positive and the larger posit ive numbers refer to lesser shielding.
For several reasons, it is advant ageous to add the TMS dircctly to lhe
solution bcingstudied asopposed to having: it in aseparatesealed capilla rytu be,
i. f ., an internal vs. an external standard. Magnetic field-induced circulati ons of
the paired elect rondensity in a molecule give ri se to a magnetic moment tha t is
opposed to Ihe applied cId.In diamagnetic substances, thi s elrect accoll nts fo r
the repulsion, or diamagnetism,experienced by these mal dais when placed in
amagnet ic field. The magnitlldcoflhi effe l varies indifTerent subli tances,gi ving
ri se to varyi ng diamagnetic susceptibil ities. Thi s di amagnetic su::;c pt ibility in
tu rn gives rise lo magnetic shielding ofa mol cule in a solvent, and is variable
for difTerent solvents. The effect is referred to as t he volume diamagnet ic
susceptibilit y of the sol vcnl. Thus, the chemical shift of a solute molecll le in a
sol vent will be influenced not only by shielding of electrons but also by the
volume diamagnetic sllscepti bilily of the sol vent. The (j va lucs oblained for a
solulion andapu/'c liquidsol ute(l hIS isoften referred to as the neatliquid)relative
lo an exlernal tandard ( "ig. 7- 17) woul d be different to the ext ent Ihal lhe
volumediamagneticsusceptibilities 01' the solventand neat liquid were difTerenl.
In solu tion, the diamagnelic contri butions to lhe .hi eldi ng ofthe olute depend
upon the average numbe r of sol ent and solute neighb r. Consequenlly, the
chemi cal shift will beconcentrat iondependent. 1'0 get l meaningful value fo r O
with anexternalstandard,it i ' n cessaryto measurevatdilferentconcenlrations
an extrapolate to infini te dil ution t produce a value for j under volume
sll scepti bility condilions of the pure sol vent.
Contri butionsto themeasured b from {he voIume diamagneti cslIscepti bili ty
Sample
ofthe solvent can be more casi ly minimized by using an internal standard. The
internal standa rd mu t, ofcourse, be unreactive with lhe solvenl and sample.
Furthermore, thesampleandslandard must b uniformlydisper 'ed.Uncl erthese
External
condi ti on lhe standard is subjected to tlle same volume susceptiblity (from standard
solventand olule molecules)as is lhe 'olule.and lhe effects wiU tend to cancel
\ hen Ihe differcnce, , is calculated. (Duc lO variat ion in t he arrangemenl of
FIGURE 7- 17 Concentri c
,olvent around different olutes, an exact cancellalion may not result. ) For
nmr sample tu be contai ning
accurate work, spectra at two different conc nlrations should be run as chec ks
an external standard . For
and lhe resullS relat ive to two i n t ~ r n l st andards compared lo insure that the
illustrati ve purposes the
external standard
compartment size s
In thecarly li te ra Iure andeven as laleas 1970 in the areaorI'JF and JI P nmr. Ihe conventio n
exaggerated. Th s s really
lI$ed istheopposite orthat descr ibcd here.Ther ader must exerciseconsiderable care in ascer laining just large enough for two lo
Ihe co nvcntion used. three drops 01 standard .
internal standard approximations are worki ng. Molecular interactions of the
solvent with the standard or solute cause complications.
7-11 INTERPRETATION OF THE CHEMICAL SHIFT
a. Local Effecls
The range of proton chemical shifts measured on pure liquids
(4
) for a series of
organic compounds is illustrated in Fig. 7-18. Proton shifts outside this total
range have been and sometimes shifts outside the range indicated for
a given functional group oceur. In general, the data in F ig. 7-18 serve to give a
fairly reliable means of distinguishing prot ons of fu nctional groups. Note the
difference in CH
3
-C::, CH
3
C=, CH
3
- O, J-1C=, HCO, elc. Very extensi ve
compilations of proton chemical shifts have been reported,(5) which can be
employed for the fingerprinl Iype of application. The reference section at the end
of this chapter lists compilations of shifts for various nuclei. The shift of OH
protons is very concentration and lemperature dependent. For example, he
spectrum of ethanol changes as a function of concentration in an inert solvent
(e.g .. CCI
4
), by 5 ppm in going from concent rated to dilute solution. At infi nite
dilut ion, the hydroxyl proton appears at a higher fi el d than t he methyl protons,
in cont rast to the spectrum of pure ethanol represented in ig. 7- 16. T here is
more hydrogen bonding in concentrated Il1a n in di lute soluli ons a nd hyd rogen
bonding of the proton causes a shift to a Iower fiel d. This bchavior on dilut ion
can be employed to erify the assignment of a pea k to a hyd roxyl group, lo
in vestigate the exi stence of sleric effects in hyd rogen bonding(6) and to d istinguish
between intermol ecular and intramolecular hydrogen bonding. SQlvent effects
are quite large whenever specific interactions occur a nd, as will be shown later,
nmr has been very valuable in establishing the existence or absence of these
interactions. The di fferenti al shift of the C- I-1 a nd O- I-I protons of methanol
or ethylene glycol is he basis of a standard technique for esti mating probe
tempcrature.(7)
The interpretation of proton chemical shifts is complicated by Ihe cxistence
of contributions from local (i .c., the atom undergoing l he transit i n) shielding
and neighbor atom anisolropic effects. Local shielding arises from magnetic fi Id-
induced electron circulation on the atom undergoing the transition. This shield-
ing is a tensor quantil y wil h (J zz giving the contribution parallel to the field when
the z-axis of t he molecule is ali gned with the field. Using pert urbation theory
and treating lhe magnetic field as a perturbation on the ground-state molecular
wave function, 10), Ieads to the Ramsey equation(8):
e
2
IX2 + y21 )
(J =--
(
O O
zz 2mc2 ,.3
(diamagnetic term)
(7-37)
(paramagnetic term)
(A)
R
/l.
y.
(B)
7- 11 Inter pretat ion of the Chemical Shi ft 233
C:==:::::I_-- ':J:::JI0-co'g. 120/ = =====_
_ I_C!f (2"
c
_ "1
C.-tH - '4)
I A, o
RC-N!:!R(HJ UJI

I

[
==========:o..
I C-C-NIjl2.l)
e
/I.-CH- -CH. - [;.
\ b .
e
r:..::::J ca ,,61
0 .....==:::::11 1291

====-__ In
[: I (1 241
C':'z- (t4001
i (300)
T"S
(A) " (PPM TO TM51
4' (PPM TO T1I5)
e
Ita -eH,.-CHe. - [;.
.
- rf-c
b
\
e
y_ COtlIl ON OIIGAHIC STRUCTURAL
GROUPS OTHE/I THAN R
TU
C:.J

- I

o

A'NCIj, (4)
RNOht7J
D ___ose!:!)ANO [tO)
c:==-__, (201
o
A,tRI(Hj- CCl:h (26)

I C-C
Ctt) (39'
-CIj,AItD
(9,
ANO
I (43)
_ I 141)
[=-:J 1'"
TlOS
FIGURE 7- 18 Hydrogen
nuclear magnetic resonance
chemical shiltcorrelation
charts, (A) lor main proton
gr oups, (B) lorCH, OH, and
NH subgroups. Open bar
denotesextreme 10% 01
data. [Irom M. W. Dietr ich
and R. E. Kell er, Anal.
Chem., 36, 258 (1964). )
I/Iustraron contirJUed on
fol/owing page.
4
(B) 4' (PPM TO TII51
7- 37)
.
11
TIIS
o
(4)
0 _______1.:1' (12) o
c=-__' (181
CII__1Il1 {151
_
FIGURE 7- 18 (continued)
0 _________-=======:::1' C.. {61
\c:
C==:..__IIIIII-=:JI Ar O!:! 1761
O ___c:::J
1
f'Ob IlOI
C::==___ C!:!RY'Y (36)
CJ__-=:J1
y. COIIMON OIUIAH IO STRUCTURAL
GftOUPS OTHER THAN R
c.. f'tII
TW'
'8
(e)
This equation is similar lo the Lambequation for an atom, and it tcll s us wha t
the applied fi eld does to ourmolecule.Apo itive sign indicates hielding, i.e. , an
upfield or a diamagnetic contri bution. The negative sign indicates deshieldi ng.
i.e., a downfiel d or a paramagnct ic cont ribut ion.
The fi r t term on the right-hand side of the equa lity is the so-call ed
diamagnet iclerm.Thesymbol <01 cor respond. to thegroundstat wavefuncti on,
and ,. is th di lance from theelectron to lhe nucleu und rgoi ng the transit ion.
Since only <01, the ground sta te wave function, is invol ed in this first term, no
exci ted ta tes a re mixed in by thi s termo The fi Id d e not dis tort l he elect ron
distribution in t he molecule. but just induce a spherical eleClron circulation. Ir
this wcre l he onl y elrecl, lhe molecular wave fu ncti on would be independent of
Ihe magnetic fleld.
The matrix clement correspond ing to lhis first term red uces to:
(7- 38)
The term ), ref rs t o the elfective numberofelectrons in t he s-orbital. This effect
givc r ise lo lhe n nnaldiamagnctism observed for S = molecul s <lnd can be
pictured as the shieldi ng ofthe nuclcll re ult ing fr om f1el d-i ndllced circul a tion
ofelectron densit y as illustrated in Fig. 7- 19.
The fie ld generated at the nuc\eus by electron circulat ions is dire tly
proportional to the strength of the appli ed fi eld and will also depend on the
e1ectron densty urr undng the nucleu . Ift his were the nly effect of the
magnetic field on a molecul e, the chemi al shift of a hyorog n nucl eu would
parallel the elect ronegat ivi ty of lhe groups att ached. This correlation is nol
observed because of the nei ghboring a ni otropic cont ributi ons to be discussed
shortly.
For simplicty, we have treated only the (Jzz comp nent to ill llstrale the
faclors thatcontribll te t tbeshielding. Therearesimilarexpressions for(JH and
Un
is (
shlel
For
larg
F.-q
rig.

13C
com
cont
corr
para
Ih
TAB
tive
7- 11 Interpretation 01 the Chemical Shilt 235
Elec{ran
ci rcula tian
FIGURE 7-19 Local diamagnetic
\\
contr ibuti on to the shielding. Electron
1 Ji- I{ \
ci rculations occur in aplane
1 ,\
perpendicular to the plane 01 the page
\
1
\ 1/ ;-i( I t
The induced lield given by the arrow in
Ha \ \ // " / ;'
the middle is opposed to Ha .
...... / /
....... - r
Lines 01 magnetic I lux
ITI'I" which, in general , a re not nec ssa ri ly equal to 1T :r;; (for (Jxx, the matrix lemenl
is '(01(y2 + z2)/r
3
0 and the hree quanLit ies mu t be averagcd to produc the
shi Id ing obscrved whcn lhe molecule is rapidly tumbling.
For a hydrogen al om, l he lhre nlribul i ns are equal for this local effect.
The range of hemi cal shifts for nuclei olher Ihan hydrogen is cOllsiderably
[arger. For exampl e, the ditference between Ihe fluorine resonances in F l and in
is 542 ppm, compared to the range of about 12 ppm for prOlon shifts (see
Fig. 7- 18). A bri ef compilation 01" fluori n shifts is contained in Table 7- 3 lo
illusl rale this point. wide range ( 500 ppm) of pho phorus chemi cal shifts and
l.i C shift s a re als observed. References are given al the en of lhis chapter for
compi!ati ons . Thc fi ng rprint a ppl ical ion is irnmedia tely ohvious for compounds
cont aining Ih. el mcnls.
The large range in chemica.1 hifls fOI" these nuclei <Irises from a local effect
corresponding l o the second term of lhe Ram ey cquation. Thi s is called the
paramagnecic lerm. '" We are not usi ng lhe word paramagnelic here lu connote
lh ame thing as when it is u ed in connection with molecules containing
TABlE 7-3. Fl uori ne Chemical Shifts of Selected Compounds (in ppm Rela-
tive to CFCl
3
-Larger Negati ve Numbers Indi cate Higher Fiel d)
CH)F -272 CF
4
-70 SOF
2
+ 70
(7 -38)
H - 203 TeF
6
-64 Ti F/- + 75
(CF]hCF -188 (CF
3
)4C -61.5 CIF] + 80
C, F
6
- 163 AsF3 - 48 BrF: + J32. +269
SiF"
- 177 BrF) -3R
F3 + 140
BeFz -1 55 CF
3
C1 - 32 CF
3
0F + 142
BFJOEl z - 153 CF1Cl z - 9 SFsOF + 178
BF.,. - - 149 CF
3
1 - 4 FOCIO) +225
BF] - 131 CF 13 O IF +238. +274
Sif
6
Z
- - 127 TF
s
+ 4 OFz + 250
(CF
3
CF
2
h - 127 SOzFz + 36 F + 288 O
2
r - (aq) -120 SF
6
+42 FNO
z
+ 394
Sb 0 - - 109 SFsOF + 48 Fl + 422
SbF
s
- 108 SeFc, +55 XeF
4
+ 438
CF]H - 88
I s + 53 FNO + 478
b ] - 86 N
2
F
4
+60 XeF
6
+550
(CP1hCO - 82 NSF] +66 UF
6
+ 746
CF)COOH -77
unpaired electrons. Ir is used here to describe the contributions from the
ticJd-induced nonspherical circulation of the electron density, i.e., the second term
on the right-hand side of the Ramsey equation. The term involves field-i nd uced
mixing in of excited states with the ground state, and this gives rise to a
mechanism for no n-s ph rical electron circulation and l he accompanying para-
magnetic contributi on to the shielding. The equation for the paramagnetic effcct
corresponds very closely to the Varamagnctic term in the Van Vleck equation
for magnelic susccpl ibility (vide infra). The following quantiti es appear: <01
ground state and <ni excited state wave functions ; i
z
, the orbital angular
moment um operalor; and En - Ea, the energy difference between the ground
state and the excited st ate being mixed in. The summalion is carried out over
all excited states ; thus, to use the equation one needs wave functions and energies
of all excited states, including those in the conl in uum. The energies of virt ual
orbitals (empty ones) are diffic ult to calculate, and thus it becomes impo ible
to employ the Ramsey equation in the rigorous calculation of the chemical shift
of most molecules.
Evaluation of lb ent ire second term of equa ti o n (7-37) and replacement of
Ihe En - Ea term in t he denominator by an average energy for the excited states
in the molecule (i .e. use of some el ectronic lran ition in lhe molecule tha! is felt
to be an average of all possi ble transili ns to excited sta tes) yi Ids Ihe para-
magnelic cont ribution, (Jp, by ave raging (Jxx , (Jyy ' and (Jzz:
2(eh)2/ 1) 1
(7-40)
(J p = - 3 me \ r
J
f..E
T he average energy approxi maliol1 is often referred to as Ihe e/osure approxima-
tan. Substiluting appropriat values fo r F2 into equation (7-40) (i.e. , the energy
of 4.3 eV for the n -> (J* transition a nd <Ilr.J) for a fluor ine atom 2p orbi tal) ne
oblatns (Jp ::::; 2000 ppm. Snce F- ha spher ical symmet ry, there can be no
angular momentum associ ated with the clectron density in t his speci es, a nd al!
the paramagnetic terms in Ihe Ramsey equation must be zero. A chemical shi ft
difference bet ween F- and F2 of about 2000 ppm is expected comp< red lo only
542 ppm observed. However, il is impossible to obtain a fluo ri de ion that is nol
solvated or ion pair d. The F 2 eh mjcal shift is found to be 625 ppm downfield
from H . This is due in part to the poor nat ure of the average energy
approxi mat ion and in pa rt to the use of an atomic O lr
3
) value. however, in
spite of lhe poo r qua ntitati ve calculation of (J p' there are several important
general izations that can be d rawn from t his discussi on. Since i
z
is zero for an
s o rbi tal in hydrogen co mpounds, one mu t invoke transitions lO lhe 2p orbital
in order to obtain a paramagnetic contributiofl . Now lhe En - Ea value is so
large thal paramagnctic cont ributions are not ver y importa nt in l he proton nmr
speclrum. These paramagnetie eonl ribulions become very large when both an
asymmetric di stri bution of p and d elect rons in the molccule and low-Iying exciled
* h ~ distinction between di amagnetic and paramagnetic cootributions in equation (8- 31) is
so mewhat artificial , for it dcpends upon t he gauge selected for the vector potential (see Slichter text.
p. 76, under Additional Refere o e ~ . The traditiona l gauge corresponds to the mcasurement of angul ar
momentum a bout he nucleus whose chemical shift is being calculated. The total shielding is gaugc
invari ant.
statl
the
eh r
par::
R,m
ha j
opcr
Thc (
el/ua!
\\-hen
~ r al
(To ~
E" -
hi ghe
J'or th
To be
ro le
rliJ ralll
a nd a
7-11 Interpretalion of the Chemical Shift 237
states exist. The paramagnetic tero' gives rise to the principal conlribution to
the shift in 19 F and \3C nmr, and a large chemical shift range is obscrved. T he
chemical shifts in 1 J B nmr have significant contributions from both local
paramagnetic and local diamagnetic effccts.
There is one additional bit of insight provided by the second term of the
Ramsey equation that will concero uso Since this tcrm is important in atoms
having accessible p orbitals, our concern will be with the behavior of the L
operator on these orbitals. The behavior of L: is summarized as follows :
[: Ipz> = m,l Pz > = OIPz> (7-41a)
[ zI Px> = ilpy> (7-41b)
[: Ip)'> = -iIPx> (7-41c)
The results for the Lx and [y operator will be presented as needed. We see from
equation (7-37) that we need to evaluate matrix elements of the type
(7-42)
where CJ. = z, x, and y fo r lhe (Jz z, (Jxx, and (J yy components of the 1 nsor
for al! possible excitations of an eleclron from the ground Sl ale m.o.'s to (J 2 [' *.
(To simplify the problem, hi gher exciled slates will be omitted because t he
E" - fo tcrm becomcs very large fo r molecular orbilals derived from 3s, 3p, and
higher atomic orbitals.) We shall illustrate the evalualion of these matrix elemcnts
for the F
2
molecule (molecular orbital description, valence rbit als
To be systematic, we shall consider the three different ori entalons in which the
molecular axes are aligned with the z-axis parallel to the fiel d, with the x-axis
parallel lO lhe field, and wi th the y-a xis para llel to the field to evaluate (J:: , (Jxx,
and (J y). , respect ively. This requires the use of the L: . L . and L
y
operat ors,
respectively, in the Ramsey equation.
Consider the cases where:
l. The z-axis of Ihe mole(:ule Is allgned wilh Ihe fleld. When the z-axis
01' the molecule is parallel to lhe applied field, the molecule senses no Hx or .y
field, so there are no field- ind ll ced [x or Ly components. All one-electron
excitations place an electron into lhe antibonding molecular o rbital, leading to
malrix elemenls sllch as:
or
where (J2
p
IL
z
l(J* > = CI2) (Pza + PZb)I(I(Pza - Pzb for a bond between fluorine
atoms A and B cvaluating the contribution at A. We know that L: lpz >= O. Thus,
all the mat rix el emcnts for Ihis orientat ion of the molecule are zero, and (Jzz is
lero. This leads lO a generali zalion that will beco me important in sllbsequent
discussion of lhe chemical sh ift. Namel y, the contribution to the chemical shift
an 'ular Im/ll paramagnetic terms, (J p' is zero when the highest-fold symmetry axis (z-axis)
15 gauge
is paral/el to the field .
,
l
238 Chapler 7 Nuclear Magneti c Resonance Spectroscopy-Elementary Aspects
2. The x-axis o, the molecul e is aligned with the fleld, That is. t he z-axis
is perpendicular to the fie ld. For the x-axis aligned this corresponds to evalualing
(Jxx, and the Lx operator. Considering one of the po sible transitions, we have
Since the last term involves the Lx opera tor centered on a operating on b, integrals
of this sort wi ll generally be small ; they are dropped here and in subsequent
discussion. Thc (Pob ILx IPza ) and ( p' <l ILxi Pzb ) terms are two-center integrals;
they, too, generally are small and wi l1 not be considered in future d iscussion. In
the case under consideration, all of these matrix elemen ts are zero beca use L" Ipz )
equals iIPx)' so:
O nly those matrix elements corresponding to (Px ILxlpz) can be non-zero
and these ,Tise from
and
There is only one such mat ri x clemen t to evaluate, namely, e / 2)( p.wl LxlPza )
(recall that <Pxa l LxlPzb) is a two-center integral and is small in compari 'on),
which is eq ual to i/ 2. This va lue c rresp nds to Ihe matrix element (rrILxl(J* ).
The elernent ( 11:* IL..I(J* ) gi ves the same result. Th us. there s a cOl1l ribution to the
paramagl1etic termfor the fi eld alol1 g the x-axis. We see that thefield has coupled
che ground state with the excileJ state; i.e. , Ive haue field-induced mixing.
3. The y-axls o, the molecule is al igned with the neld, This gives t he
same res ult. We must now concern oursel ves wi t h L
y
in th molecular coordi na tc
system. Thc re:; ult is
By analogy with om discll ssion of Lx, only Lbe mat ri elernen t (Pva l Ly!Pza) is
non-zero, a nd we al. expect a pa ramagneti c contri butio n to t he s hielding al
l'luorine when the fiel d is al ong he y-axis. As before, t he other matri x elements
are zero.
b. Remole EHects
Proton s attached to met al ions are in general very hi ghly shielded,(lOI the
resonance oflen occurri ng 5 to 15 ppm to t he high field sidc of TMS an<t in
sorne cases, occurring ove r 60 ppm upfi eld from TMS. A local cont ribut ion
cannot explain these large shift s. The cxi tence of a field-induced moment on a
neighbori ng a tom can be fel l a t lhe a tom whose nmr is being ' Iudied. These are
referred to a. I'emote efJect s or a neighbor wzisotropic cOl/lributiullS. The fi el d t
Ihis remote a t< m may be dominaled by eit her a paramagnelc or a damagneti c
effect but may make a different cont ribution a t lhe a tom being st udied. We hall
work through t he case of tbe HX molecule firs t, assumi ng t hat the diamagnetism
of the remote at om X is domi nant. As illustrated in F ig. 7- 20, the ficld at t he
FIGUF
prol O
tbe 0 1
cid,
field !
dottee
orient
protOl
at the
oren!.
lar on
intens
Wh\!n
The ce
g.i\'cn ,
where
(he prc
at X.
F
lhc pro
NOl e tt
Ihe pro
t\Vo pe.
In an)
moll!cul
by q
axis
ling
uenl

on. In
t lp)
-zero
t lp:.. )
rison),
la*).
ti lo I/e
IIlIpled
I es the
rdinale
P:a> is
Iding al
5emcnls
(l01 lhe
7-11 Interpretation 01 the Chemical Shift 239
--......,
/
/'
/
,---....
\
""-
\
I I \ \
I { V \ \
'\ X I t
\ \ t I /
Ho \" / /
" -. ,_/ /
--- .--' '--/
(Al (B)
FIGURE 7-20 Neighbor aniso!ropy in HX lordilleren!orien!a!ions.
proton in HX from the diamagneticeffect at X will be strongly dependent upon
the orienlation ofthe HX molecule with respect to the direction of the applied
field, Ho. When theapplied field is parallel to the internuclear axis,the magnetic
f1eld generated from diamagnetic electron circulations on X (indicated by the
dotted lines) will shield the proton (Fig. 7-20(A)), while in a perpendicular
orientation (Fig. 7-20(8)) this same effect at X wil! result in deshielding at the
prolon.The magnitude ofthe induced moment on atom X(and hence lhe fi eld
at the proton from this ncighbor effect) for the parallel and perpendicular
orientationswill depend upon thesusceptibilit yofXfor parallel and perpendicu-
lar orientations, XII and XL respectively The sll sceptibilit y, X, is related to lhe
intensity ofthe magnetization, M, by
M
(7-43)
X =Ho
When HX is parallel to the field, the induced moment on X is given by Xll< x/1 o
The contriblltion this remote effect makes to the ' hielding al the proton, all ' is
given by - (JIIH o; expressed in terms ofthe suscepti bility ofX,(JI I is:
(7-44)
where Ris the di stance from X to the proton, X is negat ive (and consequently
the proton is shielded), and XII P: ) is the parallel component ofthe susceptibility
at X.
or the perpendicul ar (1.. ) orientation of HX, the contribll t ion from X at
the prot on is given by
(7-45)
andoin
lri but ion
nI on a
ibcse are
ficld al
lIlagnelic
Weshall
gnctsm
d al the
Note lil a! equations (7 4) and (7-45)give the correct signs for the shielding at
lhe proton, as illustrated in f ig. 7- 20 (Xli and Xi are both negative). We have
t\Vo perpendi cularcompon nts to consider,Xx and x
y
' which are qual here and
in any molecule with a threefold or hi gher symmetry axis. In solution, the
molecuk is rapidlytumbling, O theconcern is with th average value of(J gi ven
by cquation (7-46) :
(7-46)
'
l
l
240 Chapter 7 Nuclear Magneti c Resonance Spectroscopy-Elementary Aspects
t
R
- H
H -
H
FI GURE 7-21 Illustration 01
the parameters (J and R 01
equation (8-37) .
According to equation (7-46), ir the susceptibility is isotropic (i .e., XII = X.1), there
will be no contribu tion to the shi elding a t the nucleus of in terest from diamagnetic
effects o n the neighbor. In CH
4
, for example, XII = X.1 and neither the carbon
nor the C-H bonds can make a neighbor contribution to the proton shift. I n
HX molecules, the remote contribution from X arises because XII f= X-L. The value
to use for R in equations (7-45) and (7-46) is a problem, for one must decide
whether the susceptibility arises on the remote ato m or in the bond. This question
is not a real one but results from our arbitrary factoring of the molecular
susceptibility into parts due to different atoms in the molecule. 1n spite of this
simplification, the approach is valuable and one oft n selects lhe atom or center
of the bond as the point from which to measure R.
Ir one had a molecule in which paramagnetic contributions were dominant,
the same equations would be employed, except that the signs of X would be
positi ve ; i.e., the boldface arrow on X of Fi g. 7-20 would point in the opposite
direction. Paramagnetic contributions from X (or the H-X bond) wi ll be ze ro
for the orientation in which the bond axis is parallel to the fi eld and will be a
maximum for the perpendicular orientation. Thus. the paramagnetic term will
be very anisotropic and often dominates any neighbor anisotropic conlributions
to the proton shifts. Refer to Fig. 7- 20(B) and change the directi on of the arrows
for this paramagnetic effect at X. The paramagnetic effect at X is shielding
(diamagnetic) at the proton. When discussing a remote effect, we labe! it
according to the direction of lhe etTecl on the remote atom . tf Xii and XL were
known, we woul d know its sign and which effect is dominant. This informalion
is seldom available and bolh paramagnetic and diamagnetic neighbor effects
must be quali tatively considered when interpreting proton shi fts.
Equations (7 -44) and (7-45) apply only for linear molecules. For the general
case
where Xxx, Xy'v ' and Xzz are the values along the three principal axcs of the
susceptibility tensor and ex, e
y
, and e
z
correspond to the angles betwecn these
axes and a line drawn from the center ofthe anisotropic contributor (the neighbor
atom or bond) to the atom being investigated. The angle is ill ustrated for a
molecule of C
3 u
s-yrnmetry in Fig. 7-21, where the so urce of the neighbor effect
has been taken al the iodine atom, Xzz is taken al ong the threefold axis, and
Xxx = X
YY
' When Xxx f= Xyy f= Xu' we can select o ur coordinate system such that
the .radius 'ieetor R lies in the y z- (or xz)-plane. Equation (7-47) then beco mes
(7-48)
where = X,z - Xyy and = Xzz - Xxx' When axial symmcilry pertains,
Xzz f= Xxx = Xyy and equation (7-48) beco mes (7-49):
Values for .1X for various bonds can be found in lhe \iterature.
7-12
Jnlera
electr<
of at o
is indl
to the
ar P,l
Fig. 7-
shifts
deshic
protor
cont ril
to the
is 'hiel
Thi ir
benz n
7-13
O ne in
di u .
den ity
Conlri
to accCl
basis o
posse s
val ue f
than lh
on lhe
d e nc
be signi
he hyd
when 1I
lo lhe
Ha
zero
be a
\ViII
lions
rows
lding
el it
were
ation

eneral
(7- 47)
of the
11 these
:ighbor
1 fol' a
Ir cffect
lis, ano
eh that
:comes
7-13 Examples of Chemical Shift Interprelation 241
7-12 INTERATOMIC RING CURRENTS
Interatomic ring currents develop in cyclic, conjugated systems. Field-induced
electron circulations occur in a loop around the ring and extend over a number
ofatoms.Analogous to thecirculation ofelectronsin a wire, a magneticmoment
is induced by theeffect. Themoment induced at thecenterofthe ringis opposed
to the field, but in benzene,for example, the magneticlines offlux atthe protlJns
are parallel l o the applied fi cld, and these protons are deshielded as shown in
Fig. 7-22.Foranotherori enlalionofbenzene relativeto thefield, theringcurrent
shifts the protons to a smalJer extent. The average overall orientation is
deshielding. This is the xplanation for the large deshielding observed for the
protons in benzene(ll) Johnson and Bovey(llJ have calculated the ring current
eontribution to the chemical shift for a proton located at any position relative
to the benzene ringo The acidic hydrogen, upon hyd rogen bonding to benzene,
is shielded,whereasdeshieldingis ob crved withmos! donorsotherthan benzcne.
This indicates that the proton of the Lewis acid is located on the C
axis of
benzene.
1-13 EXAMPlES OF CHEMICAl SHIFT
INTERPRETATION
One importantgeneralization can be drawn from the preceding and subsequent
discussion, viz., chemical shift data are not reli able indica tions of the electron
density around the nucleus being mcasured. Many effects contribute to b.
Contributions from nei ghbor anisotropy are q ual itatively invoked whcn needed
to aecount for difterences betw en measured b values and thoseexpected on t he
basis of chemical intuit ion. The molecule is examjned to see what property it
possesses that could account fol' t he observed discrepancies. For example, the b
vallle for HCl (in the vapor phase) indicates that this proton is more shielded
than those in methane. T his is in contrast to the greater formal posi tive cha rge
011 the proton of HCl than on t hat of CH
4
. Thus, the local iamagnetic e/fect
docs not explain this behavior. The local paramagnetic effect is not expect d to
be sionificanrrora proton.Since HCIis linearand cylindricallysymmetri cabout
the hydrogen-chlorine bond, a neighbor para magnetic contributi on is expecled
when the molecule is perpendicula r to t heapplied field butnot when it is parallel
to lbe field. The net effect will be a shielding of lhe proton in HCl from a
\ (+)
(7 -48)

FIGURE 7- 22 Ring currents in benzene.
(BI
FIGURE 7-23 Contributions
lo the shielding in acetylene.
(A) The ellect here is a
diamagnetic effect at carbon ,
which is a maximum lor this
orientation. (B) The ellect
here is a paramagnetic effect
at carbon , wh ich is a
maximum tor Ihis orientation .
paramagnetic, neighbor anisotropic effect. T he elTect is paramagnetic (deshield-
ing) at X but shielding at Ihe proton. The neighboring anisJtropic effect
dominates the differencc in CH .. and HCI shifts.
In the series HF, HCI, HBr, and Hr, the magnitude of the neighboring
paramagnetic contribul on, p' giving rise to a nisotropy increases with increas-
ing atomic number of the halogen. This parallels the decreascd di fference in lhe
energy of the ground and excited states, t.E, making a fiel d-induced mixing of
gro und and excited states in the compounds of the higher al mi c number atoms
mo re fa vorable. he Ramsey eq ua tion states that the para magnetic contribut ion
to t.(J will be proportional to
T he fo rmal positi ve eharge on t he proton for the compounds in the series
< C
Z
H4 < 1Hz increa es in t he order listed. T he b values increase in the
order C
2
H
6
< C
2
H
2
< C
z
H4' indica ting decreascd hiclding. Acetylen is more
highly shielded than is expected on the basis of its acidity, and t he shielding is
alt ribted to two effects: (1) Remote diamagnetic shieldi ng fr om electron circu la-
tions in the tri ple bond (Fig. 7-23(A)). ( his effect is a maximuIll when t he
molecular axis is aligned wit h the field, and it is classified here as a di amagneti c
effect because the momenl aris ing from the electro n ci rculati on >ppos s the
applied fteld. Recall that the paramagnet ic cont ri buti on is zero for thi orient a-
tion and is a maximum when the ax i is perpendicular to the fi eld.) (2) Remote
pa ramagnetic shi lding fr m high r sta te mixing (F ig. 7-23(B)). Both l h remote
diamagnetic and pa ramagnetic effects influence t.X so a ' to provide shielding al
the proton. T he measured proton chemical shift of acetyl ene relat ive to et hane
is thus expla ined by the r mote diamagnetic and paramagnelic contribut ions
arising from the tri ple bond.
In addition to t he trends in the population of the hyd rogen ls o rbital as a
consequence of the e\ectrollegativity of the altached group, Bucki ngha m has
proposed(12) electricfield and reaction field modcls to account fo r cha nges in the
el ectron density of a bound h drogen a tom.
Suffice it to say that in vi w of rhe many contributions descri b d a boye,
even t he qualit ative interpretation of proton chemi cal shift i t nuous. When 13C
and 19F chemical shifts are con 'idered, the dominance of t he local paramagnel i
term gives rise to such large shi fl differences in series of molecules that neighbor
anisotropy effects become sma ll in compariso n.( 13) T he q ualitati ve interpretat ion
of the shifts in these compounds has met wil h more success.(14) The problem is
still not simple by any means. Changcs in the average excit at ion energy.
one-center t rms, and two-center terms in a mol ecula r orbital description
are all import a nt,(l S.16) leading to the situation where t here a r many more
para meter influencing the measurement than lhere are experimental ob r va bl S.
The reader is refcrred to references 13, \5, and 16 in the event one is ever tempted
to propose a rational ization of chemical shift data.
T he chemica l shi fts of analogous atoms in two different enant iomers are
identical. H owever, as wilh many physical properties, differences are detected in
diaslereoisomers. Advantage has been taken of this ract(l?) to util ize nmr for the
dctermination of opt ical purity. For example, when a d,l mixture of t he phosphi ne
O
/.... C6 Hs
oxi de, C
6
H
s
CH
2
- P , is addcd to the enanti omeri solvent d-2 ,2,2-
- HI ./C 3)
triftuoro-I-phenyl ethanol C(,H - C ..... the hydrogen bonded adducts are
OH
7-14 Ellect 01 Spin-Spin Splitting on the Spectrum 243
dia tereoisomers in which the chemical shifts of the melhyl groups di fler by
1.4 Hz.The differencein shift arises fromdifferences in Ihe neighb ranisotropic
contri bulions in the diastereoisomers. These peaks can be inlegrated and the
rel ativeamountsor thed,l isomersin thephosphineoxidedetermined.Theoplical
pnrityofaresolved produclcan bea.certained bytheabsenceofoneofthepeak .
7- 14 EFFECT OF SPIN-SPIN SPLlTTING
ON THE SPECTRUM
When an nmr spectrum is examin d under high resolution, considerable fine
structureisoften observed.The difference in the high and low resolu tionspectra
ofelhanol can beseen by comparing Fig.7 24 wi th Fig.7- 15.
Thechemical shift oftheCH2 grouprel aLive to theCH) group in "ig. 7--24
is indicated by ,1 measur d from the band centers. The fine structure in lhe
CH
3
and CH
2
peak ' arise' from Ih phcnomenon known a spin-spin splitling,
and lh separation,J, betweenIhepeak comprisingth fi n st ructure isr ferred
t as the spin-spin coupling constallt. Jiuual1ye pressed in hertz, and typicaLly
H is about7HzandJ
H
eH about 5.5 Hz. As mentioned earli er,themagnit ude J
n
of ,1 depend upon' lhe applied field strength. However, lhe magnitude of the
spin-spin coupogconstant in Hz is field indepeodent.
1---!:J. ---l'1
FIGURE 7- 24 High resolution nmr spectrum 01 ethanol
(Iacsimile) . Compare with Fig. 7-15, p. 229.
Spin-Spin
SpliHing
FIGURE 7- 25 The i nterpretation in terms of the appropriate coupling constants 01
the spectrum in Fig. 7-24. The meaning 01 th is st ick-type spectrum will be made
clear shortiy i n the tex!.
The cause of the fi ne structun: and lhe rea on for lhe l1eld-independent
characterofJ can b understood byconsid ringan H- D molecule.Tf bysorne
mechanisrn the magnet ic moment of the proton can be transmitted to the
deuteron, the fi eld trcngt h al which the d uleron precesses at the probe
freq uency wi ll d pend upon the magnelic quant um number of the neighboring
hydrogen nu leus. If the proton nucleus has a spin of + 1/
2
, its magnet ic
momen! is aligned with thefi eld so thal lhe fi eld experi nced by the deuteri um
is the surn of the proton and applied fields.A lower applied field strength, Ho'
d-2,2,2-
FIGURE 7-26 NMR spectra
lar the hypathetical HD
experiment. (A) Deuterium
resonance lor HD ; (B) proton
resonance lor HD.
wiU be required to attain the precession frequency ofthe deuterium nueleus in this
molecule than in the one in which the hydrogen has a magnetic quantum number
of - 1/
2
, In the latter case the field from the proton opposes the applied field and
must be overcome by the applied field to attain a precessional frequency equal
to the probe frequency. The simulated spectrum that would result for the
deuterium resonance is indicated in Fig. 7- 26(A).The mI values for the hydrogen
nuelei in the different molecules that give rise to different peaks are indicated
aboye the respective peaks. The two peaks are of equal intensity because there
is practically equal pro bability that Ihe hydrogen wi ll have + 1/
2
or _1/2
magnetic quantum numbers. The proton resonance spectrum is indicated in Fig.
7- 26(B). These proton resonance peaks correspond to magnetic quantum num-
bers of + 1, O, and -1 for the attached deuterium nuclei in different molecules.
The spin-spin coupling constants and in F ig. 7-26(A) and 7- 26(B), J
OH
J
HO
respectively, have the same value. Subsequently, we shall discuss mechanisms for
transmitt ing the magnetic moment of a neighboring atom to the nueleus
undergoing resonance.
Returning to ethyl alcohol, we shall examine the splitting of the methyl
protons by the methylene protons. T he two equivalent proton on the CH
2
group can have the various possi ble combi na tions of nuclear oricnt a tions
indicated by the arrows in Fig. 7-27(A). In case 1, both nuel ei have mI values of
+1/
2
, giving a sum of +1 and accounting for the low fi eld peak of the HJ
resonance. Case 2 is the combi nation of CH
2
nuclear spins that gives rise
to the middle peak, and case 3 causes the high field peak. The probability thal
the spins of both nuelei will cancel (case 2) is twice as great as that of ei thcr of
the combinations represented by case 1 and case 3. (There are equal numbcrs of
+1/
2
and - 1/
2
spins.) As a result, the a rea of t he central peak will be twice lhat of
the others (sec Fig. 7-24).
The nuclear configuralions of t he CH
3
group t hat cause spli tting of the
CH
2
group are indicaled in F ig. 7- 27(B). The four different total net spins
give rise to four peaks corresponding to lhe larger separation in this mull iplet,
shown in Fig. 7-24. The relative arcas a re in the ratio 1: 3 : 3 : 1. The separat ion
between these peaks in units of Hz is referred to as J
II
--<:_ - H or as JJH_ I-I' T he
superscript in the latter symbol indicates H -H coupli ng between three bonds.
The peak separation in t he met hylene resonance from this coupli ng is equal lO
the peak separation in the methyl group. The spectrum of the resonance i H
2
further complicated by the ract t hat each of the peaks in the quartet from the
methyl splitting is further split into a smaller doubl el by the hydroxyl proton.
In the actual spectrum, sorne of the eight peaks expected from this spl itti ng
overla p, so t hey a re not all clearly seen.
Inc. field strength --
(A)
+ 1 o -1
Inc. field strength __
(B)
2
3
Case
1 '
2'
3'
4'
1
separo
the ef
CCOI
seen.
lines :
dra\\ 1
eftcct
final '
E
d nc
spli tt
can b
such
splil t
A IS 8
7-14 Effect 01 Spi n-Spin Splitting on the Spectrum 245
2 o
3
<--- -1
<---
(A)
FIGURE 7-27 Possible
m,
orientations 01 proton
Case
~
1'
~ +1.1
nuclear magnet ic moments
~ 2
lor(A) -CH
2
- and (B)
-CH
3
groups.
2' ===: ~ ~ +.1
< ~ ~ 2
--- -_. ---------- ----- -- --- -------- ----- ------- -- -.--. ----------.---
3' ::::::::= ~ ~ 1
~ <--- <--- 2
<---
4' <---
<---
(B)
The OH peak is split into a triplet by the CH
2
protons with the same
separation asH H-C-OH in the methyl ene resonance. sually, though notalways,
theeffects ofspin-spin couplingare not seen over more than three sigma b nds.
Accordingly, the interaction of the OH proton with the methyl group is not
seen. The s pectral interpretation is illustrated in ig. 7- 25 by showing which
lines arise from which coupli ngs. This " stick-type spectrum" is constructed by
drawinga line foreach chemicall y shifted different nucleus.00the next ro w, the
elfect of the largest J is shown. Additional lines are added for each .J unt il lhe
final spectrum is obtai ned.
Because ofthe selection rules for this process (vide infra), equivalent nuclei
do not split each other; e.g. , one of the protons in the CH) group cannot be
split by theothertwo protons.Ageneral rule fordeterminingt hespli tt ingpa ttern
can be formulated that eliminates the necessity for going lhrough a procedure
such as that in Fig. 7-27. For the general case of the peak from nucleus A being
split by a non-equivalent nucleus B, the number ofpeaks, n, in the spectrum of
A is given by the formula
(7-50)
TABLE 7-4. Spin-Spin Splitting in Various Molecules
a
Groups Being Groups Doing
Molecule Split(A) the Splitting (B) ESo n
CH)CI-1
2
OH CH) CH
2
3
CH)CH
2
OH CH
2
CH) ) /2 4
PF)
P )
P
F
F
P
)/2
1/
2
4
2
( H))4N+ CH) N 1 3
"Spin quantum numbers ror the most abundant isotopes or nuclei con-
tained in lhe aboye compoundsare H = 1/
2
,P = 1/" F = 1/
2
.N = l .
where LSs equals the sum ofthe spins ofequivalent B nuclei. The application
ofthis formul a is illustrated by theexamp1es in Table7-4.The relative intensitics
of the peaks can be obtained from the coefficients of the terms that result from
the binomial expansion of (1' + 1)'", where m = n - 1 and r is an undefined
r
3
variable; e.g., whcn there are four peaks, n = 4 and m = 3, leading to +
3r
2
+ 3r + 1 from the expansion of(r + 1)3. The coefficients 1:3:3: 1 produce
the relativeintensities.ThePascal triangleis aconvenientdevice fo rremembering
the coefficients ofthe binomial expansion for nuclei with 1 = 1/
2
.
2
3 J
464
5 JO 10 5
6 15 20 15 6
The triangle is readily constructed, for the sum of any two el ments in a row
equals the element between them in the row below.
When two groups ofnon-equivalent nuclei Band C split a third nucleus A,
the number ofpeaks in the A resonance is given by
I1
A
=(2LSs + 1)(2LS
c
+ 1) (7-51)
This is equivalenllo what wasdonein the di cussion of(he methylene resonance
of ethanol. Each of the four peaks from spi n coupling by eH
3
was further
split into a doublet from coupbng lo OH, leading to a tot al of eight peaks.
When l nucleus with 1 1 is coupled to t he observed nucleus, the number of
lines is still given by equal ion(7-50); however, the ill tensities are no longergi en
by the binomial e,pansion. Forinstance, in Fig.7- 26(B), the hydrogen signal is
split intothreeIines by thedeuterium,for whi ch = 1. The intensi lies ofthelbree
linesareall equaland notin the ratio 1:2 :1. si nce there isnearequal probabil ity
thal the deuterium wi ll have + 1, O, and - 1 magnetic quantum numbers. The
same situation occurs with spli tt ing from 14N.
For both chemical sh ift and spin-spin coupling applications, one mu t
recognize when nuclei in a molecule are non-equivalen!. This will be the subject
ofthe next section.
7- 15 DISCOVERING NON-EQUIVALENT PROTONS
In some molecules, a certain proton appears to be non-eq li valen! to other In
a parti ular rotamer but becomes equivalent when rapid rotation occurs; e.g.,
con,ider Ihe non-equivalence of the three methyl protons in a staggered con-
fi gurati on ofCH
3
CHCI
2
. An intere ting problern in which the nonequivalence
is not removed ven with r ~ id rotat ion is observed in the chemical shift of
sub tituteo ethanes of(he typeySJ
A X
\ /
B-C-C- H
/ \
D H
Thc
7-16
1
:l
r
:e
Ig
0\\1
-51)
ance
rther
ak.s.
er of
~ i v n
nal is
three
Ibility
i, The
must
ubject
shift of
7-16 Effect of the Number and Nature of the Bonds on Spin-Spin Coupling 247
The two protons are not equivalent [rom symmetry arguments, and no
cOl1fornwlion can be found in which the twa protons can he interchanged h y a
syml/U'try operaton. This intrinsic asymmet ry will result in different chemical
shiCts which, if large enough, will be observable. This asymmetry can be seen if
you label the two hydrogens and make atable indicating which atoms are
staggered on each side oC the two hydrogens for al! possible staggered rotamers
of (ABD)C-C(I-I
2
X).
Earlyinterpretationsofthe nonequivalence in thenmrassigned the diffErent
shift to different rotam r popul at ions. Even in the absence of population
differences lhe protons are intrinsical1y non-equivalent in all rot amers.
The criteri on to be applied in recoqnizinq this phenomenoll is the ahsence, in
uny conformer that can be drawn, of a :symmetry operatian thal interchanyes lhe
l\Vo protolls. In CH)CHzCI, all the methyl protons are interconvertible in the
\'arious rotamers that can be dra wn, as are the met hylene protons. Another
interest iog example(19)ofnon-equi alent protonsinvolves lhe methylenc rrotons
of (CH
3
H
2
0hSO. The lwo protons of a given met hylene grou p are not
stereochemically equivalent because of the lack ofsymmetry ofthe sulfur atom
with respect to rotationaboutlheS-O- C bonds.One ofthepossible rotamers
is depicted in Fig. 7-28. The small dot in the center represents the sulfur with
lim:s connecting the oxygen, the lone pair, and the ethoxyl groups. The large
cirele represents the methylene carbon wit h two hydrogens, an oxygcn, and a
met hylgroup attached.The molecule is so oriented that \Ve are looking along a
'line from sulfur tocarbono The non-equivalence ofthe two methylene hydrogcns
of a given group is secn in this rotamer, and they cannot be inte r- H
2
changed by a symmetryoperation in :.I!1y other rotamer that can be drawn. Two
non-equivalent nuclei, which cannot be intercha nged by any symmetry clement
the1l1 0lecule possesses,are caIl ed diastereotopic nuclei.
7-16 EFFECT OF THE NUMBER ANO NATURE
OF THE BONOS ON SPIN-SPIN COUPLlNG
Th nature of the spectra ofcomplex molecules \Vil! depend on the number of
bonds through which spin-spi n coupl ingcan be transmitted.F r proton-proton
courling in saturated molecule, of the light elemenls, the magni tude of J falls
off rapi dly as the number of bonds betwcen the t\Vo nuclei increases and, as
menti oned carlier, usually is negligible for coupling ofnuclei separated by more
than thrcc bonds. Long- rangc coupling (coupling over more than three bonds)
is oflenobserved in unsaluratcd molecules. A numbe rofexamplesa rec ntai ned
and discu sed in the litcral urc.(20) In unsat urated mol ecules,theefTects ofnuclear
srinaretran mitted from the C- H a bond by coupl ing ofthe resull ingelcctron
spin on carbon from the sigma bond with the n electrons. This n electron pin
polarization is easily spread over the whole molecule because of lhe extensive
delocali zat ion of the n electrons. Spi n polarization at an a tom in the n-system
can couple back into the a-system, in the same way that it coupl d into (he
rr-systeminltially. In thi s way, the effect ofa nuclear spin is transmitted several
atoms away fr om the spliUi ng nuc\eus.This problem has been treated quant itat -
ively. 1
21
1
When spin-spi neoupling invol es anat mothe rtha n hyd rogen,long-range
coupling can occur by through-space coupling.This intcraction is again one of
FIGURE 7- 28
Non-equivalence of the two
protons of a given methylene
in one of the rotamers of
(CH
3
CH
2
0)2S0
FIGURE 7-29 3'p nmr
spectrum expected lor HPI
2
il ' Jp -
F
> 'Jp -
H
. (A) Stick
interpretation. (B) Spectrum.
spin polarization, but it occurs through non-bonding pairs of electrons, and the
coupling is through space instead of through (J or 7[ bonds. In the compound
CF3CF2SF5 the coupling constant for the ftuorines of the CF 2 group and the
trans ftuorine of the SF 5 group is about 5 Hz, much smaller than that for the
C F 2 group coupling to the cis ftuorines ~ 1 6 Hz), because of the reported
contribution from through-space coupling in the latter case.(22a) This effect has
been invoked rather loosely, and it is suggested that an abnormal temperature
dependence be demonstrated before such an explanation is accepted. (22b)
In order to demonstrate one further point, it is interesting to consider the
phosphorus nuclear magnetic resonance spectrum of the compound H PF 2 ' The
" stick spectrum" in Fig. 7-29 represents the splitting of the phos phorus signal
by the two ftuorine atoms followed by the smaller l Jp_H splitting. T he resulting
spectrum is indicated.
Ifinstead of lJp_F > l Jp_H we have lJp_ H > lJp_
F
, the spectrum in Fig.
7- 30 arises. The fact that lJp_ 1l is larger than lJ
p
_
F
is illustrated in the " stick
spectrum." The spectrum is expected to be one of those shown in Figs. 7-29 or
7-30, depending upon the magnit ude of l J p_ F us. l JP-H' If the (P-F coupling
constant is greater than the P - H coupling constant, Fig. 7-29 will res ult,
whereas Fig. 7- 30 results if 1JP- H is much great er than 1J P- F ' If the two coupling
constants were similar, the spectrum would be a complex pattern intermedia te
between those shown. In most compounds studied, 1J P- F > lJ P-H ~ 1500 Hz
us. ~ 200 Hz), and as expected, the spectrum in Fig. 7-29 is found experimentally.
If two nuclei splitting another group in a molecule are magnetically non-
equivalent, the spectrum will be very much different from that in which there is
splitting by two like nuclei . Four lines of equal intensity will result from splitting
by two non-equivalent nuclei with 1 = 1/ 2, and three Iines with an intensity ratio
1: 2: 1 will be observed for splitting by two equivalent nuclei. Consequently, we
must determine what constitutes magnetically non-equivalent nuclei . Non-equiv-
alence may arise because of differences in the chemical shifts of the two splitting
nuclei or beca use of differences in the J values of the two splitting nuclei with
the nucleus being split. Equivalent nuclei have identical chemical shifts and
coupling constants to all other nuclei. Isochronous nuclei have the same chemical
shift and different couplings. In the molecule H
2
C=CF2, where the two hydro-
gens and the two ftuorines are isochronous and non-equivalen!. Each proton
sees two non-equivalent ftuorines (one cis and one trans) which have identical
chemical shifts but different J
H
-
F
coupling constants. The simple 1: 2 : 1 triplet
expected when both protons and both ftuorines are equivalent is not observed
in either the ftuorine or the proton nmr beca use of the non-equivalence that
(B)
FIGURE 7-30 3'p nmr spectrum expected lor HPF
2
il 'Jp-
H
> 'Jp -
F
. (A) Stick
interpretation. (B) Spectrum.
ex
on
eq
be!
:lit
sta
m'
nm
res!
can
del ,
1n ti
mag
here
caus
e l)n:
mol
bone
m e c ~
to tt
mole
mol
Thr
lo Sp
.., DI
3. F
1( i
;1/ (he
wherc
7-1
'ig.
ick
or
ing
ult,
ling
iate
1Hz
lIy.
\On-
re is
tting
ralio
f. we
~ v
itting
wilh
, and
mieal
I)'dro-
1I"0ton
mtical
t riplet
served
te that
7-17 Scalar Spin-Spin Coupling Mechanisms 249
exisls in lhe J values. We shall consider this eflect in more detail in the section
on second order eflects in the next chapter.
Another eflect that gives rise to spectra other than those predicted by
equation (7-50) is nuclear quadrupole relaxation. O ften splittings do not occur
becaLlse the quadrupolar nucleus to which the element being investigated is
attached undergoes rapid relaxat ion, which causes a rapid change in the spin
state or the quadrupolar nucleus. O nly the average spin state is detected; in somc
instances this relaxing quadrupolar nucleus gives rise to very broad lines in the
nmr spectrum or the 1 = j 2 nucleus bonded to it, and sometimcs a proton
resona nce absorption is broadened by this effect to such an extent that the signal
cannot be distinguished rrom the background. We shall discuss this in more
detail shortly in Section 7-25.
7-17 SCALAR SPIN-SPIN COUPlING MECHANISMS
In the preceding section the splitting in the spectrum or the HD molecule by the
magnetic moment or the a ttached nucleus was discussed. We shaU be concerned
here with the mechanism whereby information regarding the spin of the nucleus
causing the splitting is transmitted to the nucleus whose resonance is split.
Consider a nucleus A split by the nuc\eus B (which has a spin or lj 2) in the
molecule AB. The nuclear spin or B is transmitted to A by polari zation or the
bonding electrons. Various processes cause polarizal ion, and they constitute the
mechanisms ror spin-spin splilling or hydrogen in solution. They al so contribute
lo the magnitude or the scalar spin-spin coupling constan l. J, in various
molecules. Contributions lO J are transmitted via the electrvn density in lhe
molecule and consequently are not averaged lo zero as lhe molecule tumbles.
Three contributions wiJl be considered:
1. Spin-orbital effects
2. Dipolar coupling, indirect, or through-space coupling
3. Fermi contact coupling
Jt i5 worth emphasizing that all three effects are transmitted va the electron density
i/1 the molecule.
Spin-orbitaf effects involve the perturbation that the nuclear spin moment
makes on the orbital magnetic moments or the electrons around the nucleus.
For an [ = 1/
2
nucleus which we label B, ror example, the magnetic lIeld or the
nuclear dipole interacts differently ror mI = +lj 2 than ror mI = _ 1/
2
, with the
orbital magnetic moment or an appropriate electron around B causing a change
in the magnetic field rrom the orbital contribution or these electrons. The new
field rrom lhe electrons at B produces a field at the nucIeus being split , A, that
depends upon whelher the nuclear moment at Bis +lj 2 or _ 1/
2
, Consequently, a
splitting of the nmr resonance or A results. The Hamillonian ror the interaction
on 8 thal i felt at A is
(7- 52)
where L is the electron orbital angular momenlum operator, f is the nuclear spin
mament operator, and r is the distance rrom A to B.
Dipolo,. couplill g, often referred to as indireet eoupli ng, is analogous to the
c\assical dipolar int raeti on of two bar magnels. Si nee the cl assical sit uation i
simpler, we shall treat it fi rs!. It is essential that yOtl obtain a complete
underst anding of this interacti n, for we shall encounter many phenomena in
whi eh Ihis type of inleracti on i import ant in the remai nder of Ihis tex!. The
classical interaction energy E. belween two magnetie moments (wheh we shall
la be! jic and Ji ,) is given by:
(7- 53)
where r is a radiu ector from ~ l to jiN and ,. is the distance b tween tbe two
moment.
The indrect dipol ar coupling meehani sm corresponds to a polarizati on of
tbe paired el eclron density in a molecllle by lhe nuclear moment. T he polarization
of tbis electron density depcnds on whelher mI = + 1/
2
or - 1/
2
, and the modifi ed
elect ron moment is felt thwugh space by the seeond nucleus. Replaeing ji. wit h
-g{3S for lhe eleet ron magnet ic moment and JiN wi th gN{3;J for the nuclear
ma netic m m nt give. the dipolar intcracti on Hamiltonian:
(7- 54)
The nte raetion b tween the el ctron spi n moment and the nuclear m menl
polari7es the spin in the parls of the molecule near Ihe spli tting nuc\eus B. When
this effeet is averaged over Ihe cnt re wav funet ion, lhe fie ld al B is modified
and this modified fi eld 01' the eleclron densit y nets directty through spaee on Ihe
nucleus A, which is being split. The dircctlOn of the effcct depcnd' upon the mI
val ue of lhe B nucl eus, and thus this clTect makes a contri bution to J al lhe A
nucleus.
The importa nt poinl is that this indirect dipolar cOllpli ng of th nu leus B
and lhe paired etectron density, which modifi th eleclron moment felt al A,
i not averaged to zero by rotati on of the molecute. This is itl usl raled in Fig.
7- 31, her an mI = +1/
2
value is ill ustraled at B. Three differenl ori ental ions
of the molecule are shown. The lin s of fl ux from lhe moment on B are shown
affccting lhe moml:nt al the clectron. The lines of fl ux assoeiatcd with lhe change
in lhe momen! at the cleClron fr om B are shown al nucleus A. For lhe lhree
rientations shown, the direetion at \ is the ame.
/' \ ----\ /' \ Ir--
/ \ / \ ! \ I \
I I! \ r \I \
A e- B B e- A
\ ji I
\ }\ j
\ \ I
\ / \ /
\ / \ /
\ . ~ I \ ~ /
H '-./ , _ /
Ha
a
11
FIGURE 7-31 The indirect dipol ar coupling 01 the nuclear moment S to A lar
di fferent orientations 01 the molecule, AS.
\\ here
1 -
10
le
is
te
he
\1
)3)
of
The Fermi contact term is the final coupling mechanism we shaJl consider
for molecu1es rapidly rotatng in solution. This mechanism invol ves a direct
intcraction of the nuclear spin moment with the electron spin momenl such lhat
thcre is increased probabi lity that the electron near B will ha ve pin that is
anlparallel to the nuclear pi n. Since the electron pair in the bond have their
spins paired, a slight increase in the probability of finding an electron of one spin
near B wi ll rcsult in there being an increased probability of fInding an ele lron
of opposite spin near A, as shown in Fig. 7-32. Thus, A receives informati on
about the spin of nucleus B; since the effect at A is in opposi te directions when
mI equals + 1/
2
or - 1/
2
, Ihis interaction con lri butes to the magnitude of J. The
ellect is a direct inleraction of the nuclear spin and the electron spin moment ,
(i r S, where a is the coupling consta nt
If we consider the spin of ollclcll S B to be quantized along lhe z-a xi for
simplicity of presentation, we can describe lhis elTect in more ti tail. The contact
Ha miltonian becomes :
(7--55)
where S:ll has contributions from both eleclrons 1 and 2 at B given by
(7 -56)
Here ru is the radius of the nucleus and r
l
is Ihe distance from nucl eus B to the
electron. T he symbol b(r - r
s
) is lhe Dirac delta function and has a value of
!Gro unl ess elcctron I is at nucleus B. Thus, if p-orbitals were used to bond t\Vo
at oms tog ther, there would be nodes at lhe nuclei and this lerm would be zcro.
Accordingly, in molecules where the F rmi contact term dominales, e.g., Jlle- H.
corrclalions of J with the amount of s character in the bond have been reported .
The mechanism for uncou pli ng the spins in the (J-bond involves fi eld-induced
mixing of ground and excited slates. Perturbat ion theory prod uces :
(7- 57)
In lhe H
2
moleculc, J
H
-
H
(estimated fro Il1 .1
1
[_11) has an experimen tal val ue
of 280 Hz. About 200 Hz comes from the . ermi conlact term, 20 from the dipolar
contribution, and 3 from the nuclear spn-orbtal effect. In general, lhe ermi
contact contribution dominates most cOllpling constants invol ing hydrogen,
e.!f. , 1 J Il - H, 2J~ n - H etc.
lt can also be appreciatcd hat lhe value of J will si mpl y depend upon the
Gnergy difference of lhe two di fr rent k nds of molecules containing B in different
spin states. This energy diffe rence will be independent ofthe fi cl d st rength. The
fidd strength independence of J provides a criterion for determining whether
t\Vo pcaks in a spectrum are the res ult of two non-equivalent protons or
spin-spin coupling. The peak separati on in the spectrum will be diffcre nt when
60- MHz and lOO-MHz pr bes are employed ir the two peaks are due to
non-equivalent proto ns, but the separat on will be the same at diITerc nt fre-
quell cies if the lwo peaks arisc from spin-spin splitting.
7-17 Sea lar Spin-Spin Coupling Meehanisms 251
FIGURE 7- 32 The
antiparallel alignment 01 the
nucl ear moment (solid
arrow) and the electron spin
moment (hollow arrow).
.
I
I
252 Chapter 7 Nuclear Magnetic Resonance Spectroscopy-El ementary Aspects
o O
I I
/ p",
H I OH
O
/ p ",
H I OH
H
H
(A) (B)
FIGURE 7-33 Structures of
(A) phosphorous and (B)
hypophosphorous acids.
FIGURE 7-34 The structure
of P4S3'
7- 18 APPLlCATIONS OF SPIN-SPIN COUPLlNG
TO STRUCTURE DETERMINATION
There have been many applications ofspin-spin cOllpling to the determi nation
of strllctllres. For example, if the spectrllm of a sample cootains the very
characteristic fine strllctllre ofthe CH
2
and CH
j
resonances ofan ethyl group.
this is a good indication of the presence of thi s grollp in the molecllle. O lhcr
applications involve variations in the magnit ude of J io differenl types of
compoll nds. or two non-equivalenl protons on the same Sp2 carbon, e.g.,
ClBrC= CH
2
, proton-proton spin coupling con tants, J
H
-
H
, of I to 3 Hz are
observed. Coupling constants for non-equivalent trans et h lenic protons have
values in the range of 17 to 18 Hz, whereas cis protons give ri e to cOllpling
constants of8 to 11 Hz. These differences aid in determining the struct ures of
Isomers.
The characteristic chemical shift of hydrogens attached to phosphorus
occurs in a li mited ra nge, and the peaks have fi ne structure corresponding to
IJp_ H (pho phorus 1 = 1/
2
) , T he phosphorllS resonance(23) of HPO(OH}z and
H
2
PO(OH) is a doublel in lhe fonner a nd a tripl t in lhe la lter compound,
supporting the slIuct llres in Fig. 7- 33. T he coupl ing of the hydroxyl prot ns
with phos phorus is either too smaJ l to be .resol ed, or it is not observed
because of a fast proton exchange reaction, a phenornenon t o be discus' ed
shortly.Similarresults obtained from phosphorus nmrest abli sh t hest ructu res of
FPO(OH)z and F2PO(OH) as containing, res pecti vely, one and two ft uorines
attached to phosphorus.T he 31 P resonance in P4 S 3 consists oftwo peaks witb
intensity ratios ofthree to one.( 24)The more in,tense peak is a doublet and the
less intense is a quadruplet. Sjnce 1 = Ofor 32S. both the spin-spin split ting and
the relative iotensit ies ofthe p aks indi ca! thrc equiva lenl pho phorus atoms
and a unique one. Tt i ' conc\uded t hat P4S3 has the truclure in Fig. 7- 34.
Thefluorine resonance in BrFs consistsoftwo pea ks with an inten it y ratio
of four to one. The intense line is a doublet and the weak line is a qllin tet
(1 : 4:6:4 :1). Q uadrupole relaxation eliminates spli tting by bromine (l fOI"
79BI" = 81Br = 3/
2
), This indicates that the molecule is a symmet rical tet ragonal
pyramid.
Sollltions of equimolar quantities of TiF62- and TiF
4
in ethanol givc
tluorinenmrspectra( 25) consistingoftwo peakswi t htheintensity ratio4:1(/ = O
for 48Ti). The low intensi ty peak is a quintllplet and the more int nse peak a
dOllbJet. The structure [TiFs(HOC
2
H
s
)]- containing octa hedrally coordinated
titanium was proposed.
The fact ors that determine the magnitude ofthe coupli ng constant are no!
well understood for most systems. It has been shown t hat in the Hamillonian
describing theinteraction between the DCnucleusand a di rectly bonded proton.
the Fermi contact term is t he dominant one.Qualitat ivel y, this term is a measure
of the probability ofthe bonding pajr ofelectrons existing at both nuclei. Tbe
need for this can be appreciated from the earlierdiscussion ofthe ' ermi conlact
coupling mechanism. Thegreater the electron density at both nuclei , the greater
the interacti on of the nuclear moments wi t h the bonding electrons and hence
wilh each other through eleclron spin polarization. Since an electron in an s
orbital has a finite probability at the nucleus and p, d, and higher orbitals have
nodes(zero probability) at the nucleus, the Fermicontact term will bea measure
oft he s characterofthe bond at the two nuclei.
S
densi t:
depen(
the hye
Since.
1J"C-H
tom al
and IS
(7-5 )t
is abou
160 Hz,
p'S of O.
It l
proton
frum lTlI
inducti
deviat
foUowin,
hy ri diz
dra\\ing
orbi tal. I
orbitals.
hybri diz
conlribUl
carbon t
between
magnetic
prop rti
large n ~
hift whi
abre utilil
li necann
tic effect.
The
150. 152,
Ihoughtbt
I. I J"('-H I
Lion arg
i ~ opposie
elTects cad
It>wardh
a nd one si
for Ihe tht
bondi ng b
sequently
s-orbital u
m re of tb!
on
:ry
IIp,
her
of

are
,ave
ting
:$ of
orus
,g to
and
'lmd,
)tons
erved
ussed
res of
)rines
Swith
the
Ig and
atoros
4.
yratio
quintet
(1 for
gonal
mcasurc
7-18 Applications 01 Spin-Spin Coupling to Structure Determination 253
Since the s orbital of hydrogen accommodates all of the proton electron
density, the magnitude of I J"C-H for directly bonded carbon and hydrogen will
depend upon the fraction ofs character,p, in the carbon hybrid orbital bonding
the hydrogen.Thefollowingequationpermitscalculationofp from I J"C- Hdata.
(7- -58)
Since p =0.33 for an Sp2 hybrid and 0.25 for an Sp3 hybrid, it can be seen that
IJ" C_H should bea sensitive measureofcarbon hybridization.Theuse ofIJ'JC_H
to measure the hybridization ofcarbon in a ('-H bond wasstudied in detail(26)
and is supported by valence bond caJculations(27) As expected from equation
(7-58) the 13C-Hcouplingconstantfor a hydrogen in a saturated hydrocarbon
is about 125 Hz, that for the ethylenic hydrogen of a hydrocarbon is around
160 Hz, and that for an acetylenichydrogen is around 250 Hz, corresponding lO
p's of0.25, 0.33, a nd 0.50, respectively.
It has been shown that a linear rela tionship exists belween I JIJC- H and the
proton shift, (j, for a series ofmethyl derivatives in which the contribution to T
from magnetic anisotropy is approximately constant ,(28.29) or varies with the
induclve properties of the group attached to methyl. Those compounds that
deviate from this line have appreciable co:ltributions to (j from anisotropy. The
following explanation is offered for the existence of this relationship. Iso alent
hybridization arguments(30) indicate that as X becomes more e1ectron with-
drawing in the compounds CH
3
X, more p character is employed in the C-X
orbital, and there is a corresponding increase in the s character in the C- H
orbital s. Carbon becomes more electron withdrawing toward hydrogen as the
hybridization changes from Sp3 to Sp2 to Sp.(31) If there are no anisotropic
contribution,a correlation is expected betweencarbon hybridizationand b. Since
carbon hybridization, is in turn related to I JlJC-H, a correlation is expected
between I JIJC-H and b for compounds in which the contributions to (j from
magneticanisotropyareconstant(orvary linearlywith theelectron-withdrawing
properties ofgroupX). In view ofthe difficulty ofassessing the existenccofeven
large anisotropic contributions to the chemical shift (see section on chemical
shiftswhicharegreatlyinfluenced by anisotropy),this relationshipis ofconsider-
able utility. Certainly the chemical shifts ofcompounds that do not fall on the
line cannot be interpreted in terms ofinductivearguments,i.e., a local diamagne-
tic effect.
The constancy of the IJIJC_H coupling constants of the alkyl halides
150, 152, and 152 Hzrespectively for ,CI, Br, and1) is interesting to note. Even
though thereis a pronouncedchangein theelectron withdrawal by F,Cl,Br,and
1, I jllC-H doesnotchange(26)aswould be predicted from theisovalent hybridiza-
tion argument. In this series, there is an effect on the carbon hybridization that
is opposite in direction to electron withdrawal by the halogen. These two
effects cause the hybridization and electron-withdrawing properties of carbon
toward hydrogentoremainconstant.Thisothereffectis basedonorbitaloverlap,
and one should think in terms ofthe s orbital dependence ofthe bond strength
for the three hydrogens and X. As X becomes larger, the orbital used in sigma
bonding becomes more diffuse and the overlap integral beeomes smaUer. Con-
sequently, the energy ofthe C- X bond becomes less sensitive to the amount of
s-orbital used to bond X, and the total energy ofthe system is lowered by using
more ofthe s orbital in the bonds to hydrogen. Thus, as the principal quantum
number of the atom bonded to carbon increases, we expect to see, from this lalter
effect, an increase in 1JlJe _H_
It has been shown that the carbon hybridization in Si(CH
3
)4 , G e(CH
3
)4,
Sn( H
3
)4 ' and Pb(CH
3
)4 changes in such a way as to introduce more s character
into the C- H bond as the atomic number of the central element increases. An
explanation for this change in terms of changing bond energies is proposed, and
it is conclusively demonstrated that chemical shift data for these compounds
cannot be correlated with eJectronegativities of the central elemenl,(2 9J beca use
large anisotropic contributions to the proton chemical shift exist in Ge(CH
3
)4,
Sn(CH
3
)4 , and Pb(CH
3
)4 '
The 13C-H coupling constant in the carbonium ions (CH3) 2CH + and
(CoHs)zCf/' are 168 and 164 Hz, respectivel y, compared to values of 123 and
126 Hz for propane and ( 6HS)2 CH2' This is consistent with apla nar Sp 2
hybridizcd carbono
The magnitude of the coupli ng constant between two hydrogens on adjacent
carbons, 3JI! - H , is a function of (he dihed ral angle between them(32- 34
1
as shown
in Fig. 7-35. The dihedral angle 8 is shown at the top of Fig. 7-35, where (he
C-C bond is being viewed end-on with a dot representing the fron t carbon and
the cirele represcnting the back one. The function is of the form:
3J H-H = A + B cos 8 + C cos 28 (7- 59)
Fo r hydrocarbons, A is 7 Hz, B is 1 Hz, and e is 5 Hz. The end values change
in different systems, but the shape of the curve is the same. Di ffieulties a re
encountered with eleetron-withdrawing substituents and wilh systems in whieh
there are changes in the e- c bond order.
The I J I.' C-H val ues can be of use in assi gni ng peaks in a speetrum.(351 For
example, the proton ehemieal shifts of the two mel hyl resonances in
CH
3
C(O)SCH) are very similar, as shown in Fi g. 7- 36, and impossible lo assign
directly to methyl groups in the compound. Howcvcr, by vi rt ue of the faet that
sulfur is a larger atom than earbon and has a comparable eleet ronegativi ty, the
3)
o
n
11
2:
1)
FIGURE 7-35 variation in 3J
H
_
H
with the dihedral angle (1
shown al the topo
1.1 .
CH
J
lo el
10 11
aS.'ig
h y ~
CH
crupl
c u m ~
H
J
4
rnw
o s
bond
13
7-18 Applications 01 Spin-Spin Coupling to Structure Determination 255
tter
1
3
)4
. ctcr
. An
and
and
and
Sp2

angle O
7.69 7.72
FIGURE 7-36 Proton nmr
speclrum 01 S-methyl
thioacetate at high spectrum
amplitude showing satellites
arising Irom 13C. [From R. L.
Middaugh and R. S Drago, J.
Amer. Chem. Soc., 85, 2575
(1963).]
= 143 C.P.S . J
CH
131 C.P.S.
Il"e_ I'1 values for methyl groups attached to sulfur [1 = 138 to 140 Hz in
e H ]SH (CH 3h SO, (eH .llzS02J are larger (han those for methyl groups attached
to carbonyls (1 = 125 to 130 Hz). ince the proton resonance on a 12C will be
in the center of the 13C satellites, the less shielded peak is llneqllivocall y
assigned
(35
) to the acetyl methyl.
lt has been proposed(36.37) that a rela ti onshi p exist between J
Sn
-
H
and the
hybridization of tin in the tin-carbon bonds of compollnds of the type
CH
34
_"SnX". This relationshi p and res ults from other physical methods were
employed to establish the existence and structllre of five-coordinat e tin addition
compollnds ( H3hSn [. B,( 37) where B is a Lewis base [e.g., (CH
3
lzSO or
CH
3
( )N( H3lz]. The 21
Sn
_
H
vallles suggest a tri g nal bipyramida l geometr
in which the tin empl oys essent iall y sp2-orbitals in bonding to earbon, and,
eonseqllently, a three-eente r molecular orbital usi ng a tin p or p-d orbital in
bondi ng lo lhe Lewis base and ehl rine. Si mil ar results were btai ned for 2 JPb-lI
in the analogous ead eompound (38)
Jnvestigation(39) of a whole series of additi on eompounds between
(CH
3
h SnCI and vari ou. bases indieated lhat lhe 2J S n ~ H eoupling constant
changed in direct proportion to - IJ.H of adducl for mat ion with the base. This
\Vas int rpreted to indicate that as the ti n-base bond beeame stronger, the hybrids
used to bond the methyl groups approached Sp 2 from the ~ S p hybrids used in
( H
3
hSn 1. The relation fo und was:
2J, 1YSn-H = 216 P Sn (7-60)
The 2J
Sn
_ 1 values for Sn(CH
3
) 4 , Sn( CH
3
hCI, and Sn( H
3
h CI
2
- were 54, 57.6
(in k epi ng wit h the isovalent bybridizati on prediction), and 72 [whieh when
subs tituted int o cq uati on (7-60) gives PSn = 0.33]. The coupli ng constants for the
adduets ranged from 64. 2 to 71. 6; the weakest base st udied was H
3
CN, and
the strongest was [( H3)2 N]3P . The plot of -!1.H us. 2J
Sn
_
H
was extrapolated
to the value for free trimethyltin chloride at - !1.H = O.
Coupling constants of equivalent hydrogens cannot be determined directly.
Deuteration of a molecule has only a slight effect on the molecular wave function,
so thi s technique can be used to gain information about the coupling of
equivalent protons. For example, the H-H coupling in H
2
cannot be direct ly
measured, but that in HD is shown to be 45.3 Hz. Since the effect of isotopic
substitution on the magnitude of J is proportional to the magnetogyric ratio,
we have
J
HH
= YH = 6.515
(7-61)
J HO Yo
From this, we calculate lJ
H
_ = 295.1 Hz.
1I
There have been several very interesting applications of phosphorlls nmr in
the determination of structures of complexes of phosphorlls li gands.(4o) The nmr
spectrum and its interpretation a re il!ll strated in Fig. 7-37 for t he complex
Rh(CP3 PhCl
3
[l for 103(Rh) = 1/
2
]. Two isomers are possi ble, faci al and mer-
idional. Al! of the phosphorus ligands a re equivalent in the facial isomer, so the
spectrum in Fig. 7- 37 substantiates that the complex studied was meridional. In
this isomer two phospho rus atoms a re trans to one another (Iabeled P
b
) , and one
is trans to a chlorine (labeled Pa). The splittings are interpreted in the stick
di agram at the top of Fig. 7-37.
The magnitude of 2Jp_p often provides interesting information about the
stereochemistry of complexes. The magnitude of this coupli ng is usually mllch
larger when two phosphorus atoms are trans to one another than when they are
7-19
~ ~
~ ~ _ ~
/ '\ J
J p.RhPb P. RhP
b
FIGURE 7-37 The 31 p
nmr spectrllm 01
Rh( CP3PhCI 3
-OH
7-19 Effect of Fast Chemi cal Reacti ons on the Spectrum 257
cis. locis-PtCl 2(bu3P)[(C6H50 )3 P],thevalueof2Jp _ p is 20 Hz,whilea valueof
758 Hz is fouod in trans-Pd I
2
(bu
3
P)[(C
6
H
s
OhP] and 565 Hz is found in cis-
PdI
2
[(CH
3
hP][(C
2
H
5
hP]'Sorneexceptions to t his rule are found in Cro, Moo,
WO, and Mn(I) compounds. For example, in trans-W(CO)4[(C6HshP](bu3 P),
2Jp_ p is found to be 65Hz.
A very interesting res ult is obtained in the proton or carbon-13 nmrspectra
ofphosphorus complexes.Int he proton nmroftrans-PdI
2
[P(CH 3hJ 2,we might
cxpect to find a doublet methyl resonance wi th per haps a smallsplitting ofeach
peak from the second phosphorus. Although the two phosphorus atoms are
chemically equivalent (isochronous) theya re notmagnetically equivalenl. Anygi ven
methyl gro up would experience two d ifferent phosphorus couplings, 2J P- H and
4J p_
H
. When lhe 2Jp_ p is much largerthan 2 J p_
H
, as it is in t he aboye complex,
lhe proton nmr spect ru m observed is al: 2:1 triplet ; i.e., the two phosphorus
nuclei behave as t hough they were two equi valent nuclei splitting the p roton
resonance. The two phosphorus nuclei are said to be virtually coupled.(41) In a
simil a r Gis complex wherc 2J p_ p ~ 2J P- H , a doublet is obtained. 1 n iew oft he
very common larg 2 J p_ p for trans phosphorus ligands and th 'mal! 2 J p_ p
values for Gis phosphines, thi phenomenon can be used to dis ti nguish t hese t \Vo
kinds of isomers. The use of 13C nmr in this lype of applica tion(42) has been
criticized.(42) Triplets occur in the De nmr with much smaller values ofJ
p
_
p
,
so it is more probable thatcis complexes will show virt ual e upling. The reasoos
fo r virtual coupli ng have beeo discussed in t he literat ure and will be considered
in more det ail in the secti on on second order effects. Virtual coupli ng is an
attempt to treal second-order speclra in a nr t-order way. T he second-ordcr
ana.lysis should be done.
7-19 EFFECT OF FAST CHEMICAL REACTIONS Factors Influencing
ON THE SPECTRUM
the Appearance
Ifoneexamines the high resolurion spectrum ofethanol in an acidi fied solut ion,
of the NMR
th result illustrated in Fig. 7- 38 is obtained, in contrast to the spect rum shown
Spectrum
in Fig. 7-24. The ditTer nce is that the spin-spin splitting frorn Ihe hydroxyl
proton has disappeared. Acid catalyzes a very rapid exchange of t he hyd roxyl
proton. In the time it lakes fo r a met hylene proton to undergo resonance, many
different hydrogen nuclei have been attached to the oxygen. As a result, the
~ D . .
-OH
-eH
.3
1
~ C H 2
______Jl-J
Ine. field sl renglh-
FIGURE 7-38 High resolution
nmr spectrum of a sample of
ethanol (acidified) ,
258 Chapter 7 Nuclear Magneti c Resonance Speclroscopy-Elementary Aspects
methylene proton experi nces a field averaged to zero from lhe O- H nuclear
moment, and lhe 3J
HCOH
coupling disappears. In a similar fas hion, the hydroxyl
proton is att ached to many different et hanol molecules, averaging to zero the
field it experi enees from CH
2
protons, and only a single resonance is observed.
A very dramat ic ill ustrat ion of lhis efTect is the speclrum of a solution of
aqueous ammonia in which one does not see separale N- H and O- H protons,
but only a single exchange-av rage line. When exchange is rapid, the chemical
shift of thi s exchange-av raged li ne is found to be a mol e-fracli on-weighted
average of the shifts of the different types of protons b ing exchanged :
(7- 62)
Tt is importan! to emphasize that NNl h is not the mole fraction of ammoni a, but
the mole fraction of N- H protons, i .e. , NNH, = 3[N H 3J(3[ NH3J + 2[ H 20 J).
30
g
The 19F spectra of sclutions of TiF4- in donor solvents taken at - consisl
of two tri plcts of eq ual intensit y.(4-3J Six-coordinate complexes form by coordinat-
ing two solvenl molecules, and the spectrum obtained is that cxpected for lhe
cis structure. This structure contains lwo sets of non-equivalent fl uorine aloms,
wilh two eq ui val nt f1 uorines in each set. Al 0 onl a single ft uorine peak is
obtained. It is proposed lhat a rapid dissocial ion reaction occurs at O e Ill aki ng
al1 ftuorines equivalent;
At - 30 C this reaction is slowed down so thal lhe non-equivalence can be
detected by nmr. Internal rearrangement and iooic exchange mechanisllls are
also possible.
This example i!lust rates one of the possible pilfa!ls in st ructure delermi nation
using nmr spectroscopy. Ir only lhe hi gh temperalure (O C) spectrum had been
invcsti ga ted or if rapio cxchange occurred al - 30" , it could have becn
incorreclly assum d lhat the adduct had the tralls structure on lhe basis oC lhe
ingle nmr peak. Ir lhe actual structure ere trall S, onl y a singlel ft uorine
resonance would b detected at all temperalures and it woul d have been di mcult
to draw any structural c nc1l1sion because of lhe possibil ity Ihat rapid xchange
might be occu rring at both temperatures. Even in lhe prescnt case, lhe possibility
exists, on the basis of these dala alone, lhat the cis isolller is lhe structure at
- 30 C and that the t r ans isolller predomina tes at O' C.
Thc fluorine nmr spectra oCa large nllmbcr oC compounds of general formula
Rs- nPF
II
(where R is a hydrocar bon, fl uorocarbon, or hali de other Ihan fi uori ne)
ha ve ~ e n reported(44
J
The number oC peaks in the spectrum and the magnitude
of the cou pli ng constanl are employed to d ' duce structures. For a series of
compounds of lhe lypc R1PF3, a trigonal bipyramidal structure is proposed, and
il is fo und that lhe J P.-f values for a, ial ft uorines are ~ 170 Hz less than those
for equalorial ones. The mosl electronegative groups are found in the axi al
positions. The specl ra and coupling e n la nts, oblai ned on these compou nds at
low tempcraturc, indicate that the tw methyl groups in (CH
3
h PF
3
are equato-
rial and the two lrifuoromethyl groups in (CF
3
)2 PF3 are axial. At room tempera-
ture, rapid intramolecula r exchange occurs and t he cffecl of this exchange is lo
average the coupling con tants.
7- 2
or the
\\ hc::re
Con
7- 20 Quantum Mechanical Description 01 Coupling 259
7-20 QUANTUM MECHANICAL DESCRIPTION OF
COUPLlNG
When Ihe magnitude of the separalion between two peaks in the nmr, exprcs cd
in Hz, is of the same order of magni tude as the coupling constant, so-called
second-order spectra resu lt. When this occurs, the peaks in th re, ult ing spectrum
cannot be assigned by inspcct ion as we ha ve done before. Th is is illustrated in
ig. 7-41, when: the spect ra of CI F), obtained by using t'.Vo different probcs,
demonst ra te the e complications.
With a higher-frequency probe (40 MHz), J nd the spectrum in Fig.
7- 39(A) is obtained. T he molecule lF) has two long Cl - F bonds and one short
one, giving rise to non-equivalent ftuorines. The spectrum obtained at 40 MHz
is that expected for non-equ ivalent ftuorines split ting each other. As expected,
the triplet is half the intensity of the doublet. Us ing a lower-frcljuency probe
(10 MHz and the corresponding lowcr magnetic fi Id), the difference in !l for the
non-equi valent fl uorines is of the ord r of magnitude of J
1
_
1
(recall that !l is
field dependent) and the complex spcct rum in ig. 7- 39(B) is obtained. Complex
pattcrns of th i sort res ult whenever the coupli ng constants between non-
equivalent nuclei are of lhe order of magnitude of the chemical shift.
(A)
FIGURE 7-39 Fluorine
nmr speclra 01 CiF
3
. (A) al
40 MHz and (B) al 10 MHz.
,'\'" ;;;;,hl:,:,',,:,, :",: }}m}, }:::i' :::\:::,:::",, ::,:
( B)
When second-order speclra result , other strategies than going to a highcr
liel d can be used to obtain lhe chemical shi fts and coupling constanls. Our
di 'cussion will involvc prolons, but the trealment is perfectly gcneral fo r
any spin 1/
2
nucleus.
The cnergy for a proton, A, surrounded by paired electron densily in a
magnelic field is givc n by:
or the frcljuency of the transition, v, is givcn by:
(7 -63)
\ hefe va is lhe rcsonance frequcncy rO l' abare proton and the shiclding (JA
constant.
l
l
Next consider a molecule containing two different hydrogens that are
involved in spin-spin coupling. We shall focus attention only on the two
hydrogens and ignore the rest of the molecule. When the chemical shi ft difference
of the two hydrogens is very large compared to their J, we shaIl label such a
system AX. T he energy of a system of X) protons whose shi ft differences are
Jarger than J is given by equation (7- 64).
E = -hI vo(l - cr)mj + h L J)km)m
k
(7-64)
j<k
T he first summation on the right gives a difTerent chemical shift term for each
of the j different types of nuclei in the molecule. T he second summation is taken
only for pai rs of nuclei in which j < k, to insure that each palr is considered only
once. It is assumed in writi ng this equati on that J is isotropic. The signi ficance
of equation (7-64) is illustrated in Fig. 7- 40, where the energies of the various
nuclear configurations of an AX system in a magnetic fi eld are illustrated for the
case in which JAX is zera a nd for the case in which it is finite.
FIGURE 7-40 Energies far
the AX system in a magnetic
field [(A) == 1/
2
, (X) == 1/
2
1.
(A) J
AX
== O. the wave functian,
written in the arder AX, is
>-
written above the energy
CJ
a:
level; the energy is written
w
belaw the level. (B) J
AX
=P O. z
w
The J labeling indicates the
change in energy that accurs
from the dotted line, which
represents the energy when
J
AX
== O.
1313
+ [l-1(a
A
+a )] hv
x o
I
(3cx
1
- -+ (a
A
- a
x
)hv
o
cx(3
t
+1(a
A
- )hv a
x o
I
AX
I
' ,
cxcx
I
[-1 + 1(a
A
+ a
x
)] hv
o
J
AX
= O
(A)
1./ I 1 hJ
1"- -------- 4
1<0""------ -- t 1
1......... --hJ
hJ(...!..) (...!.. ) = ...!.. hJ
2 2 4
(B)
In Fig. 7-40A, where JAX =O, the energy levels for the C((:I., af3, f3a, and f3f3
nuclear spin configurations are shown. The A nuclear spin state is listed first and
that of the X nucleus second. The aa energy is the sum of
The energies of the other leveis are caIculated similarly by substituting the
appropriate mI values. The solid arrows indicate the transitions for the A type
of nucleus. O ne arrow corresponds to A nuclei bonded to X nuclei with a spin
and the other to those on X nucIei with f3 spin. The section rule is I1m = 1, so
the A and X nuclear spins cannot change simultaneously. The dashed arrows
indicate the transitions of the X nucleus. By referring to eql!,"tion (7-64) and Fig.
7-40, we see that the frequency difference between aa and f3a (v
o
- cr A v
o
)is equal
to the difference between af3 and f3f3; i.e., the two transitions of nucleus A are
degenerat e. T hus without any coupli ng, a single peak would be observed for A.
By similar reasoning, we expect a single peak for X.
differ
prodl
1 wer
the c (
freqUl
sepan
S
probl
woulc
for th
where
fregue
appea
J as il
chernil
of A b
would
the sp!
E
couplil
of the I
We no
cornpa
(A) ==
With E
O ur b a ~
and ~ 4
elernent
len )
Ielti )
l{JfJ)
are
wo
ous
the
fl{1
nd
the
typc
spin
1, so
r ows
1Fig.
tqual
are
or A.
7-20 Quantum Mechanical Descr iption 01 Coupling 261
Where J AX is finite, and considerably smaller than the chemical shift
difference of A and X, the J jk mjm
k
terms modify the energies shown in Fi g. 7-40A,
producing those shown in (B). Since the rxrx energy is raised by e/ 4) Jh and f3rx is
lowered by e/4) Jh, the arx ~ f3rx transition occurs at a frequency J/2 lower than
the corresponding transition in the JAX = Ocase. The rx f3 ~ fJf3 transition is at a
frequency J/2 higher than that of the JAX = O transition. Thus, the frequency
separation between the two peaks is equal to J in the JAX =1= Ocase.
Spin-spin coupling constants can be positive or negat ive. rn the aboye
problem, a positive J was assumed. If J was taken as negative, the arx energy
IVould be lowered and the f3rx energy would be raised. This would shift the peak
for the rxrx ~ fJrx transition to a freq uency J/2 higher than in the .JAX = O case,
whereas the other transition would occur at a frequency J/ 2 lower. (A greater
frequency corresponds to a lower field.) There would be no change in the
appearance of the spectrum, so there would be no way to determine the sign of
J as illustrated by referring to Fig. 7-41. In Fig. 7-41(A), line 1 represents the
chemical shift difference between A and X and Jine 11 shows the spin-spin splitting
of A by X when JAX is positive. If JAX were negative the result in Fig. 7-42(B)
\Vould be obtained. O ne cannot distinguish the two possibilities by examining
the spectrum obtained in the normal nmr experiment.
Equation (7-64) is the so-called first-order solution of the chemical shift-
coupling constant problem. It applies only when the chemical shift difference, ~
of the two nuclei is large compared to their coupling constant, J (usuall y ~ ~ 5J).
We now treat the more general problem using a system where ~ and .J have
comparable magnitudes. T he label AB will be used to describe this case, where
I(A) = 1/
2
and I (B) = 1/
2
, We shall solve for the energies using:
With E/ h being a frequency, the Hamiltonian is written in frequency units as:
(7-65)
Our basis set will be the nuclear spin functions <PI = Irxrx),!fJ 2 = IrxfJ ), !fJ3 = Jf3rx ) ,
and <P4 = IfJfJ ) To obtain the four energies, we need to solve for ali Ihe matrix
elements in the secular determinant:
Io: a) la(3)
liJa)
liJiJ)
E
1,"10: ) <aa IHl aa) -- <actl Alafl ) <aal AliJa) <aal AliJiJ)
h
E
laP) <aiJI Alaa) <afJIAlafl ) - <Cl.P IHIPCI. ) <aiJl HliJiJ)
h
=0
E
IPa) <iJaIAlaCl.) <f3al Hla(3 ) <f3C1.1 HIf3a) - -
<f3aIHIf3fl)
h
IflP) <PPI Al aa) <f3PI H1aP) <f3f3 IH 1pCI. ) <PPI Hlfl(3 ) - -
E
h
A X
I I
[[
rJAx-l rJXA---I
1 2 3 4
(A)
A X
I I
........JAX-l 1-- JXA--f
" 2 1 4 3
(B)
FIGURE 7-41 Effect 01 the
sign 01 J
AX
on the splitting 01
an A-X system. Here 1
relers to the aX to fJa
transili on, and 2 ref ers lo Ihe
afJ lo fJfJ Iransition.
~
:
262 Chapter 7 Nuclear Magnetic Resonance Spectroscopy-Elemenlary Aspects
The term -E/ h appears on the diagonal because only the diagonal
[- (E/ h) <<"Pnl<"Pn ) ] terms are non-zero; for example,
-(Ej h) <aalaa ) = -Ejh
while
-(Ej h)<lX fJl aa ) = O
The solution of this secular determinant for the four energies is shown in
Appendix G. The four energies are given by:
(7- 66a)
E2 1
- = -( j4)J - e (7-66b)
h
(7-66c)
(7-66d)
The corresponding wave functions are lisled below.
(7- 67a)
~ 2 = cos OlafJ ) - si n (J lfJa) (7-67b)
~ 3 = sin GlafJ ) + cos (JlfJa ) (7-67c)
(7- 67d)
We can summariz lhe results by constructing an energy diagram for lhis AB
system in ig. 7-42, as was previ ou Iy done in Fig. 7-40 fo r the AX systcm. In
Fig. 7 2(A), the situation with J AD = O (which is identical to Fig. 7-40(A)) is
pre ented as a start ing place. T he contribution to the total energy of the various
levels froro J o is shown in Fig. 7-42(B).
The arrows for the four lransitions are indicated in Fig. 7-42. When A and
B ha ve similar chemical shi fts, all four transitions wi fl appear in a narrow region
of the spectrum. The center of the spectrum is given by lhe average of the El -> E
2
and E
2
-> E4 transition energies or:
>-
t)
tI:
w
Z
w
FIGUI
spin
e n e r ~
The ti
glven
7- 5 a
depen
ereme
form
For e
Wc an
ofi ueo
pecl n
7- 21
gonal
wm In
(7-66a)
(7- 66b)
(7- 66<.:)
(7- 66d)
(7-67a)
(767b)
(7-67c)
(767d)
Ihis AB
stcm. In
OlA)) is
vanous
nAand
vreglOn
El -+ E
2
7-21 Effects 01 the Relative Magnitudes 01 J and L'> on the Spectrum 01 an AB Molecule 263
{J{J
[1 -2'
1
(OA + as)) va
>-
{Ja
1
<.:J
-2'(OA- OS)Va
o:
(C>J)
w
z
a{J
1 w
+ 2' (OA-OS)Va
aa
[-1 + 1(OA + as)) Va
(Al (B)
FIGURE 7-42 The second-order energies (written in Irequency units) lor an AS
spin system. (A) J
AS
= O. (B) The second-order result. (*These are the total
energies, where the quantity econtains the shielding constant terms.)
The tra nsi tionenergies relative to this centercan then befouod using theenergies
given above and illustrated in Fig. 7--42(8). The results are presented in Tab[e
7-5 along with the intensitics of the various lransit ions. The intensities are
dependent on Ix (recall that we discussed the fact that H l made the Ix matrix
element non-zero) and are determined from the evaluation of integrals of the
form
(7-68)
or example, the 1-> 3(i.e., El to E
3
) transition yiel ds lhe res ult:
I ( -:t al
XA
+ Ixu lfJu. cos 8+ u.{J sin 8) 1
2
=C/4)(COS 13 + sin (3)2
= e/..)(1 + sin 28)
7-21 EFFECTS OF THE RELATIVE MAGNITUDES OF J
ANO \ ON THE SPECTRUM OF AN AB
MOLECULE
We are now in a position to use lhe results,' ummarized in Table 7-5 losee what
influence the relative magnitudes of and J have on the appeara nce of the
spectrum.
TABLE 7- 5. Energies and Intensities for the
Transit i ons in an AB Molecule
Translllon Separallon Irom Cenl er Relative Inlenslly
1-+2 -(J 2) - C l - sin28
1-. 3 -(J/ 2)+ C l + sin20
2--> 4 (J 2) + e 1- sin 2e
3-+ 4 (J12 - e 1+ sin 2e
where sin 2e = J/ 2C and e= e / 2)(j2 + )1/2
I
l
7-22
264 Chapter 7 Nuclear Magneti c Resonance Spectroscopy-El ementary Aspects
-2C-J-
FI GURE7-45 Spectrum01 an
AS molecule when (TA and (Te
are clase.
A. J = O and\ #- O
The 1 ..... 2 and 3 -. 4 transitions are degenera te, as are 1 ..... 3 and 2 -. 4. The
spectrum consists of two peaks, one from A and one from B, as in the earlier
discussion of Fig. 7-40(A).
B. J #- O, \ #- O, bulJ \-anAXSystem
When L\ dominates e, we have sin 2(J = JI O. With the sin 28 equal to zero,
all fou r transitions have equal intensity. The energies beco me those shown in
Fig. 7 O(B).Relative to the ceoter, we have 1 -.2at (- l/z )J - e /z )L\ , 1-.3at
( - l/ Z)J + e / 2)L\, 2 -.4 at (' / z)J + (' / 2)\ ' and 3 -.4 at (' / 2)J - (' /2 L\ ) for a
spectrum Lhat looks like that shown io Fig. 7-43.
---- H
i nc
J J
FIGURE 7-43 Spectr um 01 an
AX system. (Greaterfrequency
corresponds lo lowerlield.)
2->4
c. \ #- O andJ #- O, bulJ \
When J L\, sin 2(J is appreciable and positive. Therefore, the I -. 3 aod 3 ..... 4
transitions will have equal intensities whi ch are greater than those of 1..... 2and
2 -.4. The I ..... 2 and 3 -.4 transitions will differ by J, as wil l Lhe 2 ..... 4 and
1 -. 3; also, the 3 -.4 and 2 -. 4 will differ by 2e, as wi ll the 1 ..... 3 and 1 -. 2.
The spectrum wi.1I ook like tha! in Fig. 7-44.
1+J/2C
1 - J/2C
FIGURE 7-44 Speclrum 01
an AS system.
I+-- J <'--- 2C I
2 -> 4 1--> 3
D. J #- O, .1 verysmall(A < J)
When erA and er eare almost equal, the value of sin 28 approaches unity and the
1 -.2 and 2 ..... 4 transitions can be easily lost in the baseline noise. The spectrum
resembles that shown in ig. 7-45.
E. J #- O, bul<fA = <f
B
, SO = O
This is the cas of equivalent protons, and we are now in a positioo to see why
equivalent protons do not split each other. When L\ = O, sin 28 equals unity and,
as can be seen from Table 7-5, lhe 1 -.2 and 2 -. 4 transitions have zero inteosity.
The 1 ..... 3 and 3 -.4 transitions have intensity, but tbey have the same energy
and occur at the center of Lhe spectrum; i.e., -C/ z)J +e = (' / 2)J - e = O. This
is a manifestation 01' a generaJ rule : magnetically equivalent nuclei do ooL split
each other.
It! tter
letter.
e.g., b
2.
order.
3.
as well
are eq
be inv
is diff(

full
coupli l
eqll iva
lhe
even tt
dichl ol

moled
th ab
COllplil

would
the teu
p4 S) i_
TI
out in
are rep
iotercs
this tn
Compl
l
lhe
lier
!ro,
in
3at
Ir a
~
->4
and
and
-> 2.
-->2
the
why
and,
y.
This
split
7-22 More Complicated Second-orderSystems 265
7-22 MORE COMPLlCATED SECOND-ORDER
SYSTEMS
It is convenient to c1assify molecules according to the general type of~ and J
systems to which they belong, for this suffices to define the Hamiltonian for the
coupling. The conventi ns that wi U be given are normally applied to spin 1/
2
systems.
1. Each type of magnetic nucleus in the molecule is assigned a capital
letterofthe Romar.. alphabet. All ofoneequivalentset ofnuc1eia re given a ingle
letter, and a subscript is used to indicate the number ofsuch nuclei in tbe set ;
e.y., benzene is A6'
2. Roman letters are assigned to different nucIei in order of decreased
shielding;i.e., t hreedifferentnuc1eiwith si milarshifts'sted in order ofdecreased
shielding woul d be labeled A, B, and . Ifthe second set of nuclei has a very
different shift than the first (i.e., ~ ~ J), a letter far removed in t he alphabet is
used (X,Y Z) to label t he low fiel d peaks. NucJei in between would be labeled
L, M, N, etc. For example, acetaldehyde, CH
3
CHO. is an A
3
X system. This
impliesa first -ordersystem. HFwould bean AXsystem. The molecule HPFCl
2
would be an AMX system. When one is not sure ofthe chemical shift difference,
nearbylettersare used to besafe,forthisimplies that thesystemcould besecond
order.
3. The system of labeli ng must providc information a bout the magnetic,
as well as the chemical. non-equivalence ofnuc1ei in t be molecule. rrtwo atoms
are equivalent by symmetry, t hey have the same chemical hift, but they coul d
be involved in spin-spin coupl ing to other nuc1e such t hat the J to one nucl eus
is different from lhe J to another; e.g., in C
6
H
2
F2Cl 2 (Fi g. 7-46) l he lwo
hydrogens are isochronous, but two different HFcouplings are needed for t he
full analysis. The H(l)-F(l) coupling consta nt is ditTerent from the H(1)- F(2)
coupling constant. The protoos and lhe fl uorines are said to e chemically
equivalent, but magnetically non-eqllivalent. AH that is meant by this is thal, in
the Hamiltonian for this system, two ditTerent HFcouplings mus! beconsidered
even though the two hydrogens and two fluorines are rel a ted by syrnmetry.The
dichloro-difluoro-benzene somer discussed aboye is thus referred to as an
AA'XX' system. The reader should now realize that in the non- planar (D
2d
)
molecul e
Ha>, /H(c)
"13C=C=13C
/ "-
~ h l H(ill
the ab pair is magnetically non-equivaJent to the cd pair because two different
coupling constants to the 13C atoms are involved. The system wi ll be labeled
A
2
A
2
' XX'.The molecul e CIF3 discussed in hapter 6(consi der only fl uorines)
would be c1assi fi ed as an AB
2
molecule (at 10 MHz). The phosphorus nmr of
the tetrapolypbosphate anion, P40 13
6
'- , would yeld an A
2
B
2
spectrum, and
P4S3is an A
3
Xsystem.
The energy levels ofvarious ki nds ofcoupIed systems have been worked
out in detail(B,45,46) in termsoftheshift differences and couplingconstants, and
are reported in the literat ure.To use these resul ts, onec1assifies the molecule of
interest according to the scheme described aboye a nd looks up the a nalysis for
this typeofsystem;e.g., onecouldfi nd theenergyleveIs foranyAA'XX'sys tem.(8)
Compuler programs are also available that fi nd the best vaJ ues of the Ps and
F(1)
(1) HOCI
(2) H Cl
F(2)
FIGURE 7-46 The molecule
1,2-di chloro, 3,6-fluoro
benzene; a nAA'XX' system.
7-23
that reproduce the chemical hifts a nd inten ites of all the peaks n t he
experimental spectrum. The interpretaton of a r lal vely ' imple second-order
0 (3 - )
/ I
spectrum s llustrated for the 3 1 P nmr of the anon H - P-\-0

ndicated in Fig. 7-47. The actual spectrum, IV, is interpreted by gcnerating it
in thre tag . Con deraton of the first tage, 1, yields two lines fr om the lwo
non-equivalent phosph rus atoms, p(,) aod P (b) , and their separation is the
chemical shift difference. The second con iderati on. JI , ineludes splitti ng by
hydrogen. Si nce the hydr gen is on p (U)' Jp",- H > Jp' h,-II ' The four ti nes which
result are inel uded in 11. The third consideralion, UI, included p(U) - P ( b ) ' plilliog
and accounts for thc final spectrum for this ABX case. Tw of th e pected lines
are not detected in lhe final spectrum beca use they ar to weak to be det ected
and another par fal l so cl ose together tha t they appear as a si ngle peak (the
most intense peak). T he analys s of the HP20S3 - speclrum to yield lhe inler-
prel tion conlained in Fig. 7-47 wa carned out(47) wi th a computer anal ysis
tha! fi tted the intensities and ehemical shifts of lhe experimental sp ctrum.
The phenomenon of virt ual coupling, which we disCll SS d earli er, is a
magnet ically non-equivalent system of, for example, the type XAA'X' where J A '
is large.
.t--dPI ,P('-1
II
.... f.-. :,::., .. .....
r-- y
Theoreticol relo hve inlensi t i es
0.15 0.009 2.3 015 0009
FIGURE 7-47 The phosphorus nmr spectrum 01 the diphosphate anion HP
2
0S
3
-
and its interpretation. 1, Chemical shift differences in p(a) and P (b)' 11, H- P splitting.
/11, P- P splitting. IV, Observed spectrum. [Reprinted with permission from C. F.
Callis, et al , J Amer . Chem. Soc , 79, 2722 (1957). copyright by the American
Chemical Society]
In a
hosl
lhe 2
lO di
appli
picku
of th
contn
only
rrad'
cxpen
11 co
Figs.
with a
7-23 Double Resonance and Spin-tickling Experiments 267
Ihe
1
TI
0009
7-23 OOUBLE RESONANCE ANO SPIN-TICKLING
EXPERIMENTS
In doubl e resonance experim nI the sampl is subjected to a econd d. source
whos frequency corresponds lO the La rmor frequency of one of lhc nuclei in
[he sampl . This field cause lhe conlribution to the speclrwn from t bis nucl eus
to disappear, and this nucleus is said to be decoilpled. The second r.f. field is
appli ed wi lh a large amplitude, at right ang1es to H1 and orthogonal 10 l he
pickup coi ls. The net elfecl Of lhis field is lO cause nuclear transitioos in, say, B
of the AB system. Decoupling of Ihe B nucleus is achievcd, and B makes no
cont ribution lO lhe A spectr um. In practice, decoupli ng can be accomplished
only if VA - V
s
> 51.1Asl When lhe speclrum of A is exami ned wilh B b ing
irradiated, lhe symbol A --+ {B} is employed lo ind ieate Ihis fae\.
For sy ' lcms where J ,on can p rform a spin-ti cklinf} e. perilllellt . In this
xperi ment, a wcak r.f. fi eld i' employed and all tran' itions having an en rgy lev 1
in common with lhe peak being irradialed wi ll undergo l hange. Referring to
igs. 7-42 and 7-44, lhe 1. --+ 2 transition is seen to have an energy level in
common wi th the 1 --+ 3 and 2 --+ 4 transitions, but nol lhe 3 --+ 4. Thus, the lal ter
peak is not plit by pio ti cHng the 1 --+ 2 peak, bUI the other spectral lines will
be split. Experimentally, it is found lhat the lickling pli ts the lines lhat havc an
cnergy level in eommon wit h the li ne b ing Furlhermore, if lhe
transit ion for the two pea s connected by a common enl!rgy level corre.' pond
lo a conscculive ehange in spi n of both nuclei, each by 1, a' in 1 --+ :: and 2 --+ 4
Ue. Y.rJ. to cxf3 and cx(J 10 f3{J) or as in 1 --+ 3 and 3 -+ 4, a sharp doublet results.
When l his is nol lhe case, as in l -+ 2 and 1 --+ 3 (i.e. , xcx lO fI. /J and (x cx (O fJcx) or
3 -+ 4 and 2 -+ 4, a broad dou blet results. Wc shall nOl go into lhe rcasons for
thi s. but simply point out lhat t his is a valuable technique for speelral assignment
and energy level ordcring in second-order systems and for detcrmining Ihe
relalive signs of J in firsl -order syslems.
The double resonance lechnique can be emplo)'cd to evaluale eh mical shift
for nuclci olhcr than proton by using a proton probc(4li l Ir nuclells Y is pli tting
a prolon, the frcq uency of Ihe d. fi eld thal is most effecli ve for d c upling Y from
the protons is mcasured, and lhus lhe chemical shift of Y is d temlned using a
proton probc. This is Ihe basis for lhe I DOR te hnique.
Th prolon nmr spectrum of diborane is illustrated in Fig. 7- 48(A). This
speclrum results fro m two sets of non -eq uivalenl prolons (bridge and terminal
protons) being sp!i t by lhe 11 B nuclei . The asteri sks indicale nne struct urc ario ing
from lhe smaller abundance of protons on lB nuclei. eOB has a natural
abul1dance of 18.83 % and I = 3 compared to 8 1.1 7% fo\' 11 B with 1 = J / 2') T n
Fig. 7 8( B), the plitting caused by 11 B has been removed by saturation of the
bor n nuclei b the doub!e resonancc technique. Two peaks of inlcnsily ralio
2: l are obtain d, corre. ponding to lhe r ur lerminal and lwo bridge proto ns.(49)
Two isomer have been obtained in lhe preparation of N
2
F2 ' One delini tely
has l Lrafl s with one flu rine on each nitrogen. In con Hicli ng reports,
the slrllct ll re of lhe second isomer has been reported to be the c:is i omer and
aIso F
2
N= . An cxccll enl diseussi on of the rcsults obtained by employing
several dillerent phy ical meth ds in an attempt to re olv this problem has b n
reported a/ ong wilh lhe flllorine nmr spect rum and re ults from a double
res nance experimenl.(50) Saturation of the 14N nuclcu in this second somer
wit h a sl rong rJ. field causes collapse f all nit rogen splitting. 11 i concluded that
268 Chapler7 Nuclear Magnetic Resonance Spectroscopy- Elementary Aspects

FIGURE 7-48 Proton nmr
spectrum 01 S2H6' (A)
.
Proton nmrwith "s and
lOS splitting. (S) Proton
nmr with "s nucleus
saturated. [From J. N.
Schoo lery, Disc.
Faraday Soc., 19, 215
(1955)]
:;:::;::::::::':':" :.:. ""':"':'::::...:::::::::;::}:::::;::;:::; :::';\
(A)
(B)
the chemical shift of lhe lwo ni trogens mu t be equivalent, and this elimina tes
the F 2N =N st ructure. Addi tional evidence is obtai ned for the cis structure from
a complete spectra l interprelal ion. The value for J -Fcalcul ated in this study
for a cis struclure is rea ona ble when compared lo J - F for NFj '
A more complete di cus, ion of lhe lheory of l he d uble reSOlla nce technique
and many more exampl es of it application are contained in a revi ew a rt icle(SI)
by Balde chwieler am! Randall .
7-24 DETERMINING SIGNS OF COUPLlNG
CONSTANTS
Th double re onance technique has been successfully emp! ycd to determine
the relative sign of coupling constants. This can b i!l ust rated by considering the
proton nmr spect rum(S2) of (C
2
H
s
hTI + in F ig. 7--49 (l = 1/
2
for 20 ST !). If JTI- Cl h
and J
11
-CH, are both positive, both low fi eld peaks correspond to interacti on witJi
po itive nuclear magnetic quanlum numbers of TI. lfthe signs of J are d iffer nt,
one low fi eld peak corresponds to interaction wi th t he moment from thall ium
nuclei where mI = +1/ 2 and the other to - 1/
2
, By irradialion al the cent r of
each of the multiplets, it wa shown that each CH.'! t riplet was coupled to lhe

I--JTI-CH2--l (628 Hz)
I (340Hz) I
Ine. field strength_
FIGURE 7-49 NMR spectrum 01 (C
2
H
5
hTI+ (Iacsimile) .
di
frel
the
J
n
10\1
mu
stn

QUI
ficle
of I
nue
Lhe
non
clou
in q
i
(a
ex pl
ym
to a
com
lead
ot11
asyn
grad
line\l
nnul
nuclJ
may
the s
of ch
or
(or n
broa
1 =
sphel
linates
efrom
study
l nique
clels1 i
to the
7-25 EHects on the Speclrum 01 Nuclei with Quadrupole Moments 269
distant methylene quarlet and vice versa. For examplc, irradiation with a
frequency corresponding to the low field triplet resulted in the disappearance of
the fine structure of the high field methylene signa!. This result ind icates lha t
J lI --CH, and J
T1
-
CH
, have opposite signs. Ir the sigo were the same the two
low field mult iplets would be coupled together as would the two high field
multiplets, and sa turation of the low field triplet would cau e collapse of the fine
structure in the low field methyicre signa!.
7- 25 EFFECTS ON THE SPECTRUM OF NUClEI
WITH QUADRUPOlE MOMENTS
Quadrupolar nuclci are often very effi ciently relaxed by the fluct uating electric
fields that arise from lhe dipolar solvenl and solute molecllles. T he mechanism
of quadrupoJe rel axation depends upon the inleract ion of l he quadrupolar
nucJells with the eJectric fi eld gradi ent al the nucleus. This gradient arises when
the qlladrupolar nucleus is in a molecllle in which it is surro unded by a
non-spherical distribution of eleet ron dens ity.
The field gradient, q, is usen to describe the deviation of l he electronic charge
cloud about lhe nucleus from spherical symmetry. Ir t he groups a bout the nu leus
in question have cubic symmetry (e .g. , T
d
or Oh point groups), the charge cloud
is spherical and the value of q is zero. Ir t he molecule has cylindrica l symmelry
(a threefold or higher symmetry axis), the deviat io n from spherical symm l ry is
expressed by the magnitude of q. If the molecule ha less than cylindrical
symmelry, two parameters are usuall y needed, q and ~ l The quanti ty '1 is referred
lO as the asymmetry parameter. T he word usually" is inserted because certain h
combinations of angles and charges can cause fortui toll s canc lIat ions 01' efl'ects
leading to '1 = O. The axis of largest q is labeled z and is described by qzz. The
other axes, described by field gradients qxx and qyy, are described by t he
asymmetry parameter, which is defined as:
(7-69)
The effectiveness of the relaxation depends upon the magnitud of the field
gradient. Rapid nuclear quadrupole relaxation has a pronounced effect on the
linewidth obtained in the nmr spectrum of the quadrupol ar nucleus, a nd it also
influences the nmr spectra of protons or other nuclei attached to this quadrupolar
nucleus. In the latter case, spl ittings of a prot on from the quadrupolar nucleus
may not be observed or the proton signal may be so ext nsively broadened thal
lhe signal itself is not observed. This can be understood by ana logy to the effect
of ehemical exchange on the proton nmr spectra. Either rapid chemical exchange
or rapid nuclear quadr upole relaxation in effect plaees the proton on a nucleus
(or nuclei, ror ehemical exchange) whose spin state is rapid ly changing. Nuclear
quadrupole relaxat ion rales often correspond to an intermediate rate of chemical
exchange, so extensive broadening i. us ua lly obser ed. As a result of quadrupole
relaxation, the proton nmr spectrum of 14NH3 e
4
N 1 = 1) c nsis ts of three ver y
broad signals; whi le in lhe absence of this effect, (he spectrum of 15 NH3 e
5
N
1 = 1/ 2) consisls of a sharp doublet. 00 the other hand, in 14NH4+ , where a
spherical distri bution of eleet ron densi ty gi ves rise to a zero field gradient, a
,
270 Chapler7 Nucl ear Magnetic Resonance Spectroscopy-Elementary Aspects
(A)
(B)
(e)
FIGURE 7- 50 Proton nmr of
AI(BH.b. (A) Proton
resonance. (B) Proton
resonance, 11 B saturated.
(C) Proton resonance, 27Al
saturated. [From R. A. Ogg,
Jr, and J. D. Ray, Disc.
Faraday Soc , 19,239 (1955) .)
sharp three-line speetrum results. In a moJeeuJe with a very large field gradient ,
a broad signaJ with no fine structure is eommonly obtained.
When one attempts to obtain an nmr speetrum of a nucleus with a
quadrupole moment (e.g., 3sCI and 14N) that undergoes relaxation readily, the
signals are sometimes broadened so extensively that no speetrum is obtained.
This is the case for most halogen (except ftuorine) compounds. Sharp signals
have been obtained for the haJide ions and symmetrical compounds of the
halogens (e.g., CI 0
4
- ), where the sphericalcharge distribution gives rise to only
small field gradients at the nucleus, leading to [arger values for TI .
Solutions of I e
2
?!. 1 = 5/
2
) give rise to an nmr signa!. When iodine is
added, the triiodide ion, 1)-, is formed, Jestroying the cubie symmetry of the
iodide ion so tha! quadrupole broadening becomes effcctive and the signal
disappears. Small amounts of iodine result in a broadening of the iodide
resonance,a nd the rateconstantfor the reaction r- +rz -> 13- can becalculated
broadening.(5)J It is interesting t o note that chlorine chemical shift s have been
observed(5 4)for the compounds: SiCl
4
,CrO zClz, VOCI), and TiCl
4
, where the
chlorine is in an environrnent oflowcr than cubic symmetry.
An interesting effect has becn reported for the ftuorine nmr spectrum of
NF). The changes in a series ofspeetra oblained as a function of temp rature
are opposite to those normally obtained for exchange processes. Al - 205"ea
sharp single peak is obtained for NF) ; as the temperature is rai scd lhe line
broadens and a spect rum consisting ofa sharp t ri plet U = 1for 14N) result s al
20C. Itis proposed that at low temperat ure lhe slow molecular motions are
most effective for quadrupole relaxation of 14N ; as a result, a single line is
obtained. At higher lemp rat ures, relaxation is not as fli ctivc and the lifetime
ofa given state for Ihe 14N nucleus is sufficient to cause pi n-spin splitting. A
similar effect is observed for pyrrole.(551 The 14N spe trum of azoxybenzene
exhibi ts only a singlet. The nirrogens are not equivalent, and it is
proposed that the field gradient at the N-O nitrogcn is so large as to makc
this resonance unobservable.
T he double resona nce technique has been ' uccessfully used on t he p rot on
nmrspectrum ofAI(BH
4
h.This molecule contai n six Al- H- B bridge bond .
Bot h Band2 7AlU = 5/
2
) havequadrupole momenls.T he prot on nmrat30 MHz
consists(56) ofasingle broadline(Fig.7-50(A)). Whenthe 11B nucleusissaturat ed
eH -> {11B}), theproton resonancespect rurn in Fig.7- 50(B) results. Fig. 7-50(C)
r prcsentsthe proton nmrspectrumwhen thesample is irradial ed with frequency
corresponding to that of 2 7Al eH -> e7Al }). The fo ur large peaks in (e) ari se
from 11 B spli tt ing of lhe proton a nd the sma ller pea ks from IBspli tting. Thc
bridgingand terminal bydrogens are notdistinguish d becau e ofa rapid prolon
exchange reaction t bat makes all hyd rogens magnetica lly equi valent.
1. H.
W
Ye
2. J.,
Re
3. (a)
(b)
4. M.
5. N.
S!
e ~
~
6. L
7. A
8. (11 )
Vol
(b)
Vol
9. E-..I
I\el
pr
JO. A I
11. '. l
12. (a)
(b).
13. w.
( 1 '}(
14. D e
15. F. J
16. (al
lb) I
17. w.
IhIJ.
18. H. '
19. J S
20. R.
1. H. S. G utowsk , ..Physical Methods of Organichemistry," 3rd Ed., part 4. A. REFERENCES
Weissberger, ed. (Vol. 1 of"Techniques of Organ ic Chemistry"), Interscience, ew
CITED
York,1960.
2. J. A. Pople,W. G.Schneider,andA. 1. Bernstcin,,.High Resolution Nuclear Magnetic
Resonance," McGraw-Hill, New York, 1959.
3. (a) J. W. Emsley,1. Feeney,and L. H.SutcJiffc,"High Resolution . udear Rcsonance
Spectroscopy," Vol. 1, Perga mon Prcss, Ncw York, 1966.
(b) Same authors and title ; Vol. 2.
4. M.W. Dietrichand R. E.Kcller,Anal.Chem., 36,258(1964)a nd rderencestherein.
5. N. S. Bhacca. L. F. J ohnson, and 1. . Shoolery," MR Spcctra Catalog," Varian
Associates, Palo Alto, Calir. , 1962 ; "The Sadtler Standard Spectra; MR," Sadtler
ResearchLaboratories,Philadelphia, 1972'L. F. Johnsonand W.C. Jankowski,"C-13
MR Spectra"(a collection), Interscience, Ncw York, 1972.
6. L. Ebcrson and S. Farsen, J. Phys. hem., 64, 767 (1960).
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8. (a)1. W. Emsleyel al., '" High Resolution Nuclear Magnetic ResonanceSpectroscopy,"
Vol. 1, Pergamon Press, New York. 1966;
(b) P. Diehl , E. Fluck, and R. Kos feld, eds. ," MR Basic Principies and Progr ss:'
Vol. 5, pringer-Verlag, New York, 1971.
9. E. Fluck,"Anorganischeund AlIgcmcine Chemi in Einzeldarstellungen. BandV. Die
Kernmagnctischc Re onanz und Ihre Anwendung in der Anorganische Chemie,"
Springer- Verlag, Berlin, 1963.
10. A. D. Buckingham and P. J. Stephens, 1. Chem. Soc., 1964, 4583.
11. C. E.Johnsonand F. A.Bovey.J. Chcm. Phys..29, 1012(1 958)and referencestherein.
12. (a) A. D. Buckingham, Can. 1. Ch m., 38, 300 (1960);
(b) J.!. Musher, J hem. Phys ., 3 7, 34 (1962).
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(1966).
14. D.Gurka and R. W. Taft, 1. Amer. Chem. Soc. , 91,4794 (1969).
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(b) R. J. Pugmire and D. M. Grant, 1. Amer. Chem. Soc., 90, 697 (I96X).
17. W. H. Pirkle, S. D. Beare, and R. L. Muntz, J. Amer. ~ h e m Soc., 91 , 4575 (1969);
ihid., 93, 2817 (1971) and refercnccs therein.
18. H. S. Gutowsky, 1. Chem. Phys., 37, 2136 (1962).
19. J.S. Waugh and F. A. Cotton, J. Phys. Chem., 65, 562 (1961).
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35. R. L. Middaugh and R. S. Drago, J. Amer. Chem. Soc. ,85,2575 (1963).
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37. N. A. Matwiyoffand R. S. Drago, Inorg. Chem. , 3,337(1964).
38. G. D. Shier and R. S. Drago, J. rganomet. Chem., 6, 359 (1966).
39. T. F. Bolles and R. S. Drago,1. Amer. Chem. Soc., 88, 5730 (1966).
40. J. . Nixon and A. Pidcock, Ann. Re\'. NMR Spectroscopy, 2, 345 (1969).
41. R. K. Harris, Canad. J. Chem., 42, 2275,2575 (1964).
42. (a) B. E. Mann, B. L. Shaw, and K. E. tainbank, Chem. Comm., 151 (1972);
(b) D. E. Axelson and C. E. Holloway, Chem. Comm. , 455 (1973).
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44. E. L. Muetterties, W. Mahler, and R. S. Schmutzler, Inorg. Chem., 2, 613 (1963).
45. 1. D. Roberts, HAn Introduction to the Spin-SpinSplitting in High Resolution MR
Spcctra:' W.A. Benjamin, New York, 1961.
46. P L. orio, hem. Rev., 60, 363 (1960).
47. C. F. allis el al., 1. Amer.Chem. Soc., 79, 2719 (1957).
48. .C. Leyy and . L. Nelson,"Carbon-13 Nuclear Magnetic Resonance for Organic
Chemists," Wiley-Interscience, New York, 1972.
49. 1. N. Shoolery, Disc. Faraday Soc., 19, 215 (1955).
SO. 1. H. Noggle,J. D.Baldeschwielcr,andC. B. Colburn, .f. Chem. Phys.,37, 182(1962).
51. J. Baldeschwieler and E. W. Randall . Chem. Rey.63, 82 (1963).
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Soc., 1962, 847.
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COMPILATIONS
OF CHEMICAL
SHIFTS
Proton Shifts
N. S. Bhacca, L. F. Johnson, and J. N. Shoolery, HNMR Spectra Catalog," Varian
Associates, Palo Alto, Calir. , 1962.
"The Sadtler Standard pectra ; NMR," Sadtler Research Laboratories, Philadelphia,
1972.
N. F.Chamberlain,"The PracticeofNMR Spectroscopy with Spectra-StructureCorrela-
tions fo r Hydrogen-I," Plenum, London and New York, 1974.
13C Shifts
L. F.Johnsonand W. C.Jankowski," C- 13 NMRSpeclra,"Wiley-Inlt.: iscience,NewYork.
1972.
G. C. Leyy. R. L. Lichter, and G. L. Nelson, "Carbon-13 Nuclear Magnetic Resonance
Spectroscopy," 2nd ed., Wiley-Interscience, 1989.
G. C.Levy,"Topics in DC NMRSpeclroscopy," Wiley-Interscience, New York,yolumes
from 1974 lO presenL
B. E. Mann and B. F. Taylor, Hl 3C NMR Data for Organomelallic Compounds,"
Academic P re s, New Y rk, 1981.
Q.T. Pham, R. Pet iaud,and H. Waton,"Proton and Carbon NMR ofPolymers," Wiley,
New York, 1983.
a.
b.
5.
R
JlpShifts
E. Fluck, "Anorganische und Allgemeine Chemie in Einzeldrstellungen. Band V. Die
Kernmagnetische Resonanz und fh re Anwendung in der Anorganische Chemie,"
Springer- Vcrlag, Berln, 1963
"Methods in Stereochemical AnaJysis," Volume 8, by J. G. Verkade and L. D. Quin,eds.,
VCH Publishers, Deerfield Beach, Fla.
"31P NMR, Principies and Applications," D. G. Gorestcin, ed., Academic Press, New
York, 1984.
19F Shifts
H. Dungan and J. R. VanWazcr, "Compilation of Reported 19 Chemical Shifts,"
Wiley-lnterscience. New York, 1970.
A. 1. Gordon and R. A. Ford,"Thl! Companion," Wiley, New York. 1972.
IIBShifts
H.Noth, " MRSpectroscopyofBoronCompounds,"Springer-Verlag,NewYork, 1978.
M.iscellaneous Nuclei Shifts
. MR of Newly Accessible Nuclci ," P. LaszJo, ed. , Academic Press, New York, 1983.
R. K. Harris and B. E. Mann, " NMR and the Periodic Ta ble," Academic Press, New
York , 1978.
General Text
A. Bovey (with L. Jelinski and P. A. Mirav) "Nuclear Magnetic Resonance Spec-
troscopy," 2nd ed., Academic Prcss, New York, 1988.
For more practice with Spectral Interpretalion
R. M.Silverstein.G.C. Bassler,andT.C. Morrill, " pectrometric ldentificationofOrganic
Compounds," 4th ed. , Wi ley, New York, 1981.
EXERCISES 1. The (j value ofa substance rclativc to the external standard, methylene chloridc, is
- 2.5. Calculate (j relative to external standards (a) benzene and (b) water using the
data in Appendix F.
2. Ass uming the relationship discussed between J
Sn
-
H
and hybridi 7.ation, what would
bethe ratioofthe couplingconst ants in a five-coordinate and six-coordinatecomplex
of( J-1 -lhSnCl [i .e., (CH3hSnCI .B and (e HJhSnCI.2BJ?
J. Thecompound B[N(CHJhJJ is prepared and dissolved in a wide numberofdifferent
solvents. Propose a met hod ofdetermining in which ones the solvent is coordinat ed
to the compound.
4. Consider the diamagnetic complex (Me
J
P)4Pt2+ Sketch the phosphorus resonance
signal if
a. Jp-
H
> Jp_ p,.
b. J,,- r, > J p- H
5. Indicate the number of isomers for cyclic compounds of formulas P-l N
3
(CHJh CI4'
andsketch the phosphorus resonanccspectrum ofeach (assume 11 > J, J P_ II is small ,
andJp-
H
can beignoredfor phosphorusatomswhichdonotcontain methylgroups).
Exercises 273
274 Chapter 7 Nuclear Magnetl c Resonance Spectroscopy-El ementary Aspects
6. Would you expect the l ~ nmrspectrum lo be sharper in NH, or H
4
+? (For 14N,
I = l.) Explain.
7. Consider all possible isomcrs lhat could be olJtained rol' the eight -membered ring
compound P4 . C1
6
(NHRh and indi cate the ideal phosphorus resonance spectrum
expected ror each. Which or the aboye are defi nitely elimil1:.l1cU ir lhe phosphorus
resonance consisls or two triplets orequa lintensi ty ?
CHz-O"
8. The proton nmr spectrum of l / S-O is not a singlet. Is the SOj group
CH
2
-O
planar ?What would lilespectrum looklike irthesulrur underwent rapid inyersion?
9. [t is ro und lhat he methylene groups in (e H J H2hSBF3 giye rise to a single
methylene resonancc. Expla in.
b. Ignore the splitting of he melhyl groups by the phenyl protons in lhe aboye
compound and assume J < tl . What would the spectrum or the methyl prolons
look like?
11. The proton nmr sp etra of a series of compounds are giyen below. Assign their
geometries and interpret the sp-:cl ra
100 MHz
(3)
H---- 10.0 9.0 8.0 ppm
60 MHz
(2)
TMS
(1)
12.0 10.0 8.0 6.0 4. 0 2.0 0.0 - 2.0 - 4.0 ppm
Exercises 275
3. The compound is R CI)[P( H)h 6HsJ J. Curve (1) is tht: I"ull spcctrum, (2)
is a more intense sweep 01" the 6.0 to 13.0 ppm region, and (3) i ~ the 100 M I L ~
spcctrum 01" lhe 7.0 to 10 ppm region.
b. Why is the spectrum in part (a) at 100 MHz difTercnl from that al 60 MHz?
Why are the chc mical shifts in ppm rclativc lo TMS the same'J
c. A compound wit h empirical I"ormul a ~ H tt .
ns
Iht: ir
d. \ compound with cmpi rical I"or mula C
2
H] F30.
e. A compound with empirical formula C
2
H
4
0 .
1.6 ppm
9.8
f. A compound with empirical formula C
4
H
6

ppm
g. A compound with emprical formela C
4
H O
2
,
8.0
6 Hz
l I
8.1
5.2
h. A compound with empirical formu la C
3
H
s
CIF
2

J = 12
H
J = 18
t----1
1.7
1.3 ppm
6 Relative
areas
o ppm
Exercises 277
l. A compound with empirical formula Cs HlOO. The peak at 2.4 ppm vanishes
in 0
2
0 .
(nondescriptmultiplet)
7.2 3.7 2.8 2.4 ppm
5 2 2 Relative
area
I J 11
I
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0. 0 ppm
k. A compound with empirical formula C ) H
5
zC!.
nlA_---....,.'
12.0 4.9 1.5 ppm
278 Chapter 7 Nuclear Magnetic Resonance Spectroscopy-El ementary Aspects
J. A compound wth emprica l formula C1HaNCI di ssolved in wa ter.
8.4 5.6 3.7 1.7 ppm
m. A compound wi th empirical formu la 14H220. .
pprn
n. A compound with empri cal formul a (Si H
3
h PSiH
2
CII
J
.
321 Hz
8 15.6
72 108
Exercises 279
o. A compound with empirical formula Pt [P(C2HsJ.J2HCI. (The peaks at 8ppm
are nondescript multiplets.)
26.9 38.2 ppm
4 Relative
areas
p. A compound with empirical formula CH6' The curves above the peaks
represent the integrated intensiticsoftllepeaks.The r-elati vearcascan be obtaineu
by comparingthe heights(numberofsquares)oflhe respectiveintegrationcurves.
1m
l
:i TIt
7.0 5.0 1.0 o ppm
q. A compound with empirical formula CsHJOO. The curves aboye the peaKs
rcpresent the integrated intensities ofthe pcaks. The relative arcascan be obtaincd
by comparing the height s,in squarcs. oft he r-espective integration curves.
-r.
+
Itr
rt+t
11m,
321Hz
7.0 5.0 3.0 2.0 1.0 0. 0
ppm
r. A compound with empirical rormula C
5
HoO. The curves above the peaks
represent the integrated intensitiesorthe peaks. The relative ancas can be obtained
by comparing the heights, in squares, of the respective integration curves.
s.
3.0 2.0 1.0
Acompound with empirical formula C
H
H
7
0F.
0.0
ppm
12.
8.0 5.0 2.0 o
&.
b.
Exercises 281
t. The 13C nmr of OSC
2
D
6
at 75.1 M Hz (D = deuterium with a spin of 1).
39.01,
1 39.
38 73
1 .
40.11-----,
I 38.45
45 40 35 30 25
ppm
12. Spectrum (a) res ult s for the methyl region of one isomer of Pd[P(CH3hC6H5J 212'
Spectrum (b) is obtained in the methyl region for the other isomer of
Pt[P(CH
3
hC
6
H 5J2'2'
(A)
2 Relative areas
(B)
4
Related areas
a. Which is cis and which is trans?
b. Explain why the areas in (b) are in the ratio of 1 to 4 to 1.
13. The I 'B nmr spectrum below is obtained for 5- 1- 2,4-C
2
B
5
H
6
. Intt.:rprct Ihe
spectrum. (Hint: B, H, " is a pentagonal bipyramid of B-H s ubunit s in which the
axial borons are numhered I and 7.)
14. Thc I<lr nmr sp ctrum of PF
J
(NH" )2 is r ported in (a), and expanded spectra o f th
indi vidual peaks are presented in (b) through (e). Propose a structure and interpret
lhe spectrum.
(A)
42.9ppm 59.7ppm 66. 6 ppm 88.1 ppm
20 cps
t-----i
(B)
42.9 ppm
(e)
59.7 ppm
(D)
66.6 ppm
(E)
88.1 pprn
15.
16. e
-
--L-
8.0
Exercises 283
15. The pro lon resonancc or lhe hydr idic hyd rogc n or H is give n as
roll ows. Propose a slr ucture ror lhi s complex.
26 Hz
lhe
16. Given the rol lowing prolon nmr spcctra and molecul a rslructu rcs, assign all peaks:
(a )
(a ) Me
M (e )
e"'--., / CH? SO(-)
Ji........ /" "-.. /" 3
Me CH
2
CH
2
Na(+)
(a ) (b) (d)
3.0 2.0 1. 0 0.0
ppm
(a)
0-
Me
1-0
j Si j
1
H
(b)
8.0 7.0 6.0 5.0 4.0 3.0 2.0 ,.0 0.0
ppm
8.0 7.0 6.0 5.0 4.0
284 Chapter 7 Nuclear Magneli c Resonance Specl roscopy-Elemenlary Aspecls
(b)
H
(b)H
H(e)
(c)H Fe
(d)H
H(e)
a ~
7.0 6.0 3.0 2.0 1.0 0.0
ppm
17. Whal properlies in a runctional group X(which can consist ormore Ihan one alom)
attached lo an isopropyl group can cause non-equivalenl melhyls to occur in Ihe
isopropyl group?
18. Therollowingprotonnmrspeclrumis Ihaloracompound with themolecularrormula
aHII NO. Proposea struclureconsistenl wilh Ihe formula and speclrum. Insofar as
possible, assign Ihe peaks. Numbers in parenlheses refer to relalive peak areas .
TMS
lL,
,.1..
) ~
I I I I I I I I I
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
(4) (2) (2) (3)
ppm
19. InterpretIhespeclrumbelowrorthecompound CH3Pt(CH2= CH2)[PC6H5(CH3)2J2.
Justiry all splittings. ls this the cis or trans isomer? (Hint: For 3ip, 1 = 1/2, abun-
dance =100%. For 195Pt , 1= 1/
2
, abundance=34%.) [See lnorg. Chem., 12,994
(1973).J
rel
are
20.
21.
re/. 4 16 4
124812 3 12 3
areas
20. Sketch the spectra for the following moleculcs a nd conditions (assume 100% a bun-
dances):
J p- F>J"_ B> J B- F, ~ = 1/
2
I
F
= 1/
2
I
p
= 1
2
1H, 19F, and :11 P resonarlce:;
b. N(CH
2
F)4+
lQF only
21. The following proton nmr spectrum is reported [Inorg. Chem. , 2, 939 (1963)] for
((NH2hPhFe(COh (the two phosphor us Jiga nds are trans).
MS
a. Explain the splittings, assuminglarge P- P coupling, and that there is no proton-
nitrogen coupling observed.
b. Why isn't the N- H coupling observed?
c. Using the A, B. X designation, label this systcm.
Exercises 285
5 = - 1.81 ppm
5 =-4.12ppm
5== -0.83 ppm
286 Chapter7 Nuclear Magnetic Resonance Spectroscopy-Elementary Aspects
22. Thespectrum ofthe following compound is a complex type. Explain how the double
resonance technique could be employed to aid in interpreting the spectrum.
23. The spectrum in the following figure is that ofan AB-type of molecule.
e
f---- 12Oeps------..
i I
!
a. Calculate J and
b. A40-MHz probe \Vas employed.Calculate the dilferenee in fJ for the two pcaks.
c. Ire occurs at a value of2.8, what are the fJ values for Aand B?
24. Consider the series i-propyl X(where X= 1, Br, 1).
a. In which compound would the remote paramagnetie effeet from the halogen be
largest? Why?
b. In whieh would the remote diamagnetic effect be largest?
25. What would the nmr spectrum of PF
s
look like under the following co nditions
Flb) > JFI.I- Fib)?
a. Very slow fluorine exchange.
b. Rapid intermolecular fluorine exehange.
c. Rapid intramoleeular Iluorine exchange.
26. Considerthe moleculeshown in problem 8. UsingtheA.B,X, ...terminology,c!as,ify
this molecule and indicate the non-equivalent protons.
27. a. List and briefly describe in your own words the factors lhat influence the
magnitudes of proton ehemicalshifts.
b. Why do 19F and 13 ehemical shift scover a much larger range than do those of
protons?
28. Ramsey's formula is uscd to calculate the localcontribulions to thechemicalshielding
ofa nucleus;it is givcn as equati on(7- 37). The nuclear magnetic resonancc spectrum
of 5"CO has been observed in a variely of environments. A corrclation has been
proposed relating the chemical shift to the wavelength of an eJcctronic absorption
observed in t hese complexes.
29.
Exercises 287
Complex /. (ngstroms)
K][Co(CNl"J 3110
[Co(enljJC1) 4700
[Co(NHj )6JCl
j
4750
(en = ethylenediaminel
:.. Do you expect the diamagnctic term in Rams y's formula to aecount for an 8l 50
ppm variation in the chemical shifl observed in thi s series ofcomplexes? hplain
brieAy.
b. Do you expect the paramagnetic contribution to the chemical shielding to val'y in
thi sseries ofcomplexes? Why?
c. List these cobalt complexes in order of incn::asing magnetic field for reso nance.
Give your rcasoning.
29. Ramsey's equation [equation (7 37).] is used to cal clllatc local contri butions to
chcmical shifts. Consider the following boron compollnds and thcir 11B chcmical
shifts (in ppm relative to BFJ etherate).
Three-coordinale Four-coordinate
BI]Cmcl l = +5.5 aBF .. =+ 2.3
BF
JI
.,,= - 9A B( H)4' = - 1.8
BCl
J
=- 47.7 BF3'pipcridine = +23
BSr
J
=40.1 aBe 6H, )4 = +8.2
B(OCI-I
3
) ] = -18.1 LiB(OCH )4 = - 2.9
B(CzHsb = - 85.0 BF)' P(C"Hsh= - OA
The generalized m.o. dcscription for three-coordinate boron eompounds consists of
bonding, non-bonding (empty boron a.o.). and antibonding molocular orbitals (l).
Four-coordinate boron compoundsaredescribed by bondingand antibonding m.o.'s
(no non-bonding m.o.) (11).
(J* (J*
n"
(JO
JI
a. Can the firs t lcrm f the Ramsey equation explain the 11Bchemical shifts of thl:
thrce-coordinatc compounds') Why or why not?
b. Rationali zc from the m.o. d scription the fact that the 11B chemical shift of the
three-coordinate complexes varies 125 ppm. whilc that of lhe four-coordinatc
spccies varies 11.1 ppm.
288 Chapler -; Nuclear Magnetic Resonance Spectroscopy-Elementary Aspects
30. It was said that there is no contribution to the local paramagnetic shielding in a
linear molecule aligned parallel to the applicd magnetic field. Construct molecular
orbitals for themolecul eHFandshowthatmatrixelements resultingfrom the Ramsey
equation Iead to the foregoing result.
31. Consider benzene and cyclohexane.
a. In which do you think the proton resonances would be further Llpfield? Why?
b. In which do you think the 13C resonances would be further upfield? Why?
c. In which would J IlC_ II be larger? Why?
32. In compounds ofthe type H3HgX, the 199Hg_2H cOllpling constant is observed to
vary by more than a factor of two, depending on the substituent X. ome examples
are given below:
X J(Hz)
CH
3
104
I 200
Br 212
CI 215
I
4
233
Propose an explanation for the observed splittings.
33. A number of ISN-Iabeled aminophosphines have been synthesized and the 15N_H
nmrcOllpling constants have been measured. Asample of the reSlllts is as follows:
Compound J(Hz)
F
4
P
IS
NH
2
90.3
(3hPISNH2 85.6
F
2
P
IS
NH
2
82.7
There are two possible explanations in terms of the bonding in this series.
a. Give the explanation that is based on the extent of N -> P n-bonding.
b. Offeranotherexplanation thatwas presented,whichalsoaccountsfor these results.
34. a. Would yOll expect the difference CH,l-bcHl in C
2
H
s
I to be ndependent of the
remote anisotropy in the C-[bond? Why?
b. Will this difference have a greater or smaller contribution from anisotropy than
C
H
2?
c. Ifin a series of compounds the
CH1
values showed a different trend than the
CH
,-
CH
, values, what cOllld you conclude about anisotropic contributions?
Exerci ses 289
35. Combine in your lhinking (reread if necessary) lhe discussion on inleratomic ring
currenls wilh the relationship between j " C-H and T (discussed in section 7-18 on
App!icatons of Spin-Spin Coupling 10 Structure Dcterminalion). Using these con-
cepls. propose a method for determining if lhere is anisolropy in the methyl
chemical shifl ofB-trimelhyl borazine.
-H
lhan
lhe
i
,
Introduction
Dynamic and
Fourier Transform NMR
In this chaptcr we con ' der l he applieations of nrnr to dynarnic systerns and then
proceed to a discu "i n of Fourier tra nsform nmr. T he chaptcr concludes with
a discll ssion of Ii qui d crystal and sol id nmr. The nmr spect ra of paramagnetic
ions ( hapter 12) is diseussed aft er sorne fundamental background in ma 'netism
is dcvcloped (Chapter 11).
Evaluation of
Thermodynan:tic
Data with NMR
As mentioned in Chapter 7, when two 'pceies undergo ra pid ex hange on the
nmr lime seal , Ihe chemieal shiCt observed is a mole-fraetion weighted averalle
oC lh two re 'onane s. Wi lh rapi d ex hange:
A + X e AX (8-1) I
the chemical shirt of Ihe A (or X) re onance wilI be a mole-Cradio n weighted
average of Ihe re. )nanee of A ( r X) and that oC th analogous atom in Ihe AX
add uct, as shown in equaton (8- 2).
(8-2)
N refe r to mole Craetion. An analogolls equation could be vri!ten fo r lhe
resonance, ob, eX) '
Thi s exchange a eraging can be used(l) to cvaluate the equil ibrum constan!
for a reacton. The approach w ll be ill u trated by dcriving <I n expres ion for the
cquil ibriurn eonst'lnl of the reacl ion illustraled in eq uat ion (8-J). Assume that
we are ob ervi ng lhe chemical shift oC a proton of molecule A that is shifted
considerably upon fo rmi ng the complex AX and that there is rapid exchange
bet een A and AX gving a rnole-fraction wei ghted shiCt as in quat ion (8-2)
' xpressing equation (8- 2) in molarity units, we obtain ror Ihe r action in
cq uation (8- 1):
A] . [AX]
ob, = [A] + [AX] DA + [A] + [AX] 6
AX
the e
DeliJ
vher
one
In \.: ql
al' ~
of sir
exper
s i m i l ~
8- 1
Tb ~
8- HA
are p
the e
vern
effecl!
xcha
lhe t I
is refe
ru rthll
lcm p
exclw
peak'
slol\' e
290
-
.lhcn
with

ctism
111 the
crage
(X- I)
ghted
I\X
2)
8-1 Rate Canstants and Activatian Enthalpies from NMR 291
Rea rranging. collecting terms. and sublract ing r\X]6
A
from bolh ';ides of
lheequal ion produccs :
(8 J)
where [A ] . the inil ial concent raton ofA,equab [ Al + [ AXl
Substitut ingequat ion (8- 3) into lhe equili brium constant cxprcssi on
K = [ AX]
([A J- [ AXJ)( XJ- [ AXJ )
one obt ainsequal ion(8- 4)
(8-4)
In equat ion(8 ). al!quanltiesareknown exc .pt K and Thetwo unknowns
are con tanl at a givGn tcmp ratme and can be obtained('l by solving a series
of simult aneou equations that rcsult from meas uring t. c5
o'
" in a series oC
cxperimenL in which [X 1and [ N] are varicd.This aspect of lhe problem is
lo tha! described 111 Chapte r4 for sys tcms tha tobey B er" law.
8-1 RATE CONSTANTS ANO ACTIVATION ENTHALPIES
FROM NMR
The proton nmr pectrll m ofa deuterat d yclohexan moleclllc.(shown in Fig.
8- 1 (A)).a a Cunction oflemperal ure is shown in Fig.8-1(8) 10 (G) Twoisomers
are possi ble where Ihe hyd rogen is in ei ther the axial or eq uatorial posi ti on oC
thecycJohexane ringoAl room lcmperature, the two Corrns are rapidlyinlercon-
vert ing and lhere is no cont ribution lo the observed Ji ne widt h from cxchange
effects.As Ihe temperaturcislowered. lheband bcgins lo broad nfrom eh mical
exchange contributions to he nuclearexcit d state lifcti m .This range, down t
the tempe ral urc at whch thetwo eparalcpeaksal' j u 1be
n
il1 l1i ng toberesolved,
is reCerred lo as lhe neor Iast n dwnge regi on. A: Ihe lcmperature is lowered
fu rlher. two peak' are een and Iheir chemical hifts change as a Cuncti on of
lemperatur lInt il curve(F)is btained.Thisrang i referreJ loasl heill lennedi a/e
exchallge reyioll. A th t mperalure is lowered further. the chemical shifrs ofIhe
peaks no longcr change, bu! lht; resonances sharpe n throughout the so-calk:d
S/OIV e.\cI/al1ge re4iol1. Finally,al - 79 and lower, here are no kinet iccontribll -
NMR Kinetics
I
l
292 Chapler 8 Dynamic and Fourier Trar.sform NMR
(A)
H
(B)
(C)
D I ~
(E)
(FIJJL
79
0
-
Fast
exchange
Near
fast
exchange
Coalescence
Intermediate
exchange
Slow
exchange
Stopped
exchange
FIGURE 8-1 Deulerated cyclohexane. CeD"H. (Al and the
lemperaluredependence 01 ils nmrspeclrum (B lo Gl-
tior
reg
Vl a
rat(
thi
Vol
We
ana
em
OI1(
the
Th.
pro
ratl
lhe
In
regl
Jife
Jife!
ex
Th
or
dis
r al
thl
Sil
u
Ce
10
8-1 Rate Constants and Activation Enthalpi es fr om NMR 293
ti ons to the shape of the spectrum, and this is referred t o as the stapped exchange
regan.
By a full analysis of the inftuence of chemical exchange on the magnetization
vi a the Bloch equations, it is possible to derive equations for the evaluation of
rate constants from the nmr spectra. The derivati o ns are beyond the scope of
this treatment and the reader is referred to Emsley, Feeney, and SutcJiffe,
Volume 1, Chapter 9, or Pople, Schneider, and Bernstein, p. 218. for more details.
We shall present the results of these derivations in a form useful for a kinetic
analysis and comment on shortcomings of the various approaches that have been
employed.
O ne of the simplest systems is one in which a given proton can be at either
one of two molecular sites; the probability that it will be at one site is equal to
the probability that it will be at the other, and it has the same lifetime at each.
The cyclohexane interconversion and many other isomer or rotamer exchange
problems satisfy these criteria. If one works with the chemical shift changes, crude
rate data can be extracted from any two-site (A and B) equal-lifetime process in
the intermediate exchange region by using equations (8-5).
In this equation (v A o - VD o) is the sepa ration of peaks in the stopped exchange
region in Hz; (VA - VB)obs is the separa tion of peaks at a particular temperature
in the intermediate exchange region. Recall that we stipulated that the two
liretimes, T
A
' and T
B
', are equal. The Iifetime T' then is the sum of the two, or the
lifetime at site A is simply T'j2.
At the coalescence temperature, the two peaks have just merged, so tha t
(VA - VB)obs equals zero. The approximations used to derive equation (8- 5) no
longer apply, and equation (8-6) is used to obtain the lifetime:
(8-6)
Equation (8-6) shows that the necessary condition for detecting two
exchanging nuclei as separate resonances is given by:
(8-7)
Thus, the farther apart the chemical shifts at sites A and B, the shorter the lifetime
or the faster the kinetic process will have to be to average them. Recall the
discussion of this effect in Chapter 4.
Utilization of t he foregoing equations [especiaIly equation (8-5)J leads to
rate constants wit h large error limi ts. Activation enthalpies are obtained from
the temperature dependence of the rate constant via the Arrhenius equation.
Since the temperature range corresponding to the intermediate exchange region
usually is very narrow, huge errors in the activation enthalpies can result.
e
Considerably more accurate information is available about the kinetic process
(8- 5)
T'
.
294 Chapter 8 Dynamic and Fourier Transform NMR
by using line width changes ovcr the entire temperature region that the spectrum
is inftuenced by the kinetic process. These regions are illust rated in Fig. 8 2,
where a tY[1ical plot is shown for the change in the ful l wid th of the resonance
line at half height as a function of liT
In the :: Iow exchange region, the observed line width, I / T
2A
' , ofa given peak
for slte A has contributions to it from the natural line width, 1/ T
2A
, and from
chemical exchange, T
A
, according to :
(8-8a)
Since this equation employs units fo r V of Hz, V
1
/
2
represents the fullline width
at half hcight.
This equation and al! those in the equation (8-8) series are for a two- ite
problem with equallifetimes at both si tes, but not neces arily equaJ populations.
Thi equation does not apply if there is pin-spin coupling of the protons, for
contributions of lhis proces' to 1/ T
2
are not incl uded. The I / T
2A
contribut ion ro
the width in the -Iow and intermediate exchange regions can be determined by
extrapolating lhe line for no exchange effeets (dotted line a). B diO'crence,
(l / T
Z
\' - I / T
2A
), one obtains I/T
A
. The same calculation could be carried out
with the B resonance.
In the near fast exchange regon, the contributions to the li,)e width are
given by
(8- 8b)
where W
A
= 21fv
A
, and w/ and w
B
o are lhe chemcal shifts in the absence of
exchange. The firsl two terms on the right-hand side of lh equality are
Peak
coalescence
FIGURE 8-2 The inlluence
01 chemical exchange on the
line width, ilV
1
/
2
, 01 a spectral
band as a lunction 01
absolule lemperalure, T
(The lag is plotted lo give
linear activalion energy plots
lar various regions .)
I
T
mo
b ~
Be
eq u
wi tl
an}
b
by
ana
usn
di lTe
cOrr
al a
pan
lhe t
spec
f ;
( D
cou p
u el
trea!
We
unde
cxp
deca
reae!
magl
rad ie
decl
or
8- 2
----
i[lectrum
Fig. 8- 2,
:sonance
en peak
lil e! rrom
(S -Sal
oc \\ id lh
two-site
ulations.
Ion,. ror
ution to
nincd by
illcrcnce.
, 'ice! out
:ie!th are
Sb)
01'
ality are
ia te
1 exchange
fec ts
8-2 Determination of Resellan Orders by NMR 295
mole-fraction wcighted averages 0 1' II T
2A
and l j T
111
fo r the A and B sites in the
absence 01' exchange. The last term is the exchange-broadened contr ibution, T he
qll an titi es N A/ T1 A and NIlIT
1B
can al so be obtained by virtlle 01' the fact that in
Lhe fast exchange region
(8 8c)
Because one can wo rk over a Jarger temperat ure range wi lh the li ne width
equations, one can obtai n more accurat e values fo r the act ivation enthalpies than
with cquations 8- 5 and 8-6.
Neither o[ the abovc approaches (chcmi cal hil'ts or line wi dlhs) are used
any more to eval ua te rate constan ts. lnstead, the ent ire pecLral li nc shape wuuld
be calculated using reportecl equati ons.l
2
) One can then obtai n Lhe exchangc rate
by varyi ng T until the calculated line shape flt s the experimental curve. This
analy::; is is generally ca rried oul by a compuler that calcul ates Ihe li ne sha pe
usi ng an cSLimatcd vat ue 01' T, i.e. ., one l' rom a rough ./'I. v
1
/
2
calclI lati on. The
dilference belween the calculatecl and experimental intensities is determined.
computer then varies T until the difference is mi nimized. Thus, [rom lhe line shape
at a gi ven tempera ture. the rate constan t can be determined and the activati on
paramcters obt ai ned in lhe usual l11all nCr rr om the temperalure dependence 01'
the rale constan t. Alypical compari son bctween a calculaled and an experi mental
speclrllJn is ill lls trated in fi g.8- 3. The spectrum
(2
) is th al 01' the m thyl proto n
of 2-picoli ne. The pieoline is undergoing exchange wit h Co(2-pichCI 2 in
(CD3hCO solvent and l he region is the near fast exchange.
Wh n One wi. hes to study a multi site probtem or when there is spin- spi n
eoupli ng lo one of the prolon involvcd in Ihe exchange, a bett er method in olves
I J S
use of the de. nsity matrix approach. - ) Thi ' approach is beyond the scopc or our
tl'eatmen! and Ihe reader is rcrcrred lo references 3 to 5 for dClails.
8-2 DETEAMINATION OF AEACTION OADEAS BY NMA
We return now to a more complete di cussion 01' lhe T' va lues in order lO
understand how to obla in information about reacti on orders. In the nmr
cxperiment, we are si ud. ing a reachon occurring al chemical equ ili bri um. A
decay in the net magnetization of t he sample results as the l'orward and reverSc
reactions OCCUf. Suppose, for example. Iha! the decay al site A is obscrved The
lmignetization decays by a fi rst -order cl ecay process jusI like the decay ol'
radioacti ve materi al. The rate constanl, I/T
A
, is a l s l-order rate constant for Ihe
deca of the ini ti al nllmbcr al' protons in oul' sample a t site A. i.c.,
or
I d[A]
- ----- (8- 9)
[A] dt T
A
(A)
(B)
(e)
(O)
(E)
FIGURE 8-3 e omparison 01
experi mental (solid line) and
theor etical (dols) nmr methyl
resonance spectra at
T = - 44". AII solutions are
0.09 M in e o( 2-pi c) , e I
2
and
contai n the loll owi ng
concentrat ions 01excess
2-picol ine : (A) 3.54M. (B)
2.64 M, (e) 2.40 M, (D)21 1M,
(E) 1.85 M [From S.S.
Zumdahl and R.S Drago, J.
Amer. ehem. Soco 89, 4319
(1967).]
l
I
296 Chapler 8 Dynamic and Fourier Transform NMR
In these expressions [A] is the initial concentration of protons at this si te and
d[A]/dt is the rate at which this initial concentration "disappears.' Thus, we are
concerned with the lifetime of the initial A and not with the bulk concentration
of A. What we measure is liTA and not the rate, so in a particular experiment a
first order decay constant is always observed.
Now consider the mechanism for the chemical reaction that is occurring
and causing A to eave site A. It could be a first-order process for which
_ d[A] = k[A]
k= __
or (8- 10)
dt [A] dt YA
Therefore, for a first-order reaction, the rate constant k equals the l i TA that is
measured. If several experiments are carried out at different concentrations of A
for a process that is fi rst order in A, there will be a change in the rate; but there
will be no change in the observable from the nmr experiment, which is li TA'
ThllS, an observation of no change in li{etime with a change in concentraton
corresponds to a first-order process.
Next consider a process that is second order in A:
_ d[A] = k[ A]Z
dt
or
l d[ A]
- [A] dt = k[A] = liTA
(8-11)
Now in a series of experiments in which [A] is changed. lITA will also change
linearly wi t h the concentration. Observation of this behavi or suggests a second-
order reacton.
Next consider a reaction t hat is first order in A and first order in "8 :
- d[A] = k[A] [S]
dt
Now we must specify whether the A resonance or the S resonance is being studied.
If we are studying the A resonance, lhen we must use
1 d[A]
- - - = k[ S] = lIT (8- 12)
[ A] dt A
Now as the concentration of A is changed in a series of experiments, the value
of l i TA remains constant; but as the concentration of B is changed in a set of
experiments, the vallle of l ITA changes in di rect proportion to the concentration
of B. The opposite result is btai ned if the B resonance is examined.
[n the system illustrated in Fig. 8-3, the exchange of free 2-picoline with the
four-coordinate complex, Co(2-pic}zCl
z
, was stll died(Z) in deuterated acetone as
a function of the concentraton of 2-picoli ne. The lifetime of the picoline on the
metal, T
M
, was independent of lhe concent ration of Co(2-pichClz, but varied
lineal
throu
oyera
parar
comr
S to
8-3
Ligar
comp
solve
and
Furt!-
one h
chan
bot h
8- 3. \
solvel
CoLz
proce
order
non-(
of a t
1
metaJ
of el-
l/ rM i
arate
when
follov
conSl1
for w
8-3 Sorne Applications 01 NMA Kinetic Studies 297
finearly with the free figand concentration. A plot of l/ rM USo [ 2- picoline] passed
through the origino This indicates a reaction mechanism that is second order
overall: first order in Co(2-pic)2C12 and first order in 2- picoline. The activation
parameters calculated in thi s a rtide rrom a rull fine shape analysis were
compared(2) with those rrom the line width equations. Errors in 1 ranging rrom
5 to 15 % were introduced by the line width approach.
8-3 SOME APPLlCATIONS OF NMR KINETIC STUDIES
lO)
Ligand exchange reactions have been studied ror many transition metal ion
complexes. In many cases, the same compound serves as both l he Ii gand and the
solvent. One cannot determine the order or the reaction in ligand when the ligand
and the solvent are the same, because its concentration cannot be varied.
Furthermore, ir one wishes to study a series or ligands in a series or experiments,
one has varying contributions to the thermodynamic parameters obtained from
changing the solvent when the ligand is changed, since the same compound serves
both purposes. These problems are avoided, as in the system reported in Fi g.
8- 3, when the complex has solubilily a nd can be studied in a non-coordinating
solvent.
In a study(6) of the exchange or fr ee L (where L is [(CH
3
h NJ ) PO) with
CoL
2
C1
2
in CDCl ) , the resulting kinetic dat a indica! d that the reaction
proceeded by both first (i.e., dependent o nly on CoL
2
C1
2
) and second (i.e., fi rst
order in CoL
2
CI
2
and fi rst order in L) order reacti on pat hs. Since CDCI } is a
non-coordinating solvent, the first order palh provides evidence for the ex.is tence,
11)
or a three coordinate cobalt(I1) complex as a n intermediate.
The mechanisms ror ligand substitution reactions in octahedral tra nsition
met a l ion complexes a re diffi cult to ascertain. A recent st udy'7,1 of the exchange
nd-
or CH) H with [ Co(CH, OH)6
2
r](BF4 -h ill ustrates the problem. T he value of
l/1M is independent or the metal complex or methanol concentra t ion, supporting
arate law:
Rate = nk [complex]
where n represents the coordination number of the exchanging ligand. T he
following mechanisms( 7a} are consistent with thi s rate law and should be
considered :
Mechanism 1: SN1(lim) or D-type
Co( MeO H)6 2 + Co( MeOH)S2+ + MeOH sl ow
k
2
Co{MeOH)/+ + MeOH* ras t
[or which the rate law is
'
(
I
I
t
Mechanism 2: S (lP) or Id
Kos
Co( MeOH )62+ + Co(M OH)62
1
} {MeOH*} fast
k[
{Co( MeOHV +} {MeOH*} + MeOH slow
which has the rate law
Ra te = k[ Kos [ o]r[MeOH]
Kos[MeOH] + 1
where
[CoJr = [Co( McOH )6
Z
1] + [ {Co(MeOH)6
2 1
} [MeOH *}]
In the second mechani sm, Kos i' th ou ter phere complex for mat ion constant.
When Kos[CHJOH] 1, lhe rate law for 11echanism 2 r duces t a fo rm identical
to lhat for mechanism 1, and lhe two cannot be di tingui hedo H lhe [ HJOH]
could be rcdllced to a maIl value, then 1 Kos[CH
3
0H] and second-order
kinet ics would be obscrved. differentiating the two mechani'ms. or a Kos of
abolll 1, changing lhe [CJ-I)OH] from 3 M to 8 M wOllld incrca e the rate
constant by only 10 % and experimental er ror would makc lhi change hard lo
delect. A larger vallle of Kos would make the difference even smaller. Al 1 wcr
[CHJOH] , di ocialion of so me melhanol from lhe complex accompanied by
anion coordinalion, becomc problem. These problems are described here
beca us th y are common lO many nmr sllldie: on syst m f Ihis lype. In order
to trllly di ti ngui h lhe e lypes of mechani m" il wi ll be necessary to study
syslems in which lhe free ligand c ncenlration, [L]. can b made ufficiently low
so Ihat 1 Kos[ L].
In an nmr kinetic st udy(7b) lIsing a density matrix analysis the kinel ic
parameters and the thermodynamics of adducl fonnation, show that the reaction
Ni(SDPT)' B + B' Ni(SDPT) ' B' + B
(where SDPT is a pentadentale ligand with lwo negal ive chargcs, B and B' i
4-methyl pyridine) proceeds by a pure di sociati ve mechani m invol ing a
five-coordinate, NiSDPT, intermediate. By comparing data obtained in toluene
and in CH
2
CI as ol vent, lhe role played by the latter solvenl in lhe reaetion
was c1early established.
The spectrum of N,N-dimethylacetamide, CH 3C(O)N(CH 3)2' has lhree peaks
al room temperalure, two of which corre pond to the diffcrenl envi r nmenls of
lhe t\Vo methyl groups 011 lbe nilrogen (one cis and one trans 1 oxygen). Th
C- N bond has multiple bond charact r and gives rise to an appreciable barrier
lO rOlation ab ut lhis bond. As a result of lhi barrier. lhe lwo non-eqlli alent
N- CH
3
group are dele ledo A the lemperalu l" is increas d, th r<lte of rotation
abollt lhe C- N bond increase and the N-methyl re onanc mergc, glVll1g rise
to a series of specLra similar to Lbose io Fig. 8-1. Thc lifelime of a particular
configuration can be determined as a fllnction of temperalllre, and the aclivation
energ)
carrie\
oucleu
of th
II1verSJ
olher
T
chlori
aeid ic
(split
peaks
fr m r
peak
relaxa
pH is
HO,
wit h n
other
to 8,
exchar
line m
NH
J
"
An ' n1
for lh
where
prol 1;
from:
and
(B' is E
analy.J
rceorol
aqueol
mea UI
I
trated
l
peak a

corresr
be Icss
soluLio
ance .
fast
,I ow
ilanl.
llical
H]
ord r
) ~ of
, rale
rd lo
lower
!d by
here
order
sludy
.y low
melle
n
B' is
8-3 Sorne Appli cations 01 NMR Kinetic Studies 299
energy for the barrier to rotalion ca n be evalua ted(8) Si mi lar studies ha ve becn
ca rried out on other amides(9) and on nit rosamines.(10) The quadrupolar 14-
nucleus mak s a temperalure dependcnt contribution to the line widths in some
of these sys tems, introcJucing error into lhe resulting paramcters. The ra tes of
inversion of subs til uted 1,2-dithiane and l,2-dioxanes(ll) are among lhe ma ny
other rales t ha t have been sl udicd.
The mechan ism of pro ton exchange for soluti ons of melhyl ammonium
chl oride(12) in waler as a funcli on of pH was eval ua led by an nmr pro edu re. In
acidic solution (pH = 1.0) the nmr speetra eonsi ! of a quadrll plet melhyl peak
(split by the three arnmonillm protons), a harp water peak, aod t hree broad
peaks [rom the '\mmonium protons. Th triplel for lhe ammonium pr lons resu lts
from nitrogen spli tt ing. No fi ne struclure is observed in lhe ammonium proton
peak from the exp et d cOllpli ng to the methyl protons. Parti aJ qlladrupole
rel axati on by lhe nitrogen ca uses these peaks 10 be broacler than J JIINCI I ' As the
pH is inereased, rapid protoo exehange reaetions begi n to oecur and the CH) ,
H
2
0, and NH
3
+ bands begin to broaden. Even tuall y, al about pH 5, two peak
wi th no fine Slructurc remain, one from lhe prolons 00 lhe CHJ group and the
other a broad peak from an average of aH other proton shifts. As lhe pH is raised
lO 8, the broad prolon peak sharpens again. The CH
o
broadenng yield ' lhe
exchange rale of protons on lhe amin nitrog n; Ihe broadening of lhe water
hne measures the lifetime of l he prolon on water, ano the broadeni ng of lhe
NHJ + t riplel measu res lhe lifelime of the proton on lhe ammonium nitrogen.
An analysis of Ihe kin tic dala yields: (1 ) th rate law and a consistent meehanism
for Ihe exehange
k
1
CH j NH ) + + B ------- CH
o
NH
2
+ BH+
\ here the base B = H 10, CH) NH 2' or Ol-r; (2) the fraeti on of Ihe aboye
protolysis that involves water; and (3) the eontributi on lO lhe exehange reaetion
[rom :
and
(B' is B wit h one hydrogen replaeeo by a differenl hydrogen). Th details of this
analysis can be obtainecl from lhe refe rence by Grunwald el al. ,(1 2 ) which is highl y
reeommended reading. In ubsequent studies the rales of prolon cxchange in
aqueou' solutions cont ain ing NH
4
+ , (CHJhNH2 + , and (CH)) NH + ere
measured and compared.(1 3J
Another example f information obtaioed fro m nmr ra le st udies i illus-
trated(14) by the 19 spectrum ofSiF
6
2
- in aqueous Iution;Fig. 8-4. Tbe main
peak arises from fl uorines 011 28 Si (J = O), and the twa small peak result fro m
spi n-spin splitting of the fluarinc by 29Si (1 = 1/
2
), The appearanee of the satell ites
corresponding lO J Si F indieates lbaL lhe rale f exehaoge of Ouori ne atoms must
be less lhan 10
3
sec -
1
[r' > l / v ~ - v
B
)] . It is al o found tha t the speetrum of
2
sol ut ions of SiF
6
- eontai ning added 17 - contains lwo separa le Huorine reson-
ances. These are assigned lO F - and SiF/ - . There are alelli te ' (JSi-F) on the
l
---
300 Chapler8 Dynami c and Fourier Transform NMR
f------J29s.-F-----.j
FIGURE 8-4 1ne tluorine ntnr spectrum
01 SiF
6
2
- See table inside back cover
(Properties 01 Selected Nuclei) lar29Si
natural abundance.
_'A_______ IL
SiF6
2
peak. When a sol ution of SiF6
2
- is acidified, ra pid exchange occurs, the
satellites disappear, and the cen tral peak broadens. T he fol!owing reactions are
proposed:
2
SiF - +H 0 + ----> HFSiF
s
-
6 3
-H,O - HF
T he D e spectrum of CO
2
In water gives rise to two peaks,(l S) one from
dissolved CO
2
and a second from H
2
0
3
, HC0
3
-,and CO/ - . Ra pid proton
excha nge gi ves rise lo a si ngl t 3C peak for these lat ter th ree pecie ' . The reaction
CO
2
+H
2
0 -. H
2
C0
3
has a half-life of a bout 20 sec, so a separa te peak for
dissolved CO
2
is detected.
8-4 INTRAMOLECULAR REARRANGEMENTS STUDIED BY
NMR-FLUXIONAL BEHAVIOR
The nmr spectrum of B) I-I s - is of interest becau e it demonstrates Ihe effect of
intramolecul a r exchange on the nmr spect rum. The truct ure of B3HS - is
il lu t rated in Fig. 8- 5, aJong with a possible mechanism for lhe int ramolecular
hydrogen exchange.< 16- 1S) The 11 B spectrum is a Donet that result fr m a splitting
of three equiva lent borons by eight equivalent protons. The process in Fig. 8- 5
is very rapid, making the three borons equivalent and t he ei ght protons eq uivalent
in the nmr spectrum. The eight hyd rogen atoros remain attached to the bor n
atoms of the same molecule duri ng lhe kinetic process and the spli tt ing does not
disappear. J
BH
is a time average of aU the difTerent B-Hcoupli ngs in the molecule.
Contrast Ihis to rapid inlermolecular exchange, in which a single boron resona nce
signa l woul d result if exchange made al! protoos equivalent.
FIGURE 8--5 The structure 01 B3He - and a proposed intermediate lorthe intra-
molecular exchange.
H
exch
wou
has
pro
of t
specl
The
The
=
prot
slgm
ance,
The
are i$
shift
subse
Ihat
difTer
ar d
in th(
woul l
than
lO H
------
---
8-4 Intramolecular Rearrangement s studied by NMR-Fluxional Behavior 301
ms. the
iOlls are
ne from
I proton
rcaction
peak for
fTect of
'3HM- is
IOlecular
.. plitting
Fig. g- 5
H
/
+30
0
1
1
I
-19
0
I
H
-25
0

H H -40
0
-52
0

-56
0
!j
H4
-60
0
H
2
-64
0
H3
-80
0
(A)
- 100
0
(B)
I
I

I

I
I
I
I
-
I
I
I
}
I

1
J.
I I f,
JI I I I I
6.5 6.0 5.5 4.4 4.0 3.5 3.0
FIGURE 8--6 The proton magnetic resonance spectra of (n-CsHs)Fe(CO) 2CSHS in CS
2
at various temperatures. The dotted line represents the resonance position of the
n-CsH
s
protons at each temperature.the amplitude of the +30- spectrum is shown
x0.1 relative to the others. [Part (B) reprinted with permission from M.J. Bennett,
Jr., el al., J. Amer . Chem.Soc., 88, 4371 (1966) . Copyright by the American
Chemical Society.]
Another possible explanati on ofthe observed spectrum, that does not involve
exchange, is based on virtual coupling. Vi rtual coupli ng of the eight prot ons
would give rise to the observed nonet in th 1 1 Br sonance. Strong boron coupling
has not been observed in the spectra of other boron hydrides.
Considerable information is ava il able regarding the mechani sm of exchange
processes from the non-symmetrical collapse of an nmr spectrum. An ill ustration
of this basic idea is provided(1 9) by the tcmperature dependence of the nmr
spectrum of (lJs-CsHs)Fe( O)2CSHS' whose st ructure is shown in Fig. 8- 6(A).
The spectrum obtained as a function 01' temperature is shown in Fig. 8--<:)(B).
The pi-bonded resonance gives rise to a single sharp peak at
b = 4.4 at all temperatures because rapid rot ation of the ring causes the five
protons to be equivalent. The rcmaini ng peaks in tbe spectrum ari se from the
sigma-bonded cyc\opentadiene ringo At -100C, thr dist inct groups of reso n-
ances are observed at 6.3 , 6.0, and 3.5 ppm with rela tive intensities 2: 2 : 1.
The most shielded resonance (6 = 3.5) is assigned to H l ' The H 2 and H 5 protons
are isochronous, as are H 3 and H
4
. Tbe two sets differ on ly slight ly in chemical
shift relative to the magnitude of tbei r coupling constant and, as shown in a
subsequent section, thi s situation gi ves rise to complicated second-order spectra
that often contain more peaks than a simple anal ysis of the chemical shift
diflerences and spin-spu1 coupling would produce. T he peaks al and
are due to the 2, 3, 4, and 5 protons. The splitting from the H 1 prot on is sma\l ;
in the limit where J J Il - H eq uals 4J 11 - ti the two resonances at 6 . .3 and 6.0
1 2 , 5 3.4
woul d be mirror images. However, since -H would be expected to be la rger J
II
1 2. 5
than 4J H ,addit ional fine structure would be expected in [he peak assigned
1 3 . 4
to H2 and H 5 ' With 3 J H - 11 _ smaU. the addit ional fine structu re would not be
I
l
\
.
l
1
FIGURE 8-7 Dagrams
showing possible
intramolecular paths leading
to the nmr equivalence of the
u-CsH
s
protons at room
temperature. [Reprinted with
permission from M. J.
Bennett, Jr, el al., J. Amer.
Chem. Soc. , 88, 4371 (1966).
Copyright by the American
Chemlc31 30ciety]
resolved but could be manifested in a broaJening of the resonances . Using this
cri lerion, the deshielded multipl et with the broader resonance (o 6.3) is assigncd
to lhe 2 anu 5 prot ons. Since the e protons are isochronou " wc shall label them
as A and the 3,4 pair a B. As the temperatll re is raised, the A resonance coll ap es
faster than lhe B resonance. Al -25"' C, they are broadened and have completdy
collapscd. Al -1- 300 , a sharp peak corresponding to a mole-fraction weighled
average re onance of lhe three typcs of protons is obtai ned.
Several mechanisms for this fluxional hehavior are possible. The non -
symmetrieal collapse of lhe speclrum rules out any bimolecul ar pl' ocess (dis-
sociali e 01' exchange in nalure). A fi rsl -order dissociuli v process is rlllcd out
becallse tlle experimentally fou nd :.l el i al ian enthalpy is too low. This Jow
activat ion enthalpy ugge ls some intcraeti on bctwc n th pi orbilals of lhe ri ng
and lh metal in lhe lran ition Slate. The three lrllctures showll in Fig. 8- 7 are
considcred as po 'sible n states or interm di ales and are referred to as
the r 5_Cp (A), 1{2- olefin (B) and r 3- all yl (C) mechanisms. The lerms 1,2 shift and
1,3 shirl ha ve also becn applied lO lhe laller two mechanisms rt: spect ivcly.
The mechanism involving (A) can be climinatcd for it would rcsu l! in a
symmelrical coll apse of lhe spectrlllll. Thc mechanisll1s involving (B) and (C )
would reslllt in l n n-symmel ri cal collapse, as shown by con idering how Ihe
la beis in Fig. 8- 7(B) are changcd by a 1,2. l1ift. This is illustraled symbolically by
A
Ha
A
Ha
B A
B B
A B
This analysi shows that aU A's are changed ioto dilTerenl typcs of bul
only halr the B' s are. so lhe A re onance . hould callapse mo re rapidly.
On t he other hand, the 1,3 shirt is descr ibed by
Ha B
A A
B --->
B A
A B
For lhis mcchanism. Ihe B resonance sh uld collapse faster. Thus, to lhe cxtcnt
that the original assignmenl of lhe A ami B resonances is correcl. the 1,2 shift
s established. The intermedi atc or transil ion slate in Ihe 1.2 shirt could be thoughl
oC as one in which lhe n-eleclron den ily 01' lhe ri ng i. arranged in a two-cen ler
(A)
( 1)
"'G
(3)
'"
(4)
(B) (C)
n bond
anion d
M;
refere nc
sort ha
Th
intral11(
]n 195 1
was a
bip. rar
intraml
systellli
HM(PI
tempts
intram
prob1e1
path\ q
and 24
W
[C
6
H
ion oh
orthe 11
are a si
group
ligands
and H
temper

TI
posi ti o
a t i: t
a poi n
lransi!
Se
lwo cLJ
axi CfI
trigo m
rotat id
by COI
tetrah
lhen 11:
and dI
bond . .
ture .
occ urs
open l
which
Th 111
and!h
and re
this
igncd
the m
apse
Jetely

no n-
. (dis-
d out
10\V
nng
7 are
to as
rt and
1 in a
Id (e )
IV. the
lll y by
11 hut
extcnl
;2 , hift
oughl
nle r
8-4 lntramolecul ar Rearrangements studied by NMR-Fluxional Behavior 303
n bond coordinated lo lhe iron, while the other three carbon atom have an al1yl
ani on distribution of electron densi ty.
Ma ny Huxional systems have been discovered and are summa rized in
reference 20. A procedure for a complete line shape analy si s on systems of this
sort has been reported. (
21
1
There has been a very considerable effort devoted to nmr studies of the
intra.molecular rearrangements of trigonal bipyrami dal and octahcdral complexes.
In 1951. Gutowsky and Hoffman(
2 1
1 reported lh at lhe 19F nmr spectrum of PF
5
wa.s a doublet , even though electron difrraction had establ ished the tri gonal
bipyramidal struct ure of thi s molccule. Si nce P-F coupli ng is mainlai ned, an
intramolecll lar process i' required to equilibrat e lhe flu ori ne at oms. Many other
syslcms show similar bchavior e.g., Fe( 0 )5 eJC I1 mr), CF3CO (CO)J PF3 ' several
HM(PFJ)4 species, and Hlr(CO)2[ P(C
6
H
s
)3J 2' There have been several at-
lempt s(23.
24
1 to systematically enumerate all of tbe physically disti nguis hable
intramoJecular modes for inlerconverting groups on a trigonal bipy ramid. The
probl em is a com plex one, for it is nccessary to in ure Ihal appa rent ly diffcrcnt
pathway are physi all y di tingui habl . Thc r adcr is rdcrr d lO refcrences 23
and 24 [or details.
We shall briefl y consider the flu xional behavior of eH 3Ir(COD)-
[C
H,P(CH
3
)2J2 to provi de an illuslralion of Ihe detailed mecha nist ic informa-
lion oblainable from work in this area f 11 11xionali ty( 25.2
6
1 The slatic strllcture
or lhe molecule al low temperature is shown in Fig. 8- 8(A). At - 3 . Ihe resonances
are assi gncd as in Fig. 8-8(C). The Iwo methyls on each dimethylphenylphosphine
grou p are not eq ui va lent (i .e., they are diastereotopic). Should lhe phospborus
ligands cha nge si tes, lhey wOllld becom equi val nI. The vinyl hydrogens, H 1
and Hz, are a lso non-eqlli alenl. The phcnyl resonance ar nol hOWIL As the
lemp ratu re is rai ed, lhe vinyl prol ol1 signa! c Ilap es in l a singlet, bul lhe
P-CH 3 proton r sona nce is not alTected up lO 67
Thc rcasonabl mecha nist ic palhs that could exchange axial and equarorial
posi tions in the trigonal bipyrami d are illllstraled in ig. 8- 9. Scheme A involves
a twist of the diene about a pselldo-twofold axis Ihrough the metal and throllgh
a poi nt midway between the two double bonds. The int erveni ng intermedia le or
lransi li on state is the di storted tetragonal pyramid labeled I.
Scbemes B and C in olve permutali ons of three si tes. In B, one axial and
IWO equal orial li gands are interchanged by a rota lion aboul a pseudo-th reefold
axi e nstruc ted h drawing a line from lhe metal lo the center of the face of Lhe
lrigonal bi yramid defined by double bond l. dou b!e bo nd 2, and P I' This
rotal ion leads t o lh transiti on stat label'tI n. Th in C is best descr ihed
by considering the group R as bcing located in the center of Lhe face of a
telrahed ron formed by P I> P
2
, dOllble bond 1, and double bo nd 2. The R group
Ihen movcs through an edge and into the center of the face [ormed by P \' Pl '
and double bond 1. The resul ting struct ure has interchanged the two doublc
bonds. Scheme D proceeds throllgh two trigonal bipyrami d intermcdiate strllc-
ures, Va and Vb. each of whi h involvcs a change of fo ur ligand . Each change
OCCll fS by a 0- a ll ed Berry p' eudorolalion mechanism: two eq ua torial groups
open up thcir angle and the two axial groups move togel ber in tbe directi on in
which lhe equatorial angle is increasing. lo form a di storted tetragonal pyramid
The motion contin ues in lhis direct ion unl l the two a -ial bonds are cquat orial
and (he two equatorial bonds bccome axial. Strllcture ' Va nd Vb areenan(iom r',
and rcady intcrconversion is expected. Paths in which (he diene pans eqll at orial
FI GURE 8-8 (A) Structure, (B)
temperature dependent proton nmr
spectra, and (C) assignment 01 low
temperature spectrum 01
CH
3
Ir(COD)[( P(C
6
H
5
)(CH
3
)2h . Solvent is
chlorobenzene and IMP relers lo acetone
impurity present Irom recrystallization.
[Reprinted with permission Irom J. R.
Shapley and J. A. Osborn, Accts . Chem .
Res., 6, 305 (1973) . Copyright by the
American Chemical Society.]
(A)
-TMS
imp
\
w hcrc
lo give
of A' ,
in AD,
(B)
(C)
(A)
(8)
(e)
P
2.
( O)
"
PI
i les hl
pref ~
pho' p
~ ith t ~
O mod
l he cxa
be obu
Sludie'
in refcr
8-5 S
T he uo
kinetic
8- 5 Spin Saturation Label ing 305
R R R
2', 2
(A)

..,. -/ --
P
1
. ---
P1

2
' r
R R R
(8)

P2ftP,
P, -
......
/
,
'tr
P
,
1C72
2
LI
R
(e) p,2,
P, ,
::16'
-
p*
R
I
m
P
R 2 PI
R
,
,1
U
t5
P
2
1 P2i-4
(D) P;t5
-
[P
\1-
[
[RI>-
R --- ... R
P,
-P,
,
2
IV Va Vb
siteshave beeneliminateda energetically unfavorabJe beca useofthegeomet rical
prderence ofthi ligand for a 90 chela te a ngle.
Examinat ion of Ihese schemes indicate Ihat B and C interchange the t wo
phosphorusligands,butAandDdonot.Thus,onlyhela llermodcsa reconsistent
lI"ith the observed spectral behavior. One cannotdis tingui sh betw en the A anel
Dmodes with nmr. There is a very extensive litera ture on this subjcct and, with
theexampl e discussed here, we have indicatcd lh kind ofinformation tha t ca n
he obtaincd. For Il!0re det a ils, the read r shoul d consult rences 25 and 26.
Studies involving ftuxional behavi or in six-coordinate eomplexes are descri bed
in refer nces 27- 29.
8-5 SPIN SATURATION LABELlNG(30)
The double-resonance experi ment can be used to label a proton and obtain
kinet ic infor mation. Consider molecules AD and A'D,
AO + A' -+ A'O +
where A and A' are lhe same molecules and the exchange rate is s low enough
to gi ve two peaks in the nmr ror A and AD. lfwe sat ura te a proton rcsonancc
ofA', thi s p a k will disappear, bul theexc hange process will also cause a partia!
sat uration,Le. , a decrease in Ihe intensity ofthec rrcspondingproton res nance
in AD, if the exchang rate of A' with AO is compa rable to the rela xal ion ra te
FIGURE 8-9 Mechanistic
schemes to account lor
axial-equatorial equilibration
01 COD vinyl protons in the
complexes 8
1
( (COD)P2'
where R is CH
3
. [Repr inted
with permission Irom J. R.
Shapley and J. A OSborn ,
Accts . Chem. Res., 6,305
(1973). Copyright by the
l
t
t
j
306 Chapler 8 Dynamie and Fouri er Transform NMR
(3)
3 2
(a)
lb)
(e)
(d)
FIGURE 8-10 The spectrum
01 Ihe heptamethyl-
benzenonium ion; (B)
spectrum (A) with the (2)
proton decoupled ; (C)
spectrum (A) wi th the (2) and
(3) protons decoupled; (D)
spectrum (A) with the (2) and
(4) protons decoupled.
at lhe two si tes. Th Iifetime for A, leaving a particular !; pin state ;n AD. r l AD'
then has conlributions fr m T
1AO
and r Ao (the li fetime of A al AD)
(8- 13)
Ir a satu rating r.L ficld is lurned on al resona nce A', satural n of this
occurs immedi ately and one can obser e (by si ttiog on !he resonance of AD) an
asymptotic approach t a ncw equ il ibrillm vallle of he magnctization at Ihis
point. The pi 1 of inlen ily versus lime and the t:quil ibrium va lue for the
magnelization can be anal yzed for <IAD' When T
1AD
i known, can be r
AD
calculated simply from Ihe equi librium valu of the magnetization of AD,
When the 11eld is turned off, lhe reso nanC al AD r turos to it initi al int ensit
a 'ymptotically, and this curve can al'o be analyzed to yield T
1AD
. Thi procedure
is sui ted for the determinati n f reaction rates in the range between 10-
3
and
l sec- l. lt thus can pr vide data on the slow side of the nmr line hape cxperiment
and is cOl11plementary to the line shape technique.
pin saturation can also be lhoughl oC as equivalent t a deuterium labeli ng
experi ment, and some of tbe same mec llanistic information is available from this
tech nique as from the lab ling F r cxample, th heptamethylben-
zenonium ion is fluxiona l:
Does the interchange proceed by a 1,2 shift or by a randoro migralion process?
Al 28. four fairIy sharp resonances result, as shown in Fig. 8 lOA. [There are
two lypes (1) CH
3
groups two ortbos, two metas. and one para,] Upon rai sing
the temperalure, lhe re onances broaden etc., and a complete line shapc analysis
lIggesls a 1,2 shift; but th differences between the expected spectrum Cor a 1,2
shift and lhat for the random process are subtle, and a simuItaneous peralion
of both processes was not ruled ou t. Saluralion of the roelhyl re onance at sile
2 produced spe lrum (B) in Fig, 8- 10, in which the inlensity al site 1 is decreased.
No addilional decrease in intensity is ob erved at si te ) when ites 2 and 3 are
saturated or when sites 2 and 4 are saturated, as shown in ig. 8- 10(C) and (O).
Ir the random mechanism were operative, a further reducti n in intensity at site
1 of 22 % would be observed upon atural ion at siles 3 and 4. The intensity
doesn 't change, within lhe 1% accuracy of it determinalion so the random
pro es is minor r absent.
H THE NUCLEAR OVERHAUSER EFFECT
An intere ting phen menon a' ciated with the double resonance experiment is
the Overhau 'er ffect, discovered in the cour of studying free radi cal , ( 310 ) When
there is a coupling of the nuclear and electron spins, un enhanccmcnt in Ihe
in te
Thi,
calle
tran
seco
but
wilh
of ea
and
(J =

dilfer
11/;:
(ilm:
80ltz
const
wil h
I
dept:n
impl
If W
2
mo r '
the
level
areN
tran 'il
Tnst al
dilfer
sy tem
popul
and
the Il fJ

of the j
This i
nOe aL
T
popul a
slate p
atBfro
for the I
I'/n - 2Wn +W + W
o
for lhe Overhauser enhancemenl with
1 - /
0
1'/ =--
1
(8 15)
8-6 The Nucl ear Overhauser Effect 307
intensity of thc nmr transit ions is observed when the esr transitions are saturatcd.
This same elTect occurs in a nuclear-nuclea r doubl -resonance experimcnt and is
caUed the nuclear Overhauser ffecl, nOe.(3 1) Changes in lhe intensity of a given
tran ition are observed wh n another transition i sal urated or perturbed by thc
econd rJ. field. Consider two uncoupled (J = O) spin /2 nuclei with the same JI
but different chemical shifts. The energy leve! diagram in Fig. 8-1l(A) results
with populat ions indicated by N and <5 . or a lotal of 4N nuclei, the populat i ns
of each leve! are indicated as N with + 3 corresponding to thc Boltzman excess
and -o corresponding to the defi ciency. The l wo transit i os of A are degenerate
(J = O) and give one lineo The B transitions givc another peak. The IXIX -> fJfi and
f3 a. -> 'Y. /3 t ransition have dm = 2 and O and are for bidden. The population
di rr rcnces for lhe transitions are ofor lhe all owed A and B lransition , O ror
dlll = O and 26 ror dm = 2. Though transitions involving lhe lattcr processes
(dl1l = O and 2) do not ecur, lhey can provide rela, al ion mechanisms if the
Bol tzmann distribution is disturbed. In Fig. 8- 11(B). lhe s umed first-order rate
con ta nts fOf Ihe various paths are indicated by W. W will labell he translt lon'
wilh rhe dm val ue as a subscripl and lhe nucleus involved as a super 'cripl.
Ir wc ere con cerned with lhe TI reJaxation of lhe A lran ilion, it would
depend on the rates fOf W \ W
2
and W
o
. When W and W
o
are lero we get our
simple definition of T
l
:
lf W
2
and W
o
are non-zero in a multispin system, our T
l
experiment become'
more complexo Now consider the case of an nOe expcriment wherc we salurate
the A transitioll and observe B after satllralion. Afler saluralion the (l" f3s -> f3APn
levels of Fig. 11 have poplllations N - e/ 2)0 while a
A
(lB -+ {JA (Xn poplllations
are N + e/2)0. These levels are given in parentheses in Fig, 8- 11. Thlls the B
lransi tions have population differences of {) whereas lhe A is satllraled and zero.
lnstead of O for dm = O and 20 ror the dm = 2 transitions, their poplllation
dilTerences are now o. We shall consider lhe adjustmenl back to the equilibrium
ystem hown in Fig. 8--11. W
I
A is f no concem for this is aturated, The
population difference across B is not affected for it is stiU {J. Thus, wilhout W
o
and W
2
there is no Overhauser effect. W
o
lransfers population from the {Ja to
the a{J state lO get back to the zero population difference. This increases the
population of the excited state of one B transition and decreases the popu(ation
of the ground stale of the other one decreasing lhe intensity of lhe B transition.
This is counterbalanced by W B but if W
o
is dominant, this willlead to a negative
nOe at B due lo saturation at A,
Th process acts lo tran fer population lo lhe C((X stal lo restare a W
2
population differenc of20. This decreases an exciled slate a lld increa ' e, a ground
SI ate population for the B trallsition, Ir it dominates W
I
B, a positive nOe arises
al B from saturation al A, Solving thc dilTerential equations for the system leads lo
(A) _ W
2
- W
o
(8 14)
--0.0.
(B)
FIGURE 8-11 (A) Transition
i n an A-B spin system
(lA = lB = 1/
2
and J = O) . The
equilibrium populations are
gi ven lar each level and
those after saturation 01 the
A transition are given in
parentheses. (B) Rate
processes that can contribute
to relaxation.
I
I
I
l
.
;
where l O is the normal intensit y and 1 is the intensity that is observed during
the pertu rbation. Ir nOe is observed, the W
2
or W
o
processes, rererred to as cross
relaxation, must occur with the sign of the nOe indicating which one is dominant.
The cross-relaxation processes are dominated by dipolar coupling and W
2
is the dominant term for sma.ll molecules in non-viscous solvents, with W
o
becoming dominant for large molecules or in viscous solution. These are the
most common cases, but there are other possibilities. Depending on the relative
signs and magnitudes of the gN values, there may be signal reduction instead of
enhancement, and even negative Overhauser enhancements (emission instead of
absorption) . The enhancement has been treated quantitatively,i3lbl and it can be
shown that for the direct cOllpling mechanism the theoretical enhancement, 11, is
given by:
(8-16)
where the 1 subscript rerers to the spin being saturated an<' the 2 subscript refers
to the spin being obscrved. The ideal enhancement is seldom obscrved because
or incomplete saturation and relaxation by other proccsses, e.g., TI rel axation.
If YI or Y2 is negative, a negative enhancement results ror the dipolar mechani sm
leading in sorne cases to no peak (YI/ h = -1) or to an inverted peak.
This effect can be lIsed to indicate whether the coupling mechanism is direct
or indirect. Furthermorc, by systematically obscrving the intensity changLs in a
proton nmr spectrum as various protons are saturated, one can determine which
nllclei are in c10se proximity. The magnitude of the indirect coupling decreases
with the sixth power of the distance. Thus, one can distinguish cis-trans iso mers
this way.
3
2
3 2
7 6 5 4
pprn
(S)
7 6 5 4
pprn
(A)
FIGURE 8-12 (A) The nmr spectrum 01 the complex indicated. (S) The nOe
difference spectrum with PMe
3
saturation.
I
nmr
reson
in wh
spectl
one o
With
corres
C-H
disapl
the str
resom
\\
effect
the ne
state r
reader
8-7
Manyl
sensiti\
is to inl
can sw
compUl
noise i5
noise te
many s
consum
advaou
be di sCI
In
shown
z-axls \1
the nuc
rotation
such nu
Larmor
rota tes i
of a refl
y-axis, f
sh ift (i.e
d shield
are mov
nuclei al
fiel d alo
inc
applied I
8-7 Principies 309
An example of the nOe enhancement is shown(32) in Fig. 8-12. The proton
nmr [(Figure 8-12(A)], with the C-CH
3
doublet at ~ 1.5 ppm and the C-H
resonance at 4.75 does not distinguish between the structure indicated and one
in which the hydrogen and methyl of the chiral carbon are interchanged. The
spectrum in Fig. 8-12B is the difference spectrum between that in Fig. 8-12 and
one obtained when the methyl protons of the coordinated PMe
3
are irradiated.
With no nOe, a straight line would be observed and with nOe a peak
corresponding to enhancement results. The significant (6 %) enhancement of the
C-H peak in the difference spectrum (indicated with an arrow) as well as the
disappearance of the C-CH
3
doublet at 1.5 ppm indicates the compound has
the structure shown. Eohancements are also observed in the C
6
(CH 3) 6 and phenyl
resonances as would be expected for both isomers.
When pairs of free radicals are produced in solution, one may observe an
effect called chemically induced dynamic nuclear polarization (CIONP) without
the need of saturating the electron spin transition to attain equal electro n spin
state populations. The mechanism for the CIONP process is involved, and the
reader is referred to reference 33 for more details.
8-7 PRINCIPLES
Many magnetic nuclei are present in nature in low abundance and also have low
sensitivity (e.g., 13C). In examining the spectra of these materials, the tendency
is to increase the d. power, but this often saturates the signa!. Alternatively, one
can sweep the spectrum many times at low power and store the spect ra in a
computer. This is called a CAT (computer averaged transients) experiment. The
noise is random and partially cancel s (the signal is proportional to N and the
noise to N
1
/
2
). The signal is reinforced by each sweep and, eventually, on adding
many sweeps, the spectrum emerges from the background. This process is time
consuming. Pulse techniques, referred to as Fourier transform (FT) nmr, are very
advantageous for this situation. In view of the many advantages of FTNMH to
be discussed in this chapter, this instrumentation now domina tes the market.
In a magnetic field Ho (z-direction), the equilibrium static magnetization is
shown io Fig. 8-13 as a bold arrow. The individual nuclei precess around the
z-axis with a Larmor frequency, w = iJ H N' where H N is the effective fiel d felt at
the nucleus (H0(1 - (J) of equation 7- 28). This leads to different frequencies of
rotation for each chemically shifted nucleus. The rotating xy-components of two
such nuclei, M and M
2
, are shown in Fig. 8-13 where they are rotating with
Larmor frequencies w and w
2
. Now define a rotating coordinate system that
rotates in the xy-plane at the same angular frequency, w
o
, as the Larmor frequency
of a reference compound e.g. , TM S. If you were an observer on the rotating
y-axis, for example, the TMS component and all nuclei with the same chemical
shift (i .e. , same w) would appear to be stationary. Nuclei in the sample that are
deshielded compared to that from TMS, precess at higher frequencies, W, and
are moving slowly relative to the rotat ing fra me at the rate w - w
o
' Since the
nuclei are either standing sti ll or moving slowly, this corresponds to an effective
field along the z-axis that is either zero or sorne small value.
Since the effect of H o has vanis hed, we can examine the efTcct of a weaker
applied magnetic field, H l' on the nuclei. In arder to exert a constant force , chis
Fourier
Transform
NMR
z
.... ...... '.J.I,
,""/
, I
I
I
,
I
,
\
\
M ,(w, t)'",
x
\
\
A r - - - ~ Y
FIGURE 8-13 Rotating
x,y-components, M, and M
2
lor two nuclei with different
chemical shilts. Mo is the
static magnetization aligned
along z field direction Ho .
l
,
I
i
310 Chapler8 Dynamic and FourierTr ansform NMR
H 1 fi eld has to be r Ol aliny al the fr equenc.l' of the nll c!ei. This rotating magnetic
fieJe! is applied by a coil of wire aroune! the x-axis energized by an osci llating
curren! at r ~ rence freqllency W
o
' The rotating H 1 fi eld is a sta tic ve tor in t he
rotating frame and appears as such to Ihe nll clei . When the H 1 fieJd is on, il is
the on!y flele! secn by M o and, as a result, M o begins to precess at Ihe rate
w = yH, in the yz plane. For a 13e nuclell , a lO-gauss rotating H1 fi eJd woul d
produce one fuJl rotation of M o (from +z lo y to - z lo - y back lo z) in 100
microseeonds. 1f lhe pul e i appli d for 25 microseconds, the M o eetor will
rotate 90and point along the y axis. The angle e, in radians, Ihrollgh which the
magnetizat ion is tipped is given by:
(8-17)
wbere 1p is the ti me of Ihe pulse. The angle of tipping is called Ihe fl ip angle and
the pul e causi ng a 90' flip i.. called l n/ 2 or 90" pu l. e. Doubling lhe t[1 of a n/2
pul e leads to a 180 ' or a n pulse.
In lhe nmr experi ment, we monitor lhe y-component of Mo' Afte r the H1
fi eld is hul oIT, Ihe individual nucle decay baek lO th ir Ho pre;es ion. For a
nucleu' ro taling al wo, our rOlaling frame and H 1 frequenc y, lhe y- omponen t
decays as shown by lhe dashed lin in Fig. 8- 14. Thi is referred to a a f n ~
inducl ion decay curve and lhe y-componenl axis is labeled ID in Fig. 8-14.
These nuclei are rotating in phase Wilh lhe rotating frame and lhe y-magnelizalion
slowly deeays to zero as the z magnetization approaches its equilibrium value.
Now consider a nucleus that is rotating in lhe xy plane at a freq uency WI>different
than Wo (MI of Fig. 8- 13), These nuclei are moving raster or sJower lhan the
rotating x y frame and rnove in and out of phase wilh the y axi, . Tbe componen!
detecled along the y axis during the time required for My lO deeay to zero i
hown by the solid li ne in Fig. 8-14.
The FID curve is the superposit ion of four d cay curves like lhal shown by
lhe solid line in Fig. 8-15. Thc e four d cay cur ves corresp n lO lh fo ur 1.le
resonance ' in lhe frequeney speclrurn lhat ari ' C fro m the pro Ion spin-spin
coupling. The F1D 13C spe tra of moleeul s conlaining more nuclei are even
m re compli caled. (43.44) Thal of progeslerone, wilh the protons dec upled, is
giv n in Fig. 8- 16.
My
+
FIGURE 8-14 A free
o O
indication decay curve (A) u..
t ---;
and its Fourier transform tor
(Al
a single absorbi ng nucleus
(B) . (The dashed line is
obtai ned when Wo equals the
~
l -----t
chemical shift, and the soli d 1
linewhen(1)0 isoffresonance.) 200 100 O -100 -200
Hz
(81
FIGI
and
Acat
rcpo
com
freql
do a
[he f
FID
puls>
curv
j js I
FID
ti me
decay
tbe n
Larm
FIGURE I
C. Farrar
Methods,
200
6-7 Principies 311
(Va - v, I
H ~ n n n ~ R 1 ~ ~
alter
Fourier
w-
transl orm
FIGURE 8-15 FID speclrum and its Fourier transform for IJCHJI . (From T. C. Farrar
and E. D. Becker , " Inlroduclion lo Pulse and Fourier Transform NMR Melhods,"
Academic Press, New York, 1971 .)
In view of the complexi ly of thi s pat tern, the FID interferQgram is seldom
reported. When we are doing repeated scans, lhe FID curves are tored in the
computer, addcd toget her and Fourier transformed. Addi ng the individual
frcquency spectra would be inefficienl beca use of lhe computer ti me requi red lo
do a Fourier transformo For a typical compound, we pulse for lO- s sec, measure
the free ind uction decay curve, store it in Ihe comp uler, pu lse agai n, measure the
fID curv , add it t the other one in lhe comp uteL and continue this for many
pulses. If the nucleus were sensi tive enough, jusI one pulse would give an FID
curve that could be Fouri r transf rmed lo gi ve lhe frcquency spectrum. When
il is not sensiti ve enough, the entire p clrum is run many times and since on
FID curve is obtained in a few seconds. many spectra can be obl ained in the
time rcq uired for a low passage experimen t. Basically, then, we measure lhe
decay of the magnetization in the L/ ,V coordinales of lhe rot aling fra me in which
Ihe Det magnetizations of the different kinds of nuclei are precessi ng at lheir
Larmor frequencies.
C. Farrar and E. D. Becker . " Introduclion lo Pulse and Fourier Transform NMR
Melhods," Academic Press, New York, 1971 .)
FIGURE 8-16 1JC resonance of progreslerone (prolon noise decoupled) . (From T.
,
t
:J

FIGURE 8-17 A sequence 01
r.1. pulses.
w
o
t-
--'
eL
:2:
w _ (frome iwt )
~ - - - - - - - - I l - - - - - - - - - - - - 1
FIGURE 8-18 The Irequency plol corresponding lo Ihe time plol 01 Fig .8-17.
P robably the easiest way LO see this is by considering how a square wave,
f(t), can be produced wiLh a series of sine waves, i.e., a Fourier series . A square
wave is illusLraLed in Fig. 8-19.
etc.
I I
I I
I I
I I
r---- 10-
6
sec - - 1-- - 2 sec---j
time
The r.f. pulse is applied for a time t p (typical times are 10 - 5 to 10 - 6 sec)
with a fixed frequency OJo and with very high power (100 watts). After waiting a
couple of seconds, Lhe pulse is applied again, as shown in Fig. X 17.
The pulse, if properly selected, causes all of the magneLic nuclei of a certain
element in the sample Lo absorb and evenLually (after a transformation) leads to
a typical nmr specLrum. The problem now is Lo show how all these nuclei with
different Larmor frequencies can be made to undergo Lransitions by a pulse of
a single frequency cvo' The maLhematical function of time, f(t) in Fig. 8-17,
corresponding to a single pulse can be reproduccd by summing together a series
of sine and cosine functions with differenL w's. This can be shown with a Fourier
transformoA Fourier transfo rm corresponds Lo a generalized transfor maLion in
function space. In this case, we wish Lo convert the time plot in ig. 8-17
to Lhe corresponding frequency plot , using equation (X- 18):
(8-18)
where f(l) is in terms of evo, Ip, and t. The result in ig. 8-18 is obLained, wherc
. is Lhe range of the principal frequency componenLs. Consequently, pulsing our
freq uency W
o
is comparable Lo ha vin g a whole disLribution of frequencies available
10 us from Lhe r.f. source.
Fig
an(
8- .
Ad<
wa\
offl
the
app
requ
decr
rang
the \
8-7 Principies 313
In the limit as n -> co, the following Fourier series will reproduce the square
wave function :
f(t) = C/
o
+L (a" cos 2nnr +b" sin 2nnt) (8-19)
Figure 8-20 shows how the superposition of the first three partial sums SI'S2'
and S) corresponding to n = 1, 2, and 3, approaches a square wave. In Fig.
8-20(A), we illustrate SI; in (B) the second term has been added to give S2 '
Adding the third term in (C) produces S)' which is beginning to resemble a square
wa ve. As n beco mes very large, the resem blance becomes better.
In a similar way to lha t just described for a square wave, the distribution
of frequencies in Fig. 8-18 can be converted to A USo t plots and added to give
[he curve in Fig. 8-19. Irthere were no pu Ise, bu t just one contin uous wa ve
approaching infinite time (the slow passage limit), only one frequency would be
required to describe this continuous wave, (Jo . As [he time, t
p
' of a single pulse
decreases, [he span of frequencies needed to descri be this pulse increases. The
range of frequcncies, t., in Fig. 8- 11:\ is obtained from the Fourier transform of
the wave in Fig. 8-17 and is given by:
(8- 20)
x
(A)
- 7T O 7T
L........1-k I
FIGURE 8-19 Graphical
representation 01 a square
wave.
x
FIGURE 8-20 Addition 01
the first three waves in the
Fourier series leading to a
square wave.
1
whcre t p is lhe durati on of the pul e. In lhe d scription of the ingle pulse, the
wa e stops after li me t
p
' A gi ven frequency continues for infin itc time. Wh n lhe
pulse is passed lhr ugh the samplc, lhe appropriate frequencics in Fig. 8- 18 are
ab orbcd by lhe samplc, causing lransit ions. Therefore, he pulse mus t be shrl
enough lo COy r the distributi n of expccled spcctral fr quencies with simi lar
intensit y freq uency components. As wc can sce in ig. 8- 18, lhe imen 'ily falIs
off a' one moves from C
o
' Accordi ngl y, t
p
shoul d be mllch less lh'lO 4rr/ . lo get
a rcasonabl e dislribul ion of simil ar inlen ity freq ucncy component . For a Iypical
pulse of 'O Il sec, lhe fl at central p rl ion f Fig. 8- 18, where !he ampli tudc is
aboul 1 % 01' the peak value is abollt 16,000 H7 wide.
8-8 OPTIMIZING THE FTNMR EXPERIMENT
On of lhe major advantages lo FTNMR is lhe abili ty to obtai n speclra of dlule
solul ions of sensitive nuclei or eoncentralcd solllt ions of insensilive nuclei (i.e..
nllclei wilh low magnetogyri c ralios e.g., Several variahles need to be
considered in order to optimize tbe exp rimenl ror difficull samples. These will
be considered br iefly here lO give an appreci al ion of the problem. The reader is
referred to references 35 and 36 for greater detail.
A single 90 pulse rotate lbe magnetizati n into the xy plane and produces
the maximum signal in the FID. If one then collect the ID for a peri o r equal
to 5T , 99. 3 % 01' Ihe recovery back to the equilibrium .:--component occurs. In
Ih usual ca e where TI T, most oftbe instrument i ' penl wait ing inslcad
of collecling data. H the e nd pulse is followed before a r equal ro 5T
I
, a , maller
magncliLalion is bserved. When ! i 1. 27TI ' only 72 % of M o is collect d, but
since more pulses can be employ d in lhe same time. a 43 % gaio in sensitivity
resulls. If a small fl ip anglc, e. g., 30 . i u ed. ,/\11 \' i now 1/2 of NI \1 (s in 30' ). bUI
sincc 'vi : is 85 % (cos 30) of il original val lle, -jt doesn'l takc a, long to decay
back to Ihe equilibrium M: and lhe cond pul e can be applied fas ter. gai n
of 50 % is achicved for r = TI and e en higher wh n r < TI' The Ilip angle
approach is used (O enhance signal to noise wit h the oplimum tlip angle giv n by:
COS (}
Qpt
= e - ' I ]' (8-2l)
!t is clear from lhi discu sion Lhal in a sample conlai ning nuclei wilh arying
TI' s, Ihe im n ity dislribulion 01' Lhe peaks ean be dis lorted because of varialions
in Ihe amount of lhe FID curve obtain d. lt can also be appreciated Iha l nuclei
wilh lu rge TI 's can be completely mi ed, e.g., Ihe earb ns of metal carbonyls
are often nol een using the landard acquisition limes b ause 0111 a smal!
rmetioo of lhe FI D cur e is oblained.
Seleetion or lhe pu lse frequency, (1) 0 ' i ' an addilional con ideralion. Changing
lets yOll vary lhe regions ver whieh one woul d carry out a 500-Hz swcep, W
o
ror example. JI' C
o
is elected at a lower frequency than a peak in lhe . p ctruffi,
Ihi peak can appear as an echo on Ihe olher of C
o
' It orten . hows up a
an inverled p ak wilh un irregular pulse.
Our final consideralion is variat ion of lhe spectral widlh. As shown in
equal ion (8- 20), 'horter pulses givc a wi der range of rrcquencies enabling one to
increase Ihe spect ral width. However, going lo a larger speclral wi dth Icad lo a
decrea ' C tn digital re olulion beca u e r the limiled numbcr of storagc channels
JO
fill
[n
in I
is il
Ihe
rot;
flI '
o t
a n(
the !
vec!
Ihe
Hll ,
tion:
dete
180 '
expt!
the I
(i .e..
can I
decr
f ar
lIdi;
con i
by a
ror
is en
wail J
is ree
Jor a
thal r
r, befi
8--9 The Measurement of T, by (FTNMR) 315
in the compuler. Techniqucs such as zero filli ng, malched fi lters. and elcctronic
filt ers can also be uscd to improve resolulion a nd nhance signal l O noi ' C.(3 6
8-9 THE MEASUREMENT OF T
1
BY FTNMR
In a stal ic fiel d. Ihe nuclear mornents precess abo ut lhe fi eld di rection as shown
in Fi g. 8- 21. As described earlier, when a secondary field H 1 is applicd. which
is in phase wilh Ihe Larmor freq ucncy, a lorque is exerted Ibat lends lO makc
Ihe moment precess about H l' If we defi ne a rOlaling coordinate system lhat
rolales as the Larmor frequency. we only have lO rry aboul Ihe lorque from
Hl ' Tf we c nsi der lhe 1/ I direction lo be p rpendicular to lhe page, lhe cone i
so lipped lhal projeclion of the magnel ic moment vectors in lhe xy plane gives
a net xy-eompo nenl (see Fig. 8- 22). Relaxal i n t nds to resto re the syslem lO
Ihe situalion in . ig. 8-21. The torque is lhe eros' produet of lhe magnet ie moment
and ji l ' 'o al resonance in lhe slow passage exper iment, H 1 tends lO lip
the nel magnelie m ment vector (whieh has no xy-componenl in Ihe ab. nce of
H 1)' inducing an xy-component. (When H t is applied, IX and f3 are no! eigenfunc-
tions, but sorne linear combination of them is.) This net xy-magnetizalion is
detected when one passes through resonance in the slow passage experirnent.
In a pulse expeJimenl. it is possible lO lip the magnetization vecl or 90',
180, or n depending on the duration f lhe pul e. In all but lhe 180' pulse
experiments, an xy-component i induced. In a 180' pulse experirnenl. we invert
lhe magnetic moment vector (1 80 inver ion) fro m the p sition where H 1 = O
U.e., fro m posiliv nI = to negative and do not generate an -,y-component as
can be se n ror the net moment in . ig. 8- 23.
After the pulse i lurned off and decay occurs, Ihe magnitude of M= ju 1
decreases at a rale g verned by the longit udina l relaxaton time TI' The series
of arrows in Fi a. 8- 24 represent lhe decay of the M= vector wilh lime. Since the
illdividual moments relax in a purely random manner, no xy-component resules.
1t is impossible to detect this decay of M for it has no xy-component. Now
z
consider an experiment in wruch we hil lhe sample wilh a 180 pulse, followed
by a 90 monit oring pulse. We can lhen delect lhe magnelization. Afler waiting
ror thermal equi librium lO be ree tablished (u uaU a time corr sponding lo 57
1
i employed), we can again ubject lhe sam pl lo the same 180 pul 'e, bUI now
wait a while, and then folJ ow wilh a 90
n
monitoring pulse. Such an exper im nt
i referred lO by (he 'ymbolism 180-1' -90. The proces can be repeated by wai ling
for al nger time l' before applying the 90
n
moni loring pulse. The er ies of spectra
that r sult from a sample is shown in Fig. 8- 25 (page 316), where Ihe delay time
r. before the 90 pulse, ncreases from left to righl.
Effect 01
180
0
pu lse
Hu
FIGURE 8-21 Precession 01
nuclear moments in a
Zeeman experi menl. (From
T. C. Far ra and E. D. Becker,
"' Introduction lo Pul se and
Fourier Transform NMR
Methods," Academic Press,
New York, 1971 .)
torque
1 to page H
1
Ha
FIGURE 8-22 Effect 01 a
seeondary lield H
1
.
FIGURE 8-23 The eHeet on
Ihe magnetization 01 a 180
0
pulse.
:
l
FIGURE 8-24 Oecay 01 the
M
z
component with time alter
a 180
0
pulse.
111
1
(A) (8) (e) (O) (E) (F) (G)
T r
*
(H)
r r
I I
u u
* 11 Q *
o
u
8
m
d
ce
de
di
a1/
Br
me
a s
me
lo:
Cor
Wh
(1)
+
FIGURE 8-25 T, determination 01 the 13e Resonances 01 allyl benzene
(e
6
H
s
eH
2
eH=eH
2
). (A) 0.469 sec; (B) 0.938 sec, (e) 1.875 sec , (O) 3.75 sec, (E) 7.5
sec, (F) 15 sec, (G) 30 sec , (H) 60 sec, (1) 120 sec alter the 180
0
pulse. The T, value
lor the eH
2
and =eH
2
resonances are 9.7 and 8.4 seco
des(
s m
reci
whi<
dese
MO The peak ass igned to the CH
2
carbon bound to the phenyl ring is marked
with an asterisk. The magnetization of carbon is seen to follow the pattern Lore
shown in Fig. 8-24. Ir ane plots the magnetization a function of time, r. the
time
curve in Fig. 8-26 is obtained, This curve is of the form:
as Ih
shall
FIGURE 8-26 ehange in obla
magnetization (peak height)
01 the z-component with time where M o is the initial magnetization. The eguation can be sol ved ror T" A value in th,
lollowing a 180
0
pulse
of 9,7 sec results ror the carbon ma rked with the asterisk in F ig. 8-25. T, can
also be estimated at ze ro signa l intensity from the relation t ' / 2 = T, In 2, NMR
instruments have the software to provide values or T, for all of the peaks in t he
spectrum. Proceeding fro m right to left in Fig. 8-25, values of 9.7 sec for C H
2
;
68,62, and 66 sec ror the CDCI
3
triplet; 8.4, 7.4, 10.6, 10.6, 15.3, and 41.4 sec
res ult. T he last value li sted corresponds to the ring carbon to which t he allyl
\
group is attached and is ba rely discernible in the spectra, T he CDCl
3
soivent T

is not accurate because the del ay time between experiments is not long enough.
An inverted resonance is obtained whenever the net magnetization or the
sample is opposed to the fi eld, ror the detection system senses this as an cmission
R(T)
(tra nsition fr om a sta te opposed to the field to one aligned), a nd vice versa for
(A) (B)
net magnetization wit h the field , Another way of looking: al thi s is that a 90
FIGURE 8--27 The effect 01 a
cJockwi e rotation aboul : or a magnetic moment vecto r opposed to the field
90 pulse on (A) - M
z
and
(8) + M
z
(in the rotating
gives rise lo a differenl phase (J 80 different) than rotation by 90 or a vector
aligned with the field. T his is ill us trated in Fig. 8- 27, where H is to be considered
Irame) . perpendicular to the page.
5
ue
rKcd
1ern
the
8-10 Use 01 T, lar Peak Assignments 317
8-10 USE OF 7; FOR PEAK ASSIGNMENTS
We wiII digress for a moment from our discussion of nmr to make c1ear what is
meant by a eorre/ation function. Correlation functions are employed in the
description of processes in which the value of x does not depend on t in a
completely definite way, i.e., a random time proeess. However, the average
dependence of x(t) on t can be wrillen in terms of probability distributions. When
discussing the self-correlation of a variable, the function is referred to as an
autoeorrelation funetion.
Correlation functions are useful for describing random processes e.g.,
Brownian motion of the fluctuating fields arising from the random motion of
molecules that cause relaxation. We can define a correlation function, R(r), for
a system in which the spin exchanges energy with some property (e.g., a magnetic
moment) that is in equilibrium with the lattice. When these motions correspond
to a large number, n, of independent and uncorrelated events, the time-dependent
correlation function is given by the relation:
(8-22)
whcre a(t) is the magnitude of the property (e.g., the nuclear magnetic moment,
uescribing the n particles, with the summation over al! particles i = O... n. The
symbol t refers to time, r to a time increment and Te a time constant whose
reciprocal is the molecular reorientation rate constan!. If we consider a case in
which an assemblage of nuclear moments were al! aligned, equation (8- 22)
describes how the vectoral sum is randomized with time.
A plot of a correlation function for some molecular process that gives a
Lorent?ian line in the frequency domain is given in Fig. 8- 28. The correlation
time Te for a process in which R(T) is an exponential in the time domain is defined
as the time required to get through l/e of the curve (curve is R(T) e- ,/r, ). As we
shall sce, the correlation time will be needed in order to interpret the values
obtained from T measurements.
The following principies underlie the use of T in making peak assignments
in the nmr spectrum of a complex molecule.
time
FIGURE 8-28 Correlation
lunction lor a process
yielding a Lorentzian li ne in
the Irequency domain.
I
1. ' 3e rclaxation times of protonated carbons in !arge or asymmetric
moleculesaredominatedbydipolarinteractionswiththedi rect ly bonded protons.
The value of l / TI for 13e relaxation by a hyd rogen comes from use ofequation
(8- 23) when mol ecular rot ati on is iso tropic, the hyd rogens are decoupled, and
(w
e
+ WH)T
cff
<:g 1(the so-caJl ed extreme narrowing limit).
(8- 23)
Here re and 1'11 are the gyromagnetic ralios of 13C a nd ' H, N is the number of
direetly attached hyd rogens, is the CH distance, and is the efti ct ive r
CII
T
eff
correlation time for rota t ional reorientation. Assume that only directly bound
hydrogenscontribute. Other wise, we have to sumther l ~ T
d r
t e r m ~ for anyo ther
proton tha t eould contribute. I n order for the limit (w
c
+ WH)T
cff
~ 1 to hold.
the atom must be rapidl y rota ting. T he equation app lies onl y undercondi tions
ofprotondecouplingwheret hescala rcoupli ngisremo cd.However,underthese
conditions, it hould be emphasizcd that t he magnetic moments of the pro tons
are not undergoing transi t io nsfast enough to average the moment to zero in the
time requi red for a rot a t ion, 'o dipolar relaxation st ill occurs. Under these
decou plcd conditions, the Fermicontact couplng makes no contribulio n to the
relaxal io n mechanis m and thedipolareffect dominales. It should b cmphasized
lhatbecauseoftheinversesixth powerin r
CH
' dipolarcontributions to I / T, from
a toms a long distance away will be negli gible. In protcins, long is usually
considercd to be ~ 5 but is longer in rigid molecules.
2. If two carbon atoms in a molecule have the same T
eff
, but one ofthem
is not prot onated and the other is, then the non-protonated onewill havea much
longer TI than the protonated one.
3. Differences in 'erf for different carbon in the same molecule may a rise
from anisotropi c rota ti on of the molecule in solution and fro m the efrects of
internal reonentati on. F r l more complete di scussi on ofthe efTects ofinterna!
rotationa nd ofproton decoupling,the reader is refe rred t o refer nces 37and 38.
Applications of thcse pr incipies a re ill ustrated in the T, measurements of
sorneofthet .le resonancesofchol csteryl chlo ridc.(391 Theresul tsa resumma rized
in Fi g. 8- 29. T he protona led carbons on t he ring backbone (no t shown) and
ot her proto nated carbons (also not shown) all have the same T
l
and hence t he
same T
eff
. The overall reori ntaton of lhe molecule is isotropic, and T, values
can be used to di stingu' h eH and CHz protons. The ca rbon with no protons
attached,C( 13),issecn to havea much larger TI (i. e., a sharper line when T, = T
2
)
thanot hers in lh molecule.Thc methyl carbonshave long TI 's, considering that
1.5 0.67 2.0
24
26
FIGURE 8-29 T
1
values in
(sec lor various 13C atoms in
cholesteryl chloride in CCI.
at 42. [Reprinted with
permission Irom A. Allerhand
and D. Doddrell , J. Amer .
2.1
Chem. Soc., 93, 2777 (1971) .
Chemical Society.]
ti
\V
Sin
\Vil
T
ro!
C'H
lhe
18
-
8-11
A br
opp
have
re'on
pect
disclI
the n'
largel
The t ta l signa l-to-noise gan hcn al! of the techniques we have been
discussingareemployedisnter Sli ngtonote.InFouriertransfonn pectroscopy,
the multipletcollapsefroro double resonanc , the nuclearOverhausereffect, the
larger si ze ofsample tube, a nd the accumulalion that can be done in t he same
of
ru
cd
land
the
lues
tons
~ T
2
)
thal
20
,@
,/
8
therearethreeprotons on sucha carbonoThi s is due to the rapid rotationabout
the C-C bond t hat decreases ' eff;as seen in equation(8- 22) thisdecreases l T
I
or inereases TI . By comparing TI' s down the long side chain at the top of the
figure, one sees that the effect ofinternal motion increases toward rhe free end
ofthe chain as expectcd.
The proton TIvaluesofvinylaceta te areshown in Fig. 1\- 30. T her-
6
di polar
effec ofIhe protons on eaeh other are seen in al! three val ues.
Adva ntage ean be taken ofthe arge differences in the TI val ues ofprotons
to simplify the nmr spectrum. For a particul a r delay time following t he inil ial
180
0
pulse, the magneti zation vecto r can decay to zero intensity. o inlcnsily
will then be dclected when this is followed by a monitoring 90 pulse (see Fig.
8- 25 and the discussi on of it). T hus, if there are two overlapping peaks wi th
di ffe rent TI's,a 180 pulse followed by a properly timed waitbeforethe90 pul se
will remove the peak with the shorter TI. A threefold or greater different ial in
the rclaxation times ofthe overlapping protons is ideal for thisa pplication.With
TI for HOO about 7 sec and that ofsolutes usuall y less, t his technique can be
used for sol vent suppression.
8-11 NMR OF QUAORUPOLAR NUCLEI
The nmr tines ofquadrupolar nuclei are very broad. Forspherical rota lion, the
width is a fUllction ofthe nuclcar quadrupole moment and the correlation time
Te as given in equation (824):
(8- 24)
Since the nuclear quadrupole cffect on the relaxation process dominates l he tine
width and since this effect is int ramolecular, onl y the rotational contribution to
TI is importan l. However it is possible to have both isot ropic and an ot ropie
rotat ion, and this compli cate the line width intcrpreta tion. For example, in
CHCl
j
, the rotational difTu ion constant at room temperature perpendicular to
the C
J
a x i ~ D.1 ' is 0.96 X 10" sec-
I
, whereas that parallel to this a is, D
II
, is
10
11
1. 8 x sec- l.
8- 12 13C
A brief discussi on of 13C magnetic resonance, a bbreviated cmr, will gi ve us an
opport unity to review alld apply several of the principIes and phenomena we
have developed: t he ourier t ra nsform technique, t he use of TI data lo assign
resonanees a nd the nuclear Overhauser enhancement that results in the LJC
spect rum by decoupling the proton nmr.
8- 12 De 319
26.9 864
H" / H
C= C
H
/ "
o
35.8 I
/ c ~
H
3
C o
FIGURE 8-30 T, values lar
th e protons 01vinyl acelate.
Applications
and Strategies
in FTNMR
220 200 180 160 140 120 100 80 60 40 20
- C OH
CH, X, X - F, CI, Br, I
ALKYNES

=C-
ALKENES
=-CH,
-CH-
=e.:.
AROMATlC HYDROCARBONS
Monoaromat ics
C- H
C-
Diaromatics
C-H
C-
C (bridge)
Tnaromatics
C- H
C-
C (bridge)
HETEROAROMATICS
Pyridnes
DI/ho C-H
ortho C-
Thiophenes
ortho C-H
orlho c-
Furans
ortho C-H
orrho c-
HETEROSUBSTITUTED AROMATlCS
C-GH
C-OR
C- CHO
C- COOR
C- COR
C- -NH,
C-- NR,
C-NO,
c-x,X =F, CI, 8r, I
ESTERS
--COOR
ConJugated
-
ACIDS
- COOH
ALKANES
CH,-
- <;:H,-
- CH-

SUBSTITUTED CYCLOHEXANES (PENTANES)
eH1
5

<.0
UNSUBSTlTUTED ,(CH,)") ,n 4-17
(CH,) ",h "------""
ALCOHOLS
CH,OH
- CH, OH

Conjugaled
ALDEHYDES
-CHO
Conjugaled
KETONES
Cycli c &Bi cyclic
AllcycJic
Conjugaled
-
- 20 O 20 40 60 80 100 120 140 160 180 200 220
8C
I
ppm
FIGURE 8-31 A 13ecorrelation chart. [From R, K. Jensen and L. Petrakis ,J. Mag _
Res , 7, 106 (1972).J
1
a
T
rr
Ir
pi
fn
111
ar
he
m,
te(
it i
th

USI
lo
,Ir!
Sud
of
eh
sp
ni

pr
8-12 "e 32 1
time al! ead to a total gain of 10
4
. Routine high resolution 13e spectra of
organic molecules can be obtained on 0.5-M solutions in 20 minutes and on as
low a concentration as 0.05 M in 20 hours.
The cmr spectra are dominated by the local paramagnetic term leading to
a wider range of shifts than protons. The shifts observed provide a very good
indication of the functional groups present in a molecule, as can be secn from
the correlation chart in Fig. 8-30. The fact that a given carbon-conlaining
functional group (e.y., a substituted benzene or heterocycle containing ring
carbons) shows a very characteristic shift has made the fingerprint type of
application even more ,' uecessful than in proton magnetic resonance.
Because of the nucl ear Overhauser effect, the integrated intensity of a 13C
resonance is not necessarily proportional to the number of carbons under the
peak. In some cases, this problem can be overcome by adding a free radical or
a paramagnetic ion to the solution. Spin-spin coupling from 13 C_13C is not seen
in the spectrum of a molecule containing several c-e bonds if il is not enriched
in l3e beca use with a 1.1 % natural abundance the probability that two DC
nuclei would be next to each other in the molecule is very low, 10-
4
In a large organic molecule, there are many l3e resonances to be assigned.
The correlation chart in Fig. 8-31 will obviously not permit an assignment of
all the resonances. As mentioned carlicr, TI measurements are a considerable aid.
There is another technique, referred to as ojFcenter douhle resonance. As
mentioned earlier, if alll he protons are decoupled in an nmr experiment, all lhe
information potentially available regarding the proton splitting ::.; lost. Ir the
proton decoupling frequency employed is off center with respect to the proton
frequencies involved, only a partial collapse of the multiplet results and some
Overhauser enhancemenl is obtained. Thc resulling coupling constants and peak
intensities are distorted(40) compared to those in the spectrum obtained without
any decoupling. Long-range coupling is eliminated. The partial multiplet structure
helps assign the resonances. This technique is more difficult at fields of 4.7 T or
more and has been replaced by polarizalion transfer and two-dimensional
techniq ues.
Since a major relaxation pa th in vol ves the dipolar cou pling of bound protons,
it is often found (particularly for non-protonated carbons, e.y., a metal carbonyl)
that a carbon signal can be saturated and is missing from the spect ru m. To
observe nuclei with very long T's, smalJ ftip angles [e of equation (8-15)] are
used in running the speclra and long pauses betwccn pu lses must be employed
to obtain the free induction decay curve. Even with these techniques, poor spectra
are often obtained. It has been shown that TI can be drastically reduced by
adding paramagnetic complexes, as mentioned earlier, for large fiuctuating
magnetic fields arise from the paramagnetic eomplex moving through the solvent
and these lead to the very effective T relaxation. Trisacetyl-acetonato chro-
mium( fI f) is a paramagnetic complex that is quite unreactive and has been
successfull y employed this way(41) A series of spectra in which the concentration
of the relaxation agent is varied should be studied to dClermine whether the
chemical shift of the l3e resonanee is being inftuenced by the paramagnetic
species. Doddrell and Allerhand(42) have uti ll ized a combination of lhese tech-
niques in the assignment of the resonances (lf vitamin B
12
, coenzyme B
12
, and
other corrinoids. The reader is referred to the discussion in this reference for a
practical illustration of Ll e peak assignments.
Another intere, ting spectral enhancemcnt tcehnique is referred to as yated
,
.
,
decouplinq.(431 When proton d coupli ng is termi nated immcdiately before pulsing,
lhe ( e - H coupling return irn medialely, bul lhe populat ons of the nuclear
energy levels are no! equilibrated as rap dly. Thus, ome Overhauser enhancement
remans. The lechnique thus involves decoupling, terminati Ol1 of decoupli ng.
pulsi ng, storage of the free induction decay, and repetition of this pr eess for all
pulse eycles. e orreel va lues of j"C- H are obtained.
Alternately, if the decoupli ng pulse is lll rned on j usI afler lhe pul e, decoupling
occurs ins tanlly bul nOe de elops slowly producing fulJ decoupled sp 'clra with
liule nOe di. lort ion. One must wail for the nO lO d cay fulJ y betw n pul s .
Thi s proc dure ha alll e in syslems with negative nOe'
A ery excili ng appli cal ion of cmr in Ive its use a. l probe, permitting
on to empl oy lable isoLOpes as !racers.<44
1
Because the (3e re onanees are
eXlremely sensitive lo the I cation of lhe alom in a molecule, the si te of
incorp ration of l he 13 can oflen be casil y identified wit hout l he timc-consuming
degradation required with radi oacti vc iso topes. Thc ineorporat ion of 13 -Iabeled
glycine lOto coproporphyrin-1I1 by lhe baeteri um RhodopseudomonGs spheroides is
an excellent ill ustrati on of the met hod.(441 The bacteria were grown on a medium
containjng glycine that wa 93 % labeled in the ex- position wilh u . Thc r su ll ing
prophyrins had the 13C alom incorporated solel y as pyrrole 'X-carbon atom.
and methine bridge carbon aLoms. This r ult is consislent wit h lhe sequence of
reaction propo ed ror the bio ynthcsi' of porphyrins. If thi typc of Lraeer
applicalion had been earried OLlt usin
o
I..e and subsequent radiochemlCal
analysis, Ihe study would have been less delini tivc and more time consuming.
The product woul d have had to be degraded into small fragments to fi nd lhe
locat ion of the radioactive 14C. There are many potent ial applicnt ions of this
lype tha t involve using Ile as a Ira er atom. One of lhe main advantage, lO
using 13e la beis in biological y temo is thal this label does not disturb lhe
eonformati on 01" lhe biornoleeule a a abel or paramagnet ic probe might.
In a 13e tudy(
45
1 orlab led eo binding to human hemoglobin, two eparate
r onance could b observed for the coordinated eo. These oceurred al 207.04
ppm and 206.60 ppm. The f rmer resonance \vas assigned lO O bound to the
;,: -ehai n and the lalter to lhat bound to lh\: f3- chain by stud ing an abnormal
hemogl bin that contains normal f3-chains bu t x-chains that do not bind CO.
In rabbit hemoglobin, three distinet iron(JI)-binding sites were fo und.(''61 A
funct ionally different hemoglobin ubunil was establi shed.
In un ther inleresling application(-I. 7
1
of 13e, TI mea. urcmcnts were arned
out on selecti vely 1.\ -Iab led hislidine bound lo intracellular and cxtraccllular
mouse hemoglobin. The intracellular and ext rae lI ular TI alues dilli red by only
25% uggesting thal lhe viscosiLy of the intrac lI ula r flui d is not unusuall y large
(al least in lhis system). Ther had been con iderab le cont roversy regardi ng this
problem.
When m I cule c ntaining two directly bonded De atoms a re investigatcd,
spin-spin splitting results. The devialion of the intensity of the rnul tiplet pattcrn
from statistical considerations in a biosynthetie cxperiment can provide a measure
of the eorrelation in rhe Sueh rmation has important meeh-
anisti c implicati ons. For example, mixtures of doubly lab led and unlabeled
material can be ludied. Di luti ol1 in lhe 13c- 13e interact ion would indicate
c1eavage of this bond in lhe biosynthesis.
Cmr has been of considerabl utilit y( 491 in identifying lhe xistence and
trueture of C<'lrbonium ions and carbocat ion' in sol ut ion. Typically, a positively
b
refi
In
Co
of
bel1
fre
Th
to S
101
beCI
inte
rece'
di ffi
mct
8-13
Thc a
ha Ic<
nude'
reccpl
quan ti
and i.
q
sharp:
seen ir
cxten
ano R
8-13 Other Nuclei 323
charged carb n will be deshielded compared to the analogous carbon in a neutral
reference compound, and it will cause an induct ive deshiel ding of 5 to 15 ppm
in el neighbor alomo
The cmr spectra of many organomctallic compounds have b n report d.(50-54)
Complexation of olefins 10 AgNO) re ultS(50) in 1 to 4 ppm hift , wherea shifts
of 30 to 110 ppm have been observed upon coordi nati on lO rhodium.( S1) Th
benzene in CH6Cr(COh are shie lded( 521 so rne 30 ppm relal ive lO
free bcn7ene, wherea those of bound CO arc usuall y de hield d from free O.
Thc d CO resonances in diamagnetic metal carbonyls are relalively in 'cn itive
to sub tit uent and metaL Sorne typical results(50) are li sted in Tablc 8- 1. The
inlerpretation of th 13C chemieal hifts in organometall ic compounds has reccntl
beco critici zed by Eva ns and orton.(551 A thorough anal yss of Ihe shift
interpreta ti on and S0l11C results on the calcul ation of the sh lding constant have
recently been summarized(5l The interpretalion of small shift differe nces is vcry
di ffi cult Consi tent inlerprctations based on in reased deshielding wi th in reas d
metal-to- Iigand rr backbonding have been olTered.
TABLE 8-1 Sorne Typl cal 13C Resonances in Metal
Carbon yls
Complex olJC of Carbonyl
Ni(CO) ..
Fc(COls
Cr(C01
6
Mo(CO)"
W(COl

V(CO)
CpCr( 0h -
CpM n( 0 )3
( C,H
S
)3 PW(CO)s
(C
6
H
s
Ol -,PW( O)
(Cp = cyclop ntadi ni de)
+19 16
+2 12
+ 211.3
+ 200.8
+19 1A
+ 225. 7
+246. 8
+ 2_5. 1
+221.3 cis; + 11 _S [ ral/ S
217.6 +2 13.9 lrClll S
8-13 OTHER NUCLEI
The advent of FTNMR enables Ihe study of nuclci with low sensitivityl57) and
has led to a sub tantia! increase in Ihe number of dements readily stud icd. Vari us
nuclea r properties of the el ments ar Usted inside lh front cove r. The rclalive
receplivit y of s me of lhe more common nuclei are li ted in Table 8- 2. This
quantity indicales lhe relalive ignal strength of 'olutions of eq ual concentration
and is proportional to ,,3 N(J + l) where N is Ihe natural abundanc .
Quadrupolar nuclei in cnvironmenlS wit h eubic ymmet ry give rea 'ona bl y
. harp lines Ihat are br adened cxtensi ely in lower- ymmet ry environmenls_ A'
seen in Fig. 8 32. the sharp line for 35 C1 in aqueou solUl i n is br adened
exlensive! by an erre t as subtle as ion pairing in R)N R' CI where R = Il-octyl
and R' = CH J' The slowcr lumbling of the arge ion pai r leads to faster relaxalion
and thi s coupled with the lowcr , ymmetry of chloride in the ion pair leads to a
broad lin
,
l
324 Chapler 8 Dynami c and Fouri er Transfor m NMR
TABLE 8-2 NMR Properties 01 Selected Nuclei
al
Relalive nmr Relalive Relalive nmr Relalive
Isolope Spln Frequency/MHz Receplivily Isolope Spin Frequency/MHz Receplivily e
107 Ag
10 9Ag
n AI
75 As
197 Au
10 B
IIB
137 Ba
9Be
z09 Bi
79 Br
81 Br
13C
43
a
Ill Cd
11 3Cd
3sCI
37 CI
S9CO
53
r
13 3CS
63CU
65CU
19 F
57Fc
6
9
Ga
71Ga
73Gc
l H
2H
177 Hf
179 Hf
199 Hg
20 lHg
127 ]
Il sln
19 1 Ir
193 1r
39 K
13 9La
6Li
7Li
25 Mg
55 Mn
95Mo
97 Mo
1/2
1/ 2
5/2
3/ 2
3/2
3
3/ 2
3, 2
3/ 2
9/ 2
3/2
3; 2
1/ 2
7/ 2
1/ 2
1/2
3/2
312
7/2
3/ 2
7/ 2
3/ 2
3/2
1/ 2
1/ 2
3/2
3/ 2
9/2
1/2
I
7/ 2
9/ 2
1/ 2
3/ 2
5/2
9/ 2
3/2
3/2
3/ 2
7/2
I
3/ 2
5/2
5/2
5/2
S/2
4.0
4.7
26.1
17 .2
17
10.7
32. 1
11.1
14. 1
16.2
25 .1
27. 1
25.1
6.7
2l.2
22.2
9.8
8.2
23.6
5.7
13.2
26.5
28A
94.1
3. 2
24.0
30.6
3.5
100.0
15A
4.0
2.5
17.9
6.6
20. 1
no
1.7
1.9
4.7
14.2
14.7
38. 9
6. 1
24.7
6.S
6.7
3. 5 x
10 - 5
4.9 x lO
5
2. 1 x 10 -
1
2.5 x
10- 2
2.6 x
10 - 5
3.9 x
10 - 3
U x
10-
1
7.9 x 10 -
4
1.4 x
10 - 2
l A x 10 -
1
4.0 x
10 -
2
4.9 x lO

1. 8 x
10 -
4
87 x
10-
6
l.2x
10- 3
lJx lO
3
3.6 x
10 - 3
6.7 x lO
4
2.8 x
10 - 1
8.6 x
10 - 5
4.8 x
10 - 2
6.5 x 10 -
2
3.6 x 10 -
2
8.3 x 10 -
1
7A x 10-
7
4.2 x
10-
2
5. 7 x
10- 2
l.l x 10-
4
1.00
1.5 x
10-
6
2.6 x
10-
4
7.4 x
10- 5
9.8 x
10 -
4
1.9 x 10 -
4
9.5 x
10-
2
3A x
10 -
1
9.8 x
10-
6
2 1 x
10- 5
4.8 x 10-
4
6.0 x 10-
2
6.3 x 10-
4
2.7 x 10-
1
2.7 x 10 -
4
1. 8 x 10 - I
S.I x 10 -
4
3.3 x 10 -
4
14N
ISN
23 Na
93 Nb
61N i
17
0
1870S
1890 S
31p
207 Pb

195 pt
87 Rb

18
7
Re
103 Rh
99R u
10 lR u
33 S
121Sb
123 Sb
45SC
77S
e
29 Si
117S
n
11 9Sn
87Sr
181Ta
12 5Te
47Ti
49Ti
203TI
2 TI
169T m
Sly
183 W
129 Xe
1
31
Xe
89 y
171Yb
67Zn
9
1
Z
r
I
1/ 2
3/2
9/2
3/ 2
5/ 2
1/ 2
3/ 2
1/ 2
Ij2
_/2
1/ 2
3/2
5/ 2
5/ 2
1/ 2
5/ 2
5j2
3/ 2
5j2
7/ 2
7/2
1/ 2
1/2
1/ 2
1/ 2
9/2
7/2
1/2
5/2
7/ 2
1/ 2
1/ 2
1/ 2
7/ 2
1/2
1/ 2
/ 2
1/ 2
1/2
5/ 2
S/2
7.2
10.1
26 .5
24 .5
8.9
13.6
2.3
7.8
40.5
20.9
4.6
21A
32.8
22 .7
22.9
3. 2
4.6
5.2
7.7
24.0
13.0
24.3
19. 1
19.9
35.6
373
4.3
12 .0
3 1.5
5.6
5.6
57. 1
57 .6
8.3
263
4.2
27.8
8.2
4.9
17.6
6.3
9.3
1.0 x
10-
3
3.9 x 10 -
6
9.3 x
lO 2
4.9 x 10 -
1
4. 1 x 10 -
1.) x 10 - 5
2.0 x 10 -
7
3.9 x
10 -
4
66 x
10 -
2
2.0 x
10 - 3
2.5 x
10 -
4
3.4 x
10- 3
4.9 x
10 - 2
5. 1 x
10- Z
8.8 x 10 - 2
3.2 x 10-
5
1.5 x
10-
4
2.8 x
10 -
4
17 x
10 - 5
9.3 x
10 - 2
2.0 x
10 - 2
JO x
10 -
1
5.3 x
10 -
4
3.7 x
10 -
4
3.5 x
10 - 3
4.5 x 10-
3
1.9 x lO 4
3.7 x 10-
2
2.2 x
10- 3
l.Sx 10 -
4
2. 1 x 10 -
4
5.7 x
10 - 2
l A x 10 -
1
5.7 x 10-
4
3.8 x
10 - I
1.1 x
10 -
5.7 x
10- 3
5.9 x
10-
4
l.2x
10-
4
7.8 x
10-
4
l.2x
10-
4
l.l x
10-
3
e
pe
ha
CO
Wl
n
del
ha!
tOI
nit
ran
the

il is
IinQ
eoo
by
dyn
ISO II
bee
111 vo
In m
ill u .
T he p
proto
reso na
a nd e
199 Hg
couplil
satellit
a risi ng
co nsist
T
8-13 Other Nuclei 325
Nitrogen nmr is an interesting example to consider(58) for it illustrates the
advantages and difficulties associated with multinuclear magnetic resonance.
Compounds containing nitrogen exist in nine stable oxidation sta tes and five
coordination numbers with lone pairs and n-systems leading to interesting
perturbations. Two isotopes can be investigated 15N(I = 1/
2
) and 14N(J = 1). 80th
have low sensi tivity with receptivities of 3.9 x 10-
6
and 1 x 10-
3
, respectively,
compared to DC at 1.8 x 10-
4
. Higher fi elds help because sensitivity increases
with y
3
H
o
3/2 ReJaxation is slow with 15N slowing down spectral acquisition and
nOe is nega tive beca use y is negative leading to diminished signals with proton
decoupling. Enriched samples or large samplcs at high fields are required. 14N
has a receptivity five times that of DC but is a quadrupolar nuc1eus. In addition
to environments with cubic symmetry, reasonably sharp lines are found in nitrates,
nitrites, nitro compounds, nitriles, and isonitriles. Correlation charts indicating
ranges of chemical shifts for a variety of nitrogen compounds can be found in
the Iiterature( 58) The range in chemical shifts fou:1d in nitrogen COl11pounds is
about three times that found in 13 . Oeshielding of nitrogen is observed when
it is involved in n-bonding to neighbor atoms and when it is bent as opposed to
linear in it s coordination to metal complexes, e.g. , bent US. linear nitrosyi
coordination.
Oeuterium nmr is of interest beca use its relaxation behavior is dominated
by a quadrupolar mechanism and consequently is indicative of molecular
dynamics at the molecular position of substitution. In a simple case of rapid
isotropic motion, the longer TI the more mobile the C-O bond. The relationship
becomes more complicated for more complex slower motion. Significant findings
involving the degree of molecular organization and dynamic processes occurring
in membranes have been reported(59)
The advantages of multinuc1ear nmr in structural elucidation are nicely
illustrated by the nmr studyl60) of:
Me Me Me Me
\/ \/
P -CH CH -P
/ / 2
H-C : Hg : C-H

-CH
/
2
"'"
CH P
;/
P - -
/ \ 2 / \
Me Me Me Me
The 1 H, 13C, 31 P, and 199Hg magnetic resonances can all be investigated.
The proton nmr shows the three signals expected for the CH
3
, CH
2
, and CH
protons with relative intensities of 12:4: 1. Observation of one .H
3
and CH
1
resonance proves that the ligands are symmetrically bound to mercury. Thc CH
3
and CH
2
groups show couplings to 31p and satellites from the 16.8% abundant
199Hg, whereas the C-H peak is a broad resonance with no resolution of
couplings. The proton decoupled 31 p spectrum has a single main peak with
satellites from 199Hg and the proton-decoupled 199Hg resonance is a quintet
arising from coupling to four equivalent 31 P nuclei. No other structure is
consistent with all these observations.
(e)
(B)
(A)
I
500 o -500
FIGURE 8-32 35el NMR 01
(A) a 5-M aqueous sodium
cloride; (B) ion-paired, 0.1 M
R
4
N+el - in butanol, and (e)
1.2 M R
4
N+el - in butanol.
l
l
)
I
x
More on
Relaxation
Processes
FIGURE 8- 33 A pl ot 01 the
spectral density 01 various
Irequencies lor syslems (A),
(8) , and (e) corresponding l o
dillerenl cor relalion times.
8-14 SPECTRAL DENSITY
In equa ti on (8-22), the autocorrelation fu nction for a partiele undergoing random
motion was di scusscd. As mentioned earlier, the Fou rier transform convcrl s a
function from the time doma in to the frequency domain. T he Fuurier tran sform
of the corrclation funct ion produces a quanlity called the speclra l den si ty, J(w) ,
which is dcfined by
(11 25)
The spectral den ly for any given freq uency, J(w) , gi ves the int nsily of the
flucruat ion at that particular frequency. The fl uct uations of importan e in nmr
inelude the rel at ive diffusion of one molecule past another, described by a
correlation time, rD; the rot ation of a molecule about its rota ti on axes, r
R
; a
rapidl rel a ing nueleus, r
s
; and chcmical ex hange, re. Classical lexts on nmr
give equations for variolls eontri but ions to relaxat ion, e.g. , dipol ar interaclion,
quadrupolar inl raeti on, chemieal shift anisolropy, scalar coupl ing, spin-rotation,
and so on, in terms of the eorr lation fu nction formalismo AH of lh se phenomena
cause a givcn nuel us to expcrienee a ftuctuating fi eld rrom another nucleus in
sol ution. T he effieieney of nuclear rel xation wi H depend upon lhe intensity of
the frequency arisi ng fr m lhe ftuctual ion, which in lllrn d pends upon the
correlali n ti mes re for the various processes. Accordingly, it is appropriate 10
examine in more detail the relat ionship between spectral density a nd re
If we pl ot the spectral den it y us. w, curves comparable to those shown in
Fi g. 33 are obtained. These differenl curves correspond to di ffercnt correlali on
times, r e' for our systems. (Reeall that R depends llpon the value of rc) The
half-i ntensi ty height indicaled by the dots correspond to Ule frequency w = re . l.
Therefore, onl y frequeneies smaller lhan ~ re - 1 are available in he sample.
The fiat portion of the curve corresponds to wr
c
~ 1, whereas the region lo t he
J( w )
(A)
(B)
(e)
ID
E
.",
e
O
~
"'
Q)
cr::
rigb
the
at 1I
any
mol
OSl.:i
und
J(w
wil l
the
tbe
rela
next
T
2
is
earli
(w =
TI al
mini
com
Fig.
beha
nter
com
par!
Ihat
mecr
Curv(
tim 1
frequ
COfi1{
8-14 Spectral Densi ty 327
10-
1
10-
5
I
I
I
I
I
(e)
I
(B)
T
1
'" E
'':;
e FIGURE 8-34 Dependences
o
'':;
01 the T
1
and T
2
relaxations ,
<O
~
rr: '"
I
1 0 9 ~ ~ ____~ ~ __-L___~ ____-L1______
10-
15
0
7
10-
3
ri ght of l he dot corre ponds to (I.n ~ 1. The area under ea eh of these curves is
e
Ihe ame. T hi s is equivalent to aying that the ki n tic energy in any Iwo samples
al he same temperal ure is Ihe same, This pI 1 gives al1 i ntensity dist ribul ion fol'
any particular frequency; e.g. , in th case of a magnelic nucl u undergoing
molecular motion, we have lhe intensity dislribut ion fo r cach frequency f the
oscilla ting fic1ds al'ising from the complex moti on that an assemblage of molecul s
undergocs.
For lhe middle curve (B). a correlation time has been seleeled lo maximize
J((I)) al w
a
(i.e ., r e I is selected lO be wo)' Any curve with a larger or smaller Te
will have a smaller value of J(w) al w
o
' lf we choose W
o
al the Larmor frequency,
lhe magnit ud of J(w) al w
a
will be prop rlional to the relaxa ti on efficiency; i.e. ,
Ih greate r th inten ity of the fl ucl uating moment, the more effectivc lhe
relaxation. e rrel ation t imes corresponding to curve (B) are mo t efficient, ( ,)
oe, t mo I of those shown, and (A) lhe lea 1 efficienl.
The TI relaxalion is caused by frequencies lhal correspond to W
a
' whereas
is caused by w = O a nd W
o
frequency components. This is con istenl wi th our T
2
earlier descript ion of the fluctuuting field causing TI relaxation and lhe static
(w = O) field in solids ca usin
a
relaxalion. If we were to plot lhe behavior of T
2
TI as a functi on of r e' we would obtain the curve labeled TI in Fig. 34. The
mnimum corresponds l O the solid dot of curve (B) in Fig. 8-33. Larger or smaller
correlation times give a smaller spectral densily al this frequency. Curve (C) of
Fig. 8-33, corresponding to lhe dash d li ne labeled (C) in Fig. 8- 34, gives Ihe
b havior a l shorter correlation times; a longer relaxa lion lime re ul ts. 11 is
inlere ting to point out tha! TI is a doublc-val ued function; i.e., a given TI can
c rrespond to two possible values of Te ' To oblain re ' one musl know on what
pan of lhe curve lhe system i I cated,
The behavior of T
2
s deseribed by the curve so labeled in Fig. 8-34. Note
Ihat for short corrclalion limes. T
1
parallels TI ; Le., lhe pin-Iattice relaxat ion
mechanism is randomzing lhe z-compooent and Ihe xy-componenl equally. Ln
curve (A) of Fig. 8- 3, we have a situaton tbal would correspond lO correlation
limes in a vi. cous liquid or solido There is a greully reduced intcnsily of Ihe
frequency componen! (Va needed for longitudinal relaxat on. However, Ihe (J) = O
comp nenl is very large and lhe tran ver e rclalion is enhanced, The zcro
'
8-1
328 Chapter 8
Multipulse
Methods
Oynamic and Fourier Transform NMR
frequency dipolar broadening thus decreases T
2
, causing line broadening in
viscous Iiquids and solids. The increased TI associated with the increased
correlation time in this region of the curve explains why spectra of solids and
viscous liquid are easily saturated.
Often in the following pages we wil! note that processes that increase 01'
decrease the correlation time can sharpen nmr peaks, i.. e., increase TI for the
protons. One should be able to deduce whether TI will increase or decrease by
knowing whether the spectral density change caused by the perturbation moves
the curve away from (B) toward (A) or (C). If the curve is broadened, the
perturbation moves the system from the (A) or (C) direction toward (B).
8-15 INTRODUCTION
The multipulse methods all depend on variation in the start time, duration,
amplitudes, frequencies, and phases of a sequence of pulses. The measuremcn!
of TI discussed earlier in Section 8-9 is a simple example of a multipulse sequence
to measure relaxation times. We can take advantage of pulse sequences to simplify
spectra, gain intensity, separate overlapping peaks to assign resonances, sludy
certain parts of the spectrum, suppress peaks, determine to which nuclei certain
nuclei are coupled even in heavily overlapped spectra, and determine which nuclei
are close by in space. The advances in this area have been phenomenal and
promise to continue. We shall briefly covera few ofthe more common applicalions
here to Iustrate the principIes and the reader is referred to the Iiterature(61) for
more details.
z
z' z'
-...
"-
v' v' v
(A) (8) (e)
z z z'
v'
v' v'
(O) (E) (F )
FIGURE 8-35 The Hahn spin-echo experiment. (A) A 90
0
pulse applied along x' at
time O causes M to tip to the positive y ' axis. (B) Ouring the time 1:, the microscopic
moments in the xy-plane dephase because 01 lield, Ho, inhomogeneity. (C) A 180
0
pulse is applied along x' . (O) The moments regroup. (E) Alter a time 1: lollowing the 180
0
pulse, the moments rephase. (F) At subsequent times, the moments dephase again.
(From T. C. Farrar and E. O. Becker, "Introduction to Pulse and Fourier Translorm
NMA Methods," Academic Press, New York, 1971.)
We
thal
to t
in t
a fa
fiel<
frar
dov
mo
can
at d
alol
out]
rot'
to I
con
cou
H01

Spl
inh
staj
an
rep
are
8-16 Spin Echoes 329
8-16 SPIN ECHOES
We can begin our introduction to this subject by considering a pulse sequence
that leads to a spin echo. A 90 pulse is applied along x' (Fig. 8-35) causing M
to tip to l. After a time 1, T
2
effects and field inhomogeneity at different places
in the sample tube lead to different rates of precession in the xy plane and cause
a fanning out of the magnetic moments in the xy plane. We shall refer to both
field homogeneity and other T
2
effects as T/, i.e., 1jT/ = 1jT
2
+ other effects.
Those nuclei precessing faster than average (the rotation rate of the rotating
frame) appear in the rotating frame to move toward the observer (i.e., looking
down the z' axis they appear to move clockwise), while those slower than average
move away [counterclockwise; Fig. 8-35(B)]. The shaded region in the figure
can be thought of as a whole series of vectors corresponding to nuc!ei precessing
at different frequencies. These are called isochromats. A 180
0
pulse is then applied
along x', moving all the moments 180 about the x' axis [i.e., they are now fanned
out about -las shown in Fig. 8-35(C)]. lt should be emphasized that a 180
G
rotation about x' is different from a 180
0
rotation about Z. The former causes a
to become a' and b to become b'. While we are waiting another time period
corresponding to 1, the faster nuc!ei move c!ockwise and the slower nuclei move
counterc!ockwise in the rotating frame, as shown by the arrows in Fig. 8-35(0).
However, now the slower nuc!ei move toward the observer and (he faster ones
away from the observer, causing them to get back in phase. After the same time
1 that was used after the 90 pulse, the is ochromals have regrouped along l.
The signal detected is shown in Fig. 8-36 and the peak at 21 is referred to as a
spin echo. Ir there had been no relaxation by mechanisms other than feld T
2
inhomogeneity, we would have the same signa! intensity in the echo as at the
start. We have, in effect, eliminated the field inhomogeneity contribution to ~
and can use the decreasc in intensity to ca!culate T
2
. The process 1-1[-1 can be
repeated from the peak of the echo to produce another echo. In practice, there
are two effects that reduce this amplitude: (1) T
2
of the nucleus, which fans out
n
'2
ECHO
PEAK
y'
al
,pie
110
FIGURE 8- 36 The FID Signal for an Echo Sequence 01 Pulses. The signal is
IBO
recorded immediately alter the n/2 pulse and alter a time, r, an pulse is applied.
ain,
The signal rebuilds lo a new peak al lime 2r (i.e., r alter Ihe n pulse) and Ihen
orm
decays. The process can be repealed by applying a n pulse al lime 3r.
1
l h magnetization randomly as opposed to th systcmatic nature of the applied
fi el d, and (2) diffusion of molecu les to di ffercnt parts of the s' mple tube in lhe
time 2r. The lalter introduces error in T
2
We shall refer to the pul'c equence
(re /2)x-r-rex-r-acquire as an echo pl/lse sequece.
Nexl, we consider how nuclei il h di fferen t chemical shifts re pond to the
echo pulse sequence. The 90 puL e rotates lhe magnetization of bolh nuc1ei lo
lhe y-axis. l n a rotat ing fmme chosen to rolate at lhe frequency of lhe most
shielded a-nucleus, the olher nucleus preccsses faster leading after a time, r, to
lbe 'ituation -11 wn in Fig. 8-37(C). The b-nucleus is prect:ssing re[alive lo a al
z
,
, ,
, ,
y
v: v: v
,
f-y
,
I
,
,
x , X ; x X
, ,
I
, , ,
,
t = O : (1(/21 ,
I
,1' , 1( , 't:
(E)
(A) (8) (C) (O)
FIGURE 8-37 The effec! of an echo pulse sequence on nuclei with two different
chemical shifts. Thi s is a simplified represenlatlon of Figure 8-35.
a frequcncy in Hz corresponding lO lhe chemical shift difference. Afler a 180
r
pulse around x. h is behind a and calches up after an addilional [Ime ras sh wn
in Fig. 8- 37(E). Thus. the chemical hifts are refocused at lhe peak of the echo.
Th us, we can carry out experiment on nuclci thal are independenl of field
inhomogeneity r chemical shift differences. We can n w concern ourse[vc with
coupl d sy tcm wilhout worrying aboul chemical shifl diffcrenccs.
Fir t, let u consider the ase of homonuclear coupled . ystems e. g., un A-X
proton-coupl d sy tem whose nmr pectrum consists of a doublet of doublct .
Focus on one of lhe doublet arising [rom coupling and let our [rame rotate al
a frequency corresponding lo lhe c nter of the doublet. Both components are
now preccssing, one at + J/ 2 and the second at -J/ 2 Hz leading after a shorl
lime to lhe siluation in ig. 8- 38(C). No wh na 180 pulse is applied it converl '
every el. nuclcu on A and X into a f3 and vice versa. AH lhe nuclei prccessing at
+ Jj2 wilh el. neighbors now have f3 neigh ors and preccss al - .1/ 2. The same
is true for the nuclei pre sing at - J/2. Thus, the n-pul e has changed lhe la beis
as shown in Fig. 8- 38(D). Now aftcr a time r the isochromal are nol refocused.
If we selecled r-value corresponding to J/4. the isochromats would be aligned
a[ong x in Fig. 8- 38(E), and genera te antiphase components al the e ho. lt is
f
' )
,
f' i
y
! ~ !
,
[+' [ ~ !-I y y
: / (+) (-) (-)
,
l it t it x : . - --- -
1-- I
(A) (9) (C) (O) (E)
FIGURE 8-38 The behavi or 01 the A doubl et in an A- X system lo an echo pulse
sequence.
n
n
b,
lr
u ~
01
8-
af
a ~
W
cq
lh!
an
w
0\'
lo
apJ
pr
13(
of
ig,
Th
PO
I
art
(-
prc
difl
oril
lh n
H
8-17 Sensitivity-Enhancement Methods 331
also important lO point out that in a heteronucl ear coupled system, the neighbor
nucleus is nOI inverted, [he abel ' ar not interchanged upon application of lhe
n-pulse (i .e.. in Fig. 8- 38( D) above), and Ihe components refocus in (E). With
appropri ate equipment, pulses could be appli ed to bOlh nuclei Lo cxchange lhe
labels and lead lo the case in Fig. 8-38. [n all these experiments we shoul d
remember thal lhe magne tizat on is rea ppearing along the z axis with a lime
constanl TI'
8-17 SENSITIVITY-ENHANCEMENT METHODS
As can be seen by its receplivity (Ta ble 8- 2), the proton is the most sensitive
nucl eus. Wben only smaJl amounts of materials containing nucle orders of
magoude less sensitive are available, it becomes impossible lO oblain their nmr
speclra by standard means. The nOe helps a Ij u le, but its advantages are limited.
Meth ds thal Iransfer the favorable properlies f the proton to olher nuclei are
advantageous. Selectiv population inver ion (SPI), insen it ive nuclei enhanced
by polarizali on lransfer (INEPT), and distortionless enhanced pola rization
transfer (DEPT) are method of accomplishing polarization transfer. DEPT,
usually the method of cboice, i more involved and requires an understanding
of the principIes of SPI and INEPT. We begin with SPL
Consider two nuclei 13C and 1H whose energy diagram is shown in Fig.
8- 39. Coupling energies are so small on lhe energy scale of the diagram thal they
are not seen. Thc magnetogyric ratio and Larmor frequency of hydrogen are
about four times thos of carbon, so lhe transitions are four times as energetic.
With a total 01' N nucJei, each level would bave a population of N/4 ir they were
equaIly populated. We shall concentrate on lhe deviation from N/4, which for
lhe ground and excited states i' represented by 2flH for tbe hydrogen transiton
and 2 e for carbon; where liH equal' 4,C from the magnetogyric rati os. Jf we
were working with 13C- H, the fourfold excess 1H population of the lower state
ovcr tha! of carbon and the fourfold larger magnet c moment of the protonleads
to a sixteenfold increase in the transverse rnagnetization when a n/2 pulse is
applied to the proton compared to carbonoThe signal depend' on lhe rate of
precession of lhe magoetization, wh ch is four times greater for the proton than
13C thus a 64-fold difference res ults. The I 0 3Rh nucleus has a }' that i 3 % that
of tbe protoo leading to a sensjtivity 32,000 tim s less. In general, the relative
signal ' are proportional to ')' 3 aod acqui 'ition time to ys.
Now consider the effect of inverting Qne line of lhe proton doublet H l'
This inverts the H 1 population ' leading to Ihe situation in Fig. 8-40. The
population diffcrences across the proton transiti ons are the same except one
is negative, However, the carbon transitions that previously were 2,C
are now (,H + ,C) - ( - flH - flC) or 21iH + 2,C fol' C 1 and
(-,H + ,C) - (llH -lle) or - 2,H + 2flC for C
2
. We have transferred th
proton population differences lo the carbon and added them to the existing
y
differences. With ,H = 4flC, we gel 101lC from 2flH + 2,C or five times the
original inten ity (which was 2,C) and we gel 6 ~ C from - 211H + 2,C or minus
three times Ihe original inten ity. This leads to lhe 13 C spectrum shown in Fig.
8-40(8).
rt would be tedious lO analyze a complex spectrum trus way [or we would
have to find and selectively invert one line of each proton doublet. Furthermore,
we cannot obtain a 13C spectrum that is proton decoupled. The I NEPT
- ll H-llC
y-
-llH + t1e
H,
~
"2\ __ll H- llC
_/c,
H+ t1e
(A)
(B)
FIGURE 8-39 (A) Energy
level diagram includi ng
population differences for an
AX system. (B)
Corresponding NMR spectra.
t1H- t1C
~
- /l H + /l e
\ - -llH-t1C
_/c,
t1H + e
(A)
FIGURE 8-40 (A) Popula!ion
differences for an AX system
alter saturatlon 01 H, (one
componen! 01 the doublet).
(B) The corresponding nmr
spectra.
J...
[II,
4J
z

[II.
FIGU RE 8-41 INEPT pulse sequence.
experiment puts pairs of proton transitions in antiphase independent of their
chemical shift by using a non-selective pulse. This is accomplished by using a
spin echo from Ihe pul se sequence shown in Fig. 8-41.
After a (n/ 2)x pulse to Lhe protons, we wait for a time of J/4 so doublet
components from spin-spin splitting move through 1/ 8 01' the cycle before the
n-pulse is applied (the components precess aLJ/2 Hz).The sensiLive nucleus,
S, (in this case the proLon) is rotated into the oLher half of the xy-plane. A
simultaneous application of Lhe n-puls to the insensitive nucleus (in this case
the carbon)causes a reversal in the sense ofthe precession ofLheJ componcnts
causing them to move as shown in Fig. 8-41. The chemical shifts anci field
inhomogeneity will be refocused in the next J/4, but the magnetization due to
spin coupling is nOL,and ends up 00 thex-axis. A90pulse to the protoosgives
us the antiphase components and the populati on eohancemeoLs we had in SPI
for all the protons. Thesimul taneous 90 pulse to 1JC enables us to acquire the
13Csigna!. Each 13C spin-spin doubletgives risetoa positiveand negativepea k.
We have transferred the sensit ive nucleus population difference to the insensitive
nucleus, but the positive and negative peaks have uoequal intensities, e.g., +S
and - 3 for a 13C doublet .Various pulse sequences enable us to elimi nate this
and to decoupleprotonsplitti ngs.The DEPTsequence has replaced TNEPTand
gives rise to a spectrum with theappearance of a normal nmr spectrum.
A further advantage of these polarization enhancement experiments arises
from the faet thatonJy the populat ion differenceofIhe sensitve nucleus, e.g .. Lhe
protons,Jeadsto thesigna!intensi ty,soit is the T
1
ofthis nucleus thatdetermines
theIPulse repetition rat eo This is a bigadvantage for thestudy ofinsensitivenuclei
with long T
1
's (e.g. , l:iN and 29Si). A further advantage arises in the applcation
of polarization enhancement techniques to nucJei that have negati ve nOe
enhancements. For nuclei thatdo not have large proton couplingconstants(e.g.,
some rhodi um-phosphine complexes), other sensitive nucl ci (e. g., phosphorus)
can be used if a probe tuned to the two frequeneies and two broadband
transmitters are available.
8-18 SELECTIVE EXCITATION ANO SUPPRESSION
The DEPT pul e sequence can be used to seleet certain multiplets for study.
Pul se sequences can be used to selectively study all the eH or CH
2
or CH ]
w

ea
ID eal
illuSL
dyna.
egua
small
8-18 Selective Excitation and Suppr ession 333
resonances; this is called spectrum editing. As an illustration of this application,
consider the 13C nmr of
C6H5 CH
/
CH " -\- " CH,
Pd
/ / CH )
/ N
H) C \ / CH 3
CH
2
-CH
2
which contains thirleen 13C resonances. Assignmenl is difficul t. T he chemical
shifts of CH
3
, CH
2
, and CH protons can be obtained(62) by selectively sludying
each group of resonances as shown in Figure 8-42. AII the coupling conslants
(A)
FIGURE 6-42 The edited 13C
spectra 01
Pd (PCHCHCH
2
) (CH
3
hNCH
2
-
CH
2
N(CH
3
}2 using the DEPT
pulse sequence. (A) The CH)
groups; (B) the CH
2
resonances; and (C) the eH
(B)
resonances . This is a
different pulse sequence
than INEPT. The spectra
come Irom mathematical
operations on sever al
spectra with different pulse
lengths.
(C)
140 100 60
Ii( 13
C
)/ppm
(O)
in each group should be wi thin about 30 % of their average value. The advant ages
illustrated are even more important in anal yzing even more complicated spect ra.
The digit izer bit) that converts lhe speclrum lo digital form has a
dynamic range of about 2000 lo 1. If the largest si gnal in the speclrum is just
equal to the capacily of lhe analogue-to-digital converler, signals 2000 times
smalIer lhan this will nol be detected a l al! . No amount of time averaging will
334 Chapter 8 Dynami c and Fourier Transform NMR
help. Because of the cti git iza lion p rocess, a peak outside lhe spect ral widlh will
fold back into lhe spect rum. Peak suppression or tailored excil ation can all eviate
lhe problem. Peak suppression is be t accomplished by pre-saturation if the ot her
necded components of th spectrum are not undergoing cxchangc with lhe
saturalcd peak. The irradiati on of lhe resonance thal induces satura li on is lurned
off immediately before the applicalion of t he pul 'es and acquis iti on of the
spect ru m. This procedure can be liS d in conjunction wilh sorne of Ihe pulse
sequences discll sed so fa r and with Ihe 1 31 experiment lo be discussed shorlly
[1 refers to (' /4)n 3 lO e/4)rr. and the line over Ihe numb r indicates a ncgalive
pulse, e.g., al ong lhe - x-axis].
Tailorcd excil at ions attempt to lailor lhe frequency disl ribul ion f lhe d.
exci lat ion 10 a void fr quenci cs corresponding to certain regions of the specl rum
(recall lhe distribution ho n in Fig. 8- 18). The seqllcnce, (rr./ 2)x-r-(n/2) - x acquire,
known as j ump and return (JR), ill llstra Les lhe principies for several experim nts
of this Iype. If the transmiller frequency is sel al the peak lo be suppressed, it
wi ll remain statie in t he r-interval whil other wil! preeess. The second {n/ 2) _x
pulse ret llrn lhe peak to be suppressed 10 lhe z-axis with no x-component
gencrated, i.e. , no peak. The peak of intere t moves r lative to lhe rotating frame
during r, thus an x-component remains after the second pul e. Thi s is illuslrated
in Fig. 8 3 where A is the resonance t be suppr 'sed and B the peak of interest.
FIGURE 8-43 The efteet of
the JR pulse sequenee on a
suppressed resonanee A
and cne 01 lnteres! B.
(7( / 21, , ----
Ideally, T should be elected so lhe B magnetization lies along X. Other pulse
sequences have been utilized that are more elfective than J R. The {1t/4l,.-
r-(3rr./4L.,-T-(3rr./4)..-T-(rr./4) _x ' equence, refcrred lo as a 1331 sequence, is part icu-
larly effective with r selected to optimize Ihe spect ral region of interest. This
sequence can provide a lOOO-fold better reduction in a solvent r sonance than
pre-salurat ion. For nucJei oth r than protons, Ihe DANTE sequenc can be
utilized for selective exci lation. This con isls of a train of hard pulses of very
small tlip angles with constant phase and constant separation.
8-19 TWO-DIMENSIONAl NMR
The two-dimensional, (2-D) nmr experiment involvcs the following scquencc of
events:
IPREPARATI ON ~ t ~ PULSE f\pv"-' t 2
TIME Evolution time L ____ -' Deteetion time
The detection peri od corresponds to the usual coll ction of the FrD. whose
transform leaos to the usual frequency spectrum. To examine lhe rest of Ihe
eql
expl
time
anOI
mag
'fn
cone
8-44
2711'/ j
rotal
in 2
Now
Ilt I l
as "
Our 11
of Ih
sliee.
am pli
fe
Lime
freq tle
to l'
oscil!;
8-19 Two-Dimensional NMR 335
of
ose
the
z
Mo ~
Y
-x--*-- - y T
(A) (B) (C) (O)
Preparation (lt/2). ---- t, ------ (lt/2) , ----- Oetection
---- v2 ------
sequence and sorne importan t conseq uences, we shall consi der a very simple
experiment involving the proton nmr of chloroform, CHC)3. Our preparation
time wi ll consist of a (n/ 2)x pulse. We will wait for a time t p a fter wh ich time
another (n/ 2)x pulse is carried out and the signa) detectcd. The behavi or of the
magnetization during Ihis pulse sequence is shown in Fig. 8 4. We shall ignore
T relaxation, for simplicity duri ng the time ti (which is not rclated to TI) and
concern oursel ve only ith the x,y-magnetization in the rotating frame. Fig.
8-44C shows the preccssion of the magneli zation at v Hz forming an angle of
2nvt
1
du ring the ti interva l. The Mv and Mx components are shown and their
rolation by a (n/2)x pul se is shown in (d). The M, component, given by M
sin 2nvt, is detected, Fourier lransformed, a nd a frequency spectrum is obtained.
Now consi der a series of 11 experiments in which t is increased by an incremcnt
~ 1 1 each time. T he M x magnet izati ol1 and resull ing speetral intensity will vary
as t is varied leading lo the series of 17 speetra shown in Fig. 8-45 for J 7 of
our n experiments with regular ~ t increment s.
Now consider a slic lhrough Fig. 8 4 5 at fixed V
2
eorresponding to the top
of t he CHCI
3
peak. Plott ing the variation in amplitude us. ti' for nOI just t he 17
sli ces but , for aH n of t he sli ces of our original ex periment, gl ves Fig. 8-46. The
amplitude is oscillating wilh a frcquency v correspond ing to the chemical shifl
of CHel ) because Mx is given by Msin 2nvt. It decays expon nt ia ll y with a
ti me constan! T
2
lf we Fourier t ra nsform the curve in Fig. 8-46 we btai n lhe
frequency spcctrum in Fig. 8-47(A), wilh its peak al a freq uency corre pond ing
to v (the cheroical shi rt of CHCI
3
) because the tran verse magnetization is
oscill ating sinusoidally at Msin 2nvt 1. If we now take a wh I series of slices
FIGURE 8-14 Behavior 01
the magnetization during a
(n/2), - t, - (n/2), sequence.
The x- and y-components are
shown in (C) and only the
rotation 01 the components
by the n/2 pulse is illustrated
in (O) .
FIGURE 8-45 Nuclear
magnetic resonance spectra
detected at increasing t, by
increments 01 ~ t lor the
pulse scheme in Fig. 8-44.
__----t,--------
FIGURE 8-46 The
interferrogram obtained by
plotting the ampl itude 01 a
slice par allel to the t,-axis 01
Fig. 8-45.
10
336 Chapter 8 Dynamic and Four ier Transform NMR
FIGURE 8-47 (A) The
Fourier transler 01 Fig B-46.
(8) The stacked plot 01
Fourier translorms 01 various
si ices 01 Fig. B-46. (C)
Contour plot 01 Fig. 8--478 .
Ihrough Fig. 8-45 al different values or V
2
and stack these spectra togethcr, we
get the plot shown in Fig. 8-47(B). The stacked plol is orten presented as a
contour plot as shown in Fig. 8-47(C). Generally two-dimensional (2-D) plots
contain V
2
along the abscissa and VI aJong the ordinate and this changeis made
in Fig. 8-47. The symbols F 1 and F 2 are orten employed to indicate the result
arter Fourier transrorm or tI and t
2
to the rrequency domain.
(A)
(8)
(e)
We have created a two-dimensional rrequency spectrum (V I' v
2
) by ouricr
transronning the two time dependencies t
j
, t
2
. In this example, we get a squarc
spectrum with both axes representing chemical shirts and a peak on the diagollal
in the rrequency domain at V, v. We have not learned any new inrormation rrom
the simple example chosen but have selected it to iJlustrate the 2-D method. Now
we move lo more interesting 2-D systems and wiIl begin by considering
homonuc/ear 2-D nmr. In principie, we can perrorm a 2-D experiment on any
system in which a modulation or the rrequency spectr um occurs during the
evolution time t I ' In the aboye example, the same modulation occurred during
both tI and t
2
. Significant results are obtained when different processes occur
during the two time intervals. Generally, normal chemical shirts and couplings
correspond lO t 2' and when a different modulation occurs on tI ' off-diagonal or
cross peaks occur in the plOI or v US. v
2
. To interpret the resulting contour plot
we need to know what the two axes represent and how Ihe two magnetizations
are related. In all 2-D experiments, the F2 dimension conlains inrormation about
the precession rrequency or the observed nucleus. The F dimension contains
inrormation about t he interaction or the observed nucleus and other magnetic
nuclei that develops during the evolution periodo
IS
elim
8-19 Two-Dimensional NMR 337
er
re
nal
m
ow
~ n
any
thc
ring
:cur
ings
Jor
plot
ions
)out
.ains
letic
Consider what happens during the second pulse for a case in which there
is a homonuclear coupling. To simplify the discussion, consider an experiment
in which one automatically increments the decoupling frequency across the region
ofinterest. Each decoupling frequency would manifest itselfby a change at coupled
protons when their partner is irradiated. It would be time consuming to march
across all the frequencies. Instead, we wiJl do this experiment by using FT in the
couphng dimensiono This pul se sequence ((n/2kt 1-(n/2)) is referred to as Jeener's
or the COSY experiment. In a homonuclear, AX, system the second (n/ 2)x pul se
causes magnetization to be redistributed among all the transitions with which a
given transition is associated. In an A-X system (four peaks), a given A Lra nsition
is associated with the other A peak and the two X peaks and likewise for the
other A and two X transitions. Thus a given line in t
2
may have components of
its amplitude modula ted as functions of the frequencies of a ll the other lines in
ti' When the two Fourier transforms are carried out, this redistribution gives
rise lo cross peaks in the 2-D spectrum. The resulting contour plot for a n AX
system is shown in Fig. 8- 48. The peaks along the diagonal arise from
magneti za tion components that have the same frequency during t and t
2
(recall
CHCI
3
). This is the portion ofthe magnetizat ion that was not transferred elsewhere
during the second pulse. Thus, looking along the di ago nal , we see the normal
spectrum- a doublet of doublet s. The cross peaks corresponding to the small
cluster arise from redi tribution within a given multipl et (AAl or XIXZ)' The
off-diagonal peaks fa rther off the diagonal correspond to redi stribution between
difkrenL nuclei . In a more complex molecule we can determine which protons
are coupled to each other by the existence of off-diagonal peaks. We can think
of the coupling as providing a pa thway through which the magnetization can
travel during the second pulse. Couplings that are less than the natural hne width
and hence unresolved in the one-dim nsi onal experiment, are easil y detected in
OSY.
COSY has had important a pplications in cluster chemistry. Typical examples
include 11 B clusters(631 a nd 183W clusters.(64
1
For quadrupolar nucl ei , the
rel axa tion times must be long enough tha t the coupling is not completely
eliminated.
The lNADEQUATE pulse sequence enables one to detect na tural abundance
Ile-
D
c couplings. In thi s experiment, the peaks from lone 13C nuclei a re
eliminated and only those involved in coupling remain. At each existing frequency
in the VI spectrum, a row exists pa rallel to V
z
correspo nding to the coupling of
adjacent 13C atoms.
In the COSY experiment we have ignored the transverse magnetizati on
returned to the z-axis by Lhe second pulse. This magnetization is also modulated
during tI' Since the component i along the z-axis, it is not detected. Ir processes
of interest modulated this z-component, a 90 pulse could be appli ed and its
behavior studied. Two such effects are chemical exchange a nd nOe. If we wait
a while T
m
after the second pulse, i.e., the sequence n/2-tl-n/2-Tm-n/2-tl, a nucleus
whose z magnetization was modulated by one chemical shift during tI migrates
to another site during Tm ' T hus, it has a different chemical shift duri ng t
l
and
the re ulting 2- D spectrum will have cross peaks between the pcaks of exchanging
si tes. Rate data is not obtai ned, but the peaks undergoing exchange are identified.
I n a similar fashion pair of nuclei , that show nOe in a one-dimensional
experiment, show cross peaks in thi' two-dimensional experiment. Spat iaJ
..
-
U
-
-
E
o.
o. -
-
-6.8
:: 1 I 1 1 1 1::
6.8 6.3
ppm
FIGURE 8-48 The conlour
plol 01 a homonuclear
Iwo-dimensi onal A-X syslem
(1 = '/
2
lor A and X) .
I
338 Chapter 8 Dynamic and Fou rier Transform NMR
CH
2
0H
" CHOH
F
2
(H')
FIGURE 8-49 The
correlated heteronuclear
('H, '3C) two-d imensional
spectrum 01 butane-1 ,3-diol.
rel ati onshi ps between protons can be determined by knowing which oncs und rgo
nOe. This technique is particularly useful in large moleculcs where nOe' are large.
The heteronuclear correlated 2- D xperiment , is similar in concept to J EfJT.
A n/ 2-t 1 period on the sensitive, S, nucleu s is followed by a n/ 2 pulse on both
the sensitive and insensitive, 1, nucleus foll owed by accumulation of the signal
of I during (2 ' This is referred to as the heteronuclear shift correlaton (HSC)
sequence. The 2-D plot gives v
2
(S) us. u (I) .e., a peak appears in the contour
plot for correlated nuclei at the chcmical shift of I on the v
2
axis and S Ofl the
V
2
axis. In order to remove coupli ng, a n-pulse is applied to the 1 nucleus halfway
through ( l ' The advantage of HSC is in assigning coupling rclationships in
heteronucl ear systems. Ir the proton spectra is assigned, assignment of the 13C
spectra in the 2- D plot is tri vial. In weakly coupled systems, contour peaks appear
onl y between protons and their directly bonded heteronuclear par tners. In the
pre ence of strong coupli ng b lween HA and H
B
in HA - C- C- He , cross peaks
to the non-bonded carbon can appea r. Often the DC spectra or that of some
nudeus other than H is easier to a ign than hydrogen beca use of less homonuclear
coupling in the former. T he e ideas are illu lrated by lhe correlalcd, heteronuclear
e H, 1 C) 2- D contour pi t of butane-I ,3-diol in Fi g, 8-4 9. T he 13C pcaks are
well scparated and their as ignment leads to assignment of t he di rectly bonded
proton peaks. The 2-D spectra ca n then be used to assign the hydrogen pectra.
Taking a slice through the H e spect ra parallel to V at the ch mical shift of a
nucleus yields the proton spcctra of its att ached proto ns.(65) his meth d i.
particularly usefu l for locating pro ton peaks that are obscured by an unrelaled
mult iplet whose attached 1 JC resonanccs are weH separated. ombinal ion of the
COSY experiment (homonuclear corr late ) n the prOlons with the HSC . pect ra
often all ows the complet fram work of a molecul to b traced.
Our final topic in 2-D nmr will involve J-spect roscopy. This involves spin
echo pul se sequences on the nucleus, observed during t 2 , lo provide information
ab ut c upling. Recall our discussion in Section 8- 16 wh re we sh wed lhe echo
coul d be u ed to cancel ou t chemical hi ft di fferences to lel us tudy coupli ngs.
The pr t n decoupled spectrum will be along one axis and the car bon-proton
or proton-proton coupling constants spread ou t along the other. The decoupling
is modul aled dllring the evol uti on period of lhe echo sequence wi th galed
decoll pl ing or other techniques. The technique aids in the assi gnment of Ihe
rcsonances and peak s due lo spin-spin coupling in badly overlapping spectra.
The prolon dec upl d 13C spect ru l11 of a mixture of deuterat d deriva tives of
loluene is shown in Fig, 8- 50( A) . (Deuteri um has an I-value of one and C- D
cou plin gs lead to the spect ral complexi ty. ) T he J -resolved 2-D nmr is run by
employing gated dcutcri um e H) decoupling produci ng lhe 13C- 2H coupling
informat ion on th F1 axis. The 13C chcmical shi ft s of the four carbons are seen
0 0 the F2 axis. The slices paralJel to F1 and through the different ca rbons show
the si ngle, t hree, fi ve, and seven peaks for coupling constanls of the subst ituents
eH
J
CHzD, CHD
z
' and C0
3
0 A stick diagram of overlapping resonances can
now be readi ly const ructed to ntcrprel the spectra in Fig. 8- S0(A),
In specl ra that contain bol h homonuclear and heteronuclcar coupling, J
spect rosco py can be u ed to separate and assi gn the homonuclear and hetero-
nucl ear coupling conslants, e.g., proton-proton coupli ngs can be distingui ' hed
11
O
fro m
co up
arep
Cp-
grou
cons
ad
2-D.
8--19 Two-Dimensi onal NMR 339
F
2
(Hz) --
o 30 60 90 120
I I I I
-40
I
F,(Hz)
- 20/
(e)
r - - - ~ - - - - ~ - - - - ~ - - - - ~ - - - ,+40
r- +20
-o F(Hz)
1- - 20
I I I I
o 30
,
60
,
90
I
'-,- F
2
(Hz)
(B)
FIGURE 8-50 The proton decoupled,
two-dir::ensional J-resolved ' 3C spectra
01 a mi xture 01 methyl deuterated
toluenes e H has an 1= 1). J coupling is
shown on the F,-axis and the
corresponding 13C Shifts on the F
2
- axis.
The single peak lor CH
3
, triplet lor
-CH
2
D, pentet lor -CHD
2
, and septet
lo; CD
3
are seen on the F, axis lor slices
ihtough F
2
corresponding to the
analogous 13C chemical shilt. The
one-dimensi onal 13C spectrum is shown
in (A) . Dashed l ines connect the
chemical shilts of the two-dimens ional
and one-d imensional spectrum.
(A)
from phosphorus-proton coupli ng . Thc reason for this is that if fhe profon-proton
coupl ing is mod ulated du rin g tI ' lh ph phorus-pr ton coupli ngs remain and
are present 00 the \'z-axis. Ao example is ill usl ralcd in Fig. 8-51(A) for lhe com plex
Cp- Ru- (CH= CHz)( P( "Hsh)z The speclrum of the proton on the vi n I
group f the ca rbon bound to ruthenium is shown in Fig. 8-51(A). Tls should
consiSI of overlapping lriplets from two equivalent phosphorus atoms spli t int o
a doublet of doublets from non-equivalent CH
2
protons of rhe vi n I group. The
2-D, J -resolved, I H nmr speclrum shows th phosphorus spli tti ng on l he F (b)
a.xi ,as seen by l he triplet in lhe spectrum in Fig. 8-51(C), The F2 a ' is (J) contains
lhe information aboul lhe proton-proton coupli ng. The doublet of doublets is
indicated. Usi ng the resolved coupling constanls, a stick diagram can be con-
slructed lo show how the overlap of peaks leads to the spectra in Fig, 8-51(A).
340 Chapler 8 Dynamic and FourierTransform NMR
I I
I I
8.20 8.15
FIGURE 8-51 (A) The prolon speclrum
: (A) :
I , I
ofIhe vinyl eH prolon of epRu(eH=eH
2
)
:
, I I
(PcP3)2. (B) The J-resolved,
Iwo-dimensional speclrum. (e) The
1HA
prolon speclra wilh 31p splillings.
__

: I
(e)
reL
di::
exr
Illl(
ofi
wht
dirc
nuc

lS n
ind
the)
in! I
At 1
anis'
8-2'
In s
oriel
to e
Inve!
solve
and
prol,
resol
ofso
inter
mole
resor
mOlll
lhe q
magl
NMR in Solids
and Liquid
Crystals
8-20 DIRECT DIPOLAR COUPLl NG
We shall begin this discussion by considering the direct dipole-dipole interaction
betweentwonuclei.Thisis doneby consideringfixed orientations oftwo hydrogen
atoms in a molecule relative to an external field, as shown in Fig. 8-52. The
dashed line is the internuclear axis connecting the two hydrogen atoms, the
boldface arrow indicates the orientation of the nuclear moment on b relative to
thefield, and thecurvedarrowrepresentstheIines offluxarisingfrom this nuclear
moment. We see that for this fixed orientation ofthe moJecule,we would obtai n
two different peaks in the nmr of the Ha resonance as a consequence ofthe two
different fields from b. This is a through-space effect which, in contrast to the
coupling mechanisms discussed earlier, does not involve the e!ectron density in
themolecule.Thepeakseparationis indicated by acouplingconstantB
dir
(where
dir stands for direct). B can be very large and, for example, is about 120,000 Hz
for t\Vo protons separated by 1 when the H-Hinternuclear axis is aligned
with the field.
Ho
n

h /
__Molecule I
n

(A) (B)
FIGURE 8-52 The directdipolar inleraction 01 Iwo
hydrogens in a molecule.
1
r
)
e
n
e
z
d
~ b
]
8-21
The magnitude of B will vary with the position of the internuclear axis in
relation to the field. The mathematical expression for the magnitude of the direct
dipolar interaction between two nuclei p and q, Bpqdir, is derived from the
expression for the magnetic field due to a point magnetic dipole (i.e., the other
nucleus) and the expression for the potential energy of a point dipole (the proton
of interest) in a magnetic field. The result is:
2
. h 1 [3 cos 8 - 1J
B dlf(Hz) = - - y y - pq
(8-26)
pq 4n
2
p q 2 r 3
pq
where 8
pq
is the angle that the pq-internuclear axis makes with the external field
direction. For a complicated molecule there is one B
dir
for every pair of magnetic
nuclei in the sample.
In a normal solvent , any given internuclear axis is randomly oriented with
respect to the external field and rapidly changing its position because the molecule
is rotating. The direct dipole-dipole interaction is averaged to zero. Since the
indirect coupling constants proceed through the electron density of the molecule,
they are not averaged to zero in a solvent. However, the direct dipole-dipole
interaction is through space: it is given by equation (8-26) and is averaged out.
At very high fields ~ 1 4 T), the effects of imperfectly averaged diamagnetic
anisotropy are seen, e.g., broadening of aromatic proton peaks.
8-21 NMR STUOIES OF SOLIOS
In single crystals, the H-H internuclear axes in the molecules have a fixed
orientation relative to the applied field and Bdir is not averaged out. According
to equation (8-26), if one were to study [he angular variation of Bdir by
investigating different orientations of a single crystal, it would be possible to
solve the resulting simultaneous equations for 1/r
3
and lO find the magnitude
and direction of the H-H internuclear axes. Unfortunalely, only rarely are the
protons in the crystal few enough in number and far enough apart to permit
resolution of the spectrallines and determination of B
dir
. Generally, the spectra
of solids consist of very broad, poorly resolved bands beca use of the direct dipolar
interaction between protons in Ihe molecule and between those from the nearby
molecules. However, structural information can be obtained from the broadened
resonance line of single crystals or powders by the so-called method of second
moments(66) The second moment is the mean square width (t.H)2 measured from
[he center of the resonance lineo The center of the resonance line is the average
magnetic field, as seen in equation (8-27).
Hav = Lce Hf(H) dH (8-27)
where f(H) represents the normalized line shape. The second moment is then
given by equation (8-28),
(8-28)
NMR Studies 01 Solids 341
which can be evaluated graphically from the observed line shape. M ost obscrvcd
pea ks ha ve a Ga ussian shape and are described by
I(H) = e -:(II - II .I'"2(MI)'J
(8 29)
I'lH 2n
The second moment is then determined from the integration of the analytical
expression obtained from equations (8-28) and (8-29). The second momenl for
a single crystal or powder is related to r and e, and gives struclural
information. The reader is r fe rred to references 66 through 68, for more dctails.
This technique has been used to show that the infusible white precipi tat from
the reaction of NH
3
wit h HgC! 2 i H
2
HgCl and not NHg
2
INH
4
C! or
XHgO( l - X ) HgCI
2
2Nll
j
.(69l T hese studies can be carried out on more
complex molecules in eonj unction with deuteration studies. he magnetic momenl
of the deuteron is very small, and dipolar interactions that involve deuteriulll
can usually be neglected.
T hc tempcrature dependence of the second moment has also been employed
to provide information on molecular motion in s o l i d ~ lt has been hown that
benzene is fixed in the solid below 90 K, but rotates ra pidly a bout lh sixfold
axis between 120 a nd 280 K. Thc second moment change. raduall y fr om 9.7
2
gauss below 90 K to 1.6 gaus 2 al 120 K, and remai ns at this value to 280 K.
Rotat ion of cyclohexane about t he S6 axis has also b n dcmonstrated. This is
an extremel y sensi t ive technique, fo r lhe rate of rot alion required to narrow lhe
resonance is not much higher than the proton re ona nce fr equency in a !i Id of
a few gauss, i.e., 10
4
Hz. econd-moment stud ies demonstraled(70) l he rot ation
of the benzene a nd cyclopentadi ene rings in dibenzene-chromium and ferroccne
as well as(7ll rotat ion of benzene in lhe benzcnc-sil ver perchlorate complexo A
sl udy(72) of [Me
3
Si NSi MeJ 2 demonstrated that at 77 K lhe methyl gr ups rolale
aboul the Si- C bond, and lhis is lhe only mot ion in the 100lecule. At room
temperat ure, methyl groups rot te a bo ul the C-Si bond. (CHJhSi group rotate
about lhe Si-N bond, and t he wholc molecule rotates about a molecular l 'i:.
Thermodynamic dat a can be obtai ned for the various mOlional proc sses from
the temp ral ure dependence of the spectrum.
8-22 NMR STUDIES IN LlQUID CRYSTAL SOLVENTS
Certain materials e.g.,
and
rnelt to pr d uce a lurbid fluid in which certain dornains exi sl whcre lhere is
considerable orderi ng of lhe mole ule . The resu lt ing flu id ha", som propt: rtics
of 1
pr
of n
a
(A)
(B)
m
le
IS.
m
e LS
tic
of both Iiquids and crystals. The liquid is strongly anisotropic in many of its
properties,(73) but further heating produces an isotropic liquid. This general class
of materials is referred to as Ihermolropic [quid cryslals (i.e. , produced by melting
a solid). Three subclassifications are illustrated in Fig. 8-53 by schematically
Nematic Smectic Cholesteric
FIGURE 8-53 Types 01 ordered domains in a liquid crystal.
indicating the type of ordcring in the The representations in Fig. 8-53
are of smal! dornains in the whole 'ljuid sampk. These domains tend to become
aligned in the presence of a magnetic field.
The nmr spectra of the molecules that constitute the liquid crystal are very
broad, nondescript resonances that sometimcs are so broad as not to be observed.
The broadening reslllts beca use the viscous solvent molecul es contain many
hydrogens and consequen tly there are a Jarge number of direct H-H dipole-dipole
intcractions that are not averaged out in the partialIy ordered olvent.
If sorne ben/cne is dissolvcd in the liquid crystal as solvent, lhe spectrum
illusHated in Fig. 8-- 54(A) results(74) This spectrum of benzcnc consisls of a large
number of sharp Iines spread out over approximately 2400 Hz. ame of the broad
rcsonances of the solvent are di scernible under the sharp benzcne peaks. The
benzene spectrum is thus somewhere bet ween that obtained in a non-viscoLls
solvent (a single sharp line) and that of a solid (a broad linc spread over a wide
(A)
1000 Hz -
(8)
FIGURE 8-54 (A) Liquid crystal nmr spectrum 01
benzene; (B) si mulated spectrum.
field). In an isotropic solvent, the various axes in a solute molecule assume all
possible orientations with respect to the magnetic field with equal probabitity,
and B is averaged to zero. As mentioned before, the indirect couplings proceed
via the electron density in the molecule and are not averaged to zero. When all
orientations of an axis with respect to the field are not equally probable, the
contribution to the field at a proton from each surrounding nucleus depends on
the orientation of the nuclear moment in the neighbor, and the position of that
neighbor nucl eus relative to the one being observed. In a solid where thc nuclei
are fixed and where so many protons affect the fi eld of any one kind of proton,
a continuous very broad single peak results. We now must explain why we sec
such sharp peaks for the solute in the liquid crystal spectrum and why there are
so many peaks.
In a liquid crystal, certain orientations of the solute are more favored than
others ('long axes tine up with the solvent long axis) because the magnetic field
tends to align the solvent and solute molecules in the field direction. Solute
molecules diffuse freely and tumble freely enough so that there is no co ntribuon
B
di r
to from the solvent or other solute molecules. AH the couplings are
intramolecular. Since the molecule is tumbling rapidly, sharp tines are observed
in the nmr. We see many lines in the spectrum because Bpqdir [ equation (8- 26)J
makes an observed contribution to the resonanee tine positions. The aniso tropic
motion does not average this quantity to zero. Each (Jpq of equation (8- 26} now
becomes sorne average value for the net orientation of each of the respective H-H
axes in this rapidly and anisotropically tumbling molecule.
In benzene, for example, we have six protons and need a matrix of all possible
combinations of six spins (i.e., a basis set acxacxaa, aaaaa{3, etc.) to describe this
system. Thus, we have peaks corresponding to molecules with all these different
permutations of spins with B and ) values for all pairs of hydrogens. Oflen,
second-order spcctra result , further complicating the appearance of the spectrum.
The energies are described by the spin Hamiltonian matrix for this system, which
is similar to that discussed in treating second-order spectra except that , for every
) on the diagonal in the solution problem, we now have a ) + 2B; and for every
) previously on the off diagonal we now have a ) - B. This problem is solved,
vide infra. by finding ) and B values [JorthO(O)' )me, a( mP )para(p B o , B
m
, and BpJ
that will reproduce the experimental spectrum. The calculated spectrum is shown
in Fig. 8-54(8). For benzene, the resulting values are Bo = - 639.5 Hz,
Bm = -123.1 Hz, Bp = -79,93 Hz, )0 = 6.0 Hz, ) m = 2.0 Hz, and ) p = 1.0 Hz.
The dipolar couplings are related to the nuclear coordinates by
<Bpq ) = 8 ~ ~ ~ ) q ~ ) [Szz(3 cos
2
8pqz - 1)
n Y
pq
2
+ (Sxx - S y) (cos
2
8
pqx
- cos (Jpqy) + 4Sxy cos 8 cos (Jpqy
pqx
+ 4Sxz cos 8
pqx
cos 8
pqz
+ 4Syz cos 8
pqy
cos OpqJ
(8-30)
where rpq is the internuclear separation of the coupled nuclei , (JpqZ is the angle r
p
,
makes with the z-coordinate, etc. for 8
pqx
and (Jpqy' The axes are fixed within tme
molecule and S is an averaged-order matrix that relates to the extent of orientation
of the molecule by the tiquid crystaI. H the axis is completely aligned with the
field, S pq is l. If the axis is aligned perpendicular to the field, then Spq = - C/2)' For
a random orientation, Spq = O.
con
onl
dia
thr
ten
hig
as
Bu
and
ma
equ
aIl
oft
kno
unk
equ
r by
to a
dista
info
sy te
of tt
Ihe 1
be
(R-
~ un
ha
is ~ I
an el
of tb
that
d'
r
are
COOI
ben'
-
e
n
d
te
le
:his
ent
ten,
um.
!ch
lery
lery
ved,
Bp]
Dwn
Hz.
Hz.
, 30)
~ l rP'l
in the
,ation
lh the
t). For
Ir we knew Spq, we could calculate rpq from the experimental Bpqdir and get
distances and geometries of molecules in solution. In a rigid molecule, the values
of Spq for the various axes must be interrelated. This interrelationship between
the axes and the orientation of the molecule in three-dimensions can be described
with the tensor S. The S tensor is 3 x 3, symmetric and traceless, so that only
five of the nine elements are independent. As discussed in Chapter 2, we can
define a molecular coordinate system that diagonalizes the tensor. This usually
corresponds to symmetry axes if the molecule has symmetry; then there will be
only two independent elements. (AH off-diagonal elements are zero and the
diagonal ones are traceless, i.e., their sum equals zero.) For a molecule with a
threefold or higher axis, Sxx = Syy = -e/1)Szz and there is only one independent
tensor element. Note that the tensor is independent of r. With a threefold or
high-order axis, equation (8-30) becomes
(8-31)
We can illustrate the method by considering paradichlorobenzene, Fig. 8-55,
as an example. Analysis of the spectra yields three dipolar coupling constants,
Bo, Bm, and Bp shown in Fig. 8-55. There are two unknown tensor elements Szz
and (Sxx - Syy) and two distances corresponding to the two sides of the triangle
made by B
p
, B
m
, and H-H in Fig. 8-55. We are thus confronted with three CI
equations and four unknowns. Therefore, it is only possible to get the ratios of
all the distances; or, if we can assume one, the others can be calculated. It is
often the case in these systems that there is one more unknown than there are
knowns. However, even if a particular system has more coupling constanls than
unknowns, we cannot obtain a unique solution. This can be seen by referring to
FIGURE 8-55 The Bpo
equation (8-31). For a given S and r that satisfy eq uation (8-31) we could m ultiply interactions in p-CI
2
C
6
H
4
.
,. by a factor and S by the cube of that factor and get the same B. T his corresponds
to a uniform expansion of the structure without any change in the ratios of the
distances. In spite of this severe Iimitation, a very considerable amount of
information can still be obtained from nmr studies in Iiquid crystals.
In molecules with a threefold axis or higher, equation (8- 31) applies. These
systems require only one S element to relate the B pq values to structure. T he ratios
of the dipolar coupling constants are independent of S and give us the shape of
the molecule. The ratio of the dipolar coupling for all proton pair Bpq values can
be calculated for a regular hexagon by taking the corresponding ratios of equation
(8-31) to yield 1 to 0.192 to 0. 125. Experimental ratios of 1 to 0.192 to 0.125 are
found for benzene, showing that it is a regular hexagon in solution. CpNiNO
has two Bq values whose ratio for a regular pentagon is 4.236. A value of 4.211
is found indicating a regular polygon. O n the other hand, C pMn(COh produces
an experimental ratio of 4.11 indicating that distortion exists.(7S,76) In a studi
77
)
of the liquid crystal nmr spectrum of trans-[CI
1
Pt(C
2
H
4
)C
s
HsN], the inl1uences
lhat various dynamic processes in solution have on the resulting spectra are
discussed. The ordering factor S is very low and severe overlapping of the
resonances results. A method was developed in which the spectrum intensities
are fitted in the spectral analysis. The ratio of the rgem/rci' protons in the
coordinated ethy1ene is consistent with a st ruc.ture in which the C- H bonds are
bent back away fr om the metal. Except for the dynamic process occurring in
H H
CI
FIGURE 8-56 (A) Structure
01 H
3
Ru
3
(CO)CH
3
. (B)
Experimental liquid crystal
spectrum (broad absorption
is 110m the liquid crystal) . (C)
Simulated liquid crystal
spectrum. [Reprinted with
permission Irom A. D.
Buckingham, el al, J. Amer.
Chem. Soc, 95, 2732 (1973).
Chemical Soclety.]
solulion (th ethylene rotales rapi dly aboll t the bond lo platinllm), lhe sollllion
strllcture of lhe ethyl ne fragment is simil ar to tha t in lhe olid.
When th chemical shift di fferen ces of the protons invol ed are large and
fi r t-a rder spectra are obtained, the spectrum is readily interpreted by in pcction.
and informatian about the symmetry of the molecule can be obtai ned fr om lhe
spectrllm in a st rai ghtforward ma nner. Consi der the re ' ult s reported(nl ror
H
3
Ru
3
( O) H3' which led to lhe proposcd struct ure shown in Fi g. 8 56 along
wit h the spectrllm observed for this molecule in a li quid crystaL T he mct hyl
o O O
C C c
\ 1!
H
/ RU

/ CH3!
oc " I / co
OC-Ru ./Ru-CO
OC / ""co
H
(Al
I--j
200 Hz
(e )

group is rapidly rotati ng about lhe - C bond axis. The quartets arise from Lhe
lhree equivalent methyl protons splitt ing th three bridging prolons and vice
versa. The three meth I protons are equival nt wi th rcspect to the bridgi ng
hydrides h cau'e of the rapid r tati on. Tn a fi xed st aggercd conCigurati on U. e.,
CH
3
versus metal hydrides), lbe hydride protons would be split by a set of two
equivalent proton and one non-equivalent methyl pro ton, producing six peaks
in each triplet component , .e., 36 peaks tolal. One 01' lhe two groups of triplets
arises from direct dipolar coupling of lhe methyl protons wiLh cach and
the second (more c10sely spaced) triplel arises from the dipolar coupling of the
lhree bridged hydrides wilh each other. If we consider one of lhe prot oll s of the
m
( -
ro
ca
l}U
a e
TI
fro
CO I
quadr
! i2) is
br ad

a t!Cl
b com
8-23 High Resolution NMR 01 Solids 347
methyl group. it can be split by the ol her lwo beca use (+ + ),( + -), (- + ), and
(- -) combinat ions of nuclear moments in different molecules cause this proton
to experience different fields, since the molecule is not undergoi ng isotropic
rotation and the direct dipol a r cou pling is not a veraged to zero. T he larger
coupling constants a rise when the protons causing he splitting are doser to each
olher.
Deuterium nmr in liquid cryslal s(7s.79) leads to a determination of Ihe
quadrupole coupling constant q,: (Chapt r 14). The interaction of a proto n with
a deuteron in a partially al igned molecule wi ll givc rise to a four- li ne pattern.
The large doublet arises from the quadrupole interaction and the small er doublet
from the dipolar coupling. The value of qP' : is related to the quadrupole coupli ng
constant by
(8- 32)
8-23 HIGH RESOLUTION NMR OF SOLlDS(80)
As described in Sect ion 8- 21 , dipolar cou pling leads to ery broad nmr spectra
of solids, Also contributi ng to the broadness is chemica l shift a nd scalar spin-spin
coupli ng (J) a ni sotropy ....... it h bot h quantitics bei ng represen ted by tensors. The
enl ire range of chemical shift s and couplings spanned by a ll oricnta tions of
crystall ites is mani fested io t he spectra leadi ng lo wid ths of 50-200 ppm in De
spectra. The firs t attempls to reduce dipol a r coupli ng in so!ids invol ved rapi d
. pi nni ng of lhe sa mpl aboul a n axi., incl ined a l Ihe so-calJ ed magic aogle of
54"44'. AII of th momenl veclors are poinling in a ll di rect io ns in t he stat ic
sample. One such moment is ilIusl raled by Ihe vect or pq rel at ive lo Ho in Fig.
8 SS. If we spin rapidly, we average a1l of these leading lo a n t momenl (ha!
point along the spinning axis. Thi s can be seen in Fig. 8- 58 where spinning
along the axis at 5444' sweeps oul two ci rcles for opposi le ends of pe. The ne!
01' all t he orienlati ons along t he circles is l hc vect or p' q' Iy ing on l his spinning
axis. At Ihis magic angle for the axis, 3 cos
2
0- 1 equa ls zcro. Onc musl spin
the sample ra pidl y compared to lhe magnilude of the intcract ion lO a verage the
momenls. Dipolar coupling of lwo prolons typicall y is 5 x 10
4
Hz. enlrifugal
force wi ll cau e rotors (O disinlegra le a t thi s pecd. Convent ional spinning rat es
are fast lo remove chcmica l s hift and J coupling ani ol ropy. Large
chernical s hi ft anisol ropy produces sev re spinning idebands.
T his approach, which wiU be ca Bed magic aogle sample spi nning, MASS,
can remove dipolar coupli ng in ma gnet icall y dilule sa mpl es, e. g., 13 . ote in
equat ion (8- 26) lhat Ihe direct coupli ng is a fun tion of 1/ ,.] AIso note (equati on
(8- 26)) Ihal a low)' alue for lhe nu leu' ol' intereSl aIso lcnds to red uce di polar
eoupling Thus, 13e and 29Si give sharp onu spectra [romoMASS.
Quadr upolar l1 ucl ci al so lead t o li ne broadening hro ugh t he electric
quadrupole interaction. For 1 = n + 1/
2
nucJei, lhe ceo ter t ra nsil ion (_1/
2
-+
1/
1
) is nol affected and a sharp Une results. T he l her Ira n il ions are. generall y
broadened beyond detecti on. For nucl i with integer valucs of 1, t here is no
- 1/
2
-> 1/
2
lransition a nd very br ad spectra result. Even wit h 1 = 11/ 2 syslems,
a econd-order quadrup le effecl broaden lh e ntral t ra n ilion. Thi effect
beco mes less imporlant al high field .
n 1 I

qpzz =Spq q u
FIGURE 8-57 Splitting 01
the deuterium resonance by
a proton.
FIGURE 8-58 Aver aging 01
! he mamen! pq to p' q' by
spinning abou! the axis a!
54' 44' to the applied He fi eld
I
.
.
~
~
~
(e)
FIGURE 8-59 13e nmr 01
polysullone
(-Q-e(eH
3
h-Q-O-Q-
S02-Q-O-) (A) double
resonance; (B) double
resonance plus MASS; (e)
solulion speclrum.
RE FE RENCES
CITED
Low values ofy and chemical dilution permits detection of 100% 14N and
31p in solids with broadband proton decoupling. Long Tl's can be shortened by
cross polarizing,(8l
J
CP, dilute, and abundant spins. 111 the CP technique, the
proton spin poJarization is transferred( 82) to the less abundant nuclei , e.y., De
by applying a proton rf field (H 1,J and then a DC field (H le) such that
yHH1H = Yc H l e' Efficienttra nsfe rofenergyoccursbetween thetwospinmanifolds
generating l3C magnetization along H le and increasing the intensity of the
transition. Cross polarization depends on the static component of the dipolar
interact ion and has the greatest effect on neighboring nuclei. It is most efficient
for immobilespeciesa nd ineffective for mobilespecies. heseconceptshavcbec;
employed( 83.84) to study the surface structure a nd reactivity of silica gel and
zeolites. Complementary information about the bulk st ructurc can be obtaincd
using a pulse-delay-obse rve sequence.
Combining chemical dilution with MASS leads to a fu rther sharpening 01'
the resonances as shown in Fig. 8-59. A pulse sequence refer red to as
WAHUHA(85) mod ula tes thespi nand has reducedli ne widthsfrom 10
4
to ~ 10
2
Hz. These experiments have the potential for determi ning chemical shift and
dipolar anisotropes. Ca rbon-hydrogen dipolar couplings and with them C- H
di stances havebeenobtainedonsolids by a 2-D pulsesequence(86lT heevolut ion
periodcorresponds to variable times,t,for theapplicationofa WAH HA pulse.
The 2- D plot contains the chemi cal shift as one axis and the dipolar splitt ings
as the ot her.
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25.
26.
27.
28.
29.
30.
31.
32.
33. t
r
34.
35. (
36. I
37.
38. 1
39. .
40. ~
41. (:
(1
((
42. [
43. e
44. l\
45. P
e
46.
47. R
48. R
(1
49. G
50. R
51. G
52. G.
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55. J.
56. R.
ed
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ctS.
nd
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57. R. K. Harris and B. E. Mann,"NMR and the PerodicTab1e," Academic Press, New
York,1978.
58. J Mason, Chem. Brit. , 654 (1983).
59. (a) 1. C. P.Smith,G. W.Stoekton, A. P.Tulloeh,C. F. Polnaszek and K.G.Johnson,
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Resonanee Speetroseopy," ed. J. W. Emsley, J Feeney and L. H.SuteliA.e, Pergamon
Press, London, 1977.
60. H.Sehmidba ur, .Gasser, T. E. Frase rand E. A. V. Ebswo rth ,1. Chem.Soe., Chem.
Comm. 34 (1971).
61. A. Derome. "Modern MR Techniques for Chemistry Rcscareh," Pcrgamon Press,
London, 1987.
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(b) R. G. Fuke, B. Rapho, R. J. Sext on a nd P J. Vomaill e, J. Am. hem. Soc., /08,
2947 (1986).
65, See, for example, . W. Alcoch,J. M. Brown,A. E. Derome and A. R. Luey,J.Chem.
Soc., Chem. Comm., 757, (1985).
66. C. P.Slichter,"Principies ofMagnetic Resonance," Chapter 3, Ha rpe r & Row, w
Yo rk, 1963.
67. A. Abragam, " T he Principies of Nuclear Magnetism," Chapter 4, Clarendon Press,
Oxford, 1%l.
68. L R. AndrclI'. " Nucl ea r Magnetic Reso na nee," Chapter 6, Cambridge niversit y
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(1966).
69. C. M. Decl y a nd R. E. Rieha rds, J Chem. Soe., 3697 (1954).
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therein.
72. H Levy and W. E. Gri zz le, 1. Chem. Phys., 45, 1954 (1966).
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74. L. C. Snyder and E. W. nderson, J m. Chem. Soe., 86, 5023 (1964)
75. 1. W. Emsley and C. S. Lunon, Mol. Phys., 28, 1373 (1974).
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83. D. W. Si ndorfand G. E. Maciel, 1. Am. he m. Soc. / 05, 1487,3767 (1983).
84. . A. Fyfe, G. C. Gobbi, 1. Kl inowski, 1. M. Thomas and S. Ramdas, atu re 296,
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85. 1. S. Wa ugh. L. M. Huber a nd U. Haeberl en, Phys. Rev. Lett., 20, 180 (1968).
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e
F
A.
G
"T
A.
W.
:s
w
1. W. Emsley el al. , "High Resolution Nuclear Magnetic Resonance Spectroscopy," Vols.
I and 2, Pergamon Press,New York, \966.
T. C. Farrar and E. D. Beckcr, "Inlroduction to Pulse and Fourier Transform MR
Methods," Academic Press, New York, \97L
C. P. Slchter, "Principies of Magnetic Resonance," Harper & Row, ew York, 1963.
A. Abragam,"The Principi es of Nuclear Magnetism," larendon Pr-:ss, Oxford, 1961.
G. C. L-:vy and G. L. Nelso n, " Carbon-I3 NtIcI-:ar Magnctic Reso nance for Organic
Chemists." Wiley-Interscience, New York, 1972.
J. B. Stothers,"Carbon-13 MR Spectroscopy." Academic Press, ew York , 1972.
[ Bertini, H. Mollnari amI iccolai , " MR and Biomolecular Structure," CH
Publisbers, ew York. 1991.
"Nuclea r Magnctic Resonance Shift Reagents," ed. R. E. Sievers, Academic Press, New
York, \973.
C. P. Poole, Jr. and H. A. l'arach, "The Theo ry of Magnetic Resonance," Wilcy-
Inltersciencc. ew York, 1972.
E.Breitmaierand W Voelter,"Carbon-1 3NMRSpectroscopy: Hi gh-Resolution Met hods
and Applications in Organic Chemistry and Biochemi stry," VCH Publishing, New
York, 1987.
A. Derome, "Modern NMR l'echniques for Chemi stry Research," Pcrgamon Press,
London, 1987.
G. E. Martin and 1\. S. Zektl.er, "Two- Dimensional MR Methods for Establishing
Molecular Conncctivity: A Chemist 's Guide lo Experimcnt Selection, Performance
and Int erpretation," VCH Publishing, Ncw York, 1989.
" Two-Dimensional NMRSpectroscopy :Applicationsfor Chcmistsand Biochemists,"eds.
W. R. Croasmun and R. M. K. Carlson, CH Publishing, Ncw York, \987.
A. E. Tonelli, ,.NMR Spectroscopy and Polymer Microstructure: Thc Conformational
Connection," VCH Publi shing, Ncw York. \989.
W.S. Brey,ed. " Pulse Methods in I-D and 2- D Liquid Phase MR," I\cademic Prcss,
ew York, 1988.
R. Freeman,"A Hand book of uclear Magnetic Resonance," Wiley, ew York, 1987.
R. R. Ernst ,G. Bodenhausenand A.Wokaun,"PrincipIesof ucl earMagnetic Resonance
in One and Two Dimensions,' Oxford Un iversity Prc$s, Oxford. 1987.
Aseri es ofarticles by R. W. King and K. R.Willi ams providcsa clearexplanation ofFT
methods:
"The Fourier Transform in Chcmistry. Nuclear Magnetic Rcsonance: lntroduction," J.
Chem. Educ., 66, A213- A219 (1989)
"The Fourier Transform in Chemistry. Part 2. Nuclear Magnetic Rcsonance :The Single
Pulse Ex periment," J. Chem. Educ. ,66, A243-A248 ([ 989).
" The Fourier Transform in Chemis try. Part 3. Nuclear Magnetic Resonance: Multiple
Pulse Expcriments," J. Chem. duc., 67, A93 A99 (1990).
" TheFourierTransfor min .hcmislry. ucl ear agnctic Resonance :AGlossa ry of MR
Terms," J. hem. Educ., 67, Al00- AI04 (1990).
"The Fourier Transform in Chcmi stry. Part 4. Nuclear Magneti c Rcsonance: Two-
Dimensional Mclhods," J. Chem. Educ., 67, Al25 A\37 (1990).
Series
"Annual Reports on NMR Spectroscopy," Academic Prcss, Ncw York. 1968-.
"I\ dvancesin MagneticResonance," ed. byJ. S. Waugh.Academic Press, ewYork, 1965- .
"Advances in agnetic Resonance, upplement 1: High Resolution MR in Solids," U.
Haeberlen, Academic Press, cw Yor k, 1976.
.. MR Abstracts and 1 ndcx," Preston Technical Abstracts Co. , Evanston, !II. , 1968.
ADDITIONAL
REFERENCES
"Nuclear Magnetic Resonance," The Chemical Society (Specialist Periodical Report),
London, 1972-.
" Topicsin Carbon-13 NMRSpectroscopy,"ed. G. C. Levy, Wiley- Interscience,New York,
1974-.
EXERCISES
1. Consider the molecule
where M and X have = 1/
2
,Sketch the nmr spectra for the following conditions,
assuming > J in all cases(when necessary toassume ordersofmagnitudefor various
coupling constants, state your assumption). Ignore eoupling if the atoms are not
directly bonded.
a. nmr spcctrum of X, no exchange.
b. nmr spectrum of M, no exchange.
c. nmr spectrum of Xwith rapid intermolecular exchange of all Xgroups.
d. nmr spectrum of M with rapid [e' < l/(v
A
- v
n
)] intermolecularexchange ofall X
groups.
e. nmr spectrum of Xwith rapid intramolecular exchange.
f. nmr spectrum ofM with rapid intramolecular exchange.
2. In the absence ofanyexchange, two peaksA- H and B H areseparat ed by 250 Hz.
At room temperature, exchange occurs and the peaks are separated by 25 Hz. The
spin-Iattice relaxation ofA Hand B-His long, and there are equalconcentrations
(0.2 M) ofeach. Calculatethe lifetimeofa protononA,and from this the rateconstan!
for the exchange (specify units).
3. In a given compound MF
4
(for M, = 1/
2
) the J
M
-
F
value is 150 Hz. In the absence
of chemical exchange, the F- and M .: signals are separated by 400 Hz. At room
temperature the F- and MF
4
exchange at arate such that the fine structure just
disappears. Assuming equal concentrations of M F and F- species and no stable
intermedi ates, calculate e' for F-. What will be the separation of the M- F and F -
peaks under these conditions?
4. The following are 31P nmr spectra, 1p = F = 1/
2
, No J p_11 couplingis ever resolved.
s.
~
1000 Hz
t---I
6.
10111
Exercises 353
a. Explain the low temperature spectr um.
b. Explain the high temperalure spectrum.
c. On the basis ofthese spectra, what canyou say aboul the mechanism of
d. What is the relationship belween coupling conSlants in lhe slow and fasl exchange
regions'l
5. The eomplex [(CF,)Co(CO)J(PF3)] [J. Amer.Chem. Soc., 9/,526 (1969)] is assumed
lO be trigonal bipyramidal. The 19F nmr sreclra al +30- and - 70 (' are given
below. Splillings from 59CO are nol observed.
x
J = 3 Hz 9 Hz
lJllL .1
1
11
9 HI'I

o
3 Hz
I
.1,
9 Hz
JI,
3 Hz
,O
6 Hz 6 Hz

he
ons
tant
11111111
CF3
I
500 O
Ref.
111,
I
500
I
1000
H -
.11
1500
PF
3
30C
Hz
.!lee
jusI
ab\c
n
irst consider the -70C spectrum.
a. Explain the reason why four quarlels are obscrved for the fluorincs bonded lO
phosphorus. (No 59CO spin-spin coupling is detected.)
b. Exp lain how lhe FJ resonances arc consi stenl wilh your explanalion in part a.
C. Describe the reason for lhe smal ler number of PF3 resonances al 3WC.
d. What is the signifi cance of lhe PF
J
resonances being observed as quarlel Sin lhe
30'('speclrum?
6. The line width of lhc melhyl prolon resonance of 3-picoline-N-oxide in solulions
eontaining and excess ligand has becn sludied as a funclion
oftemperalure [Inorg. Chem., /0, 1212 (1971)J. The following plOl was oblained.
o o
o
o
o o o
o
o o o 00 o
o o
O.O
2.5 4.0 4.5 5. 5.5
10
3
/ T
a. Label the fas t,nearfast ,intcrmcdiat c.and slow exchangeregi cns. Do thi sby giving
approximate boundaries lO the region in units of I03 T ; e.y., fas\: .'(L to X l unil s.
b. Thescdatawcre analyzcdusingfull lineshapeanalysi sfrom thedas lcal treatment.
Why wasn't pyridine-N-oxide used as lhe ligand?
7. a. When the nmr spcctrum of benzoni tril e in a liquid crystal is observed, why do
solvenI rcsonanccs not ilppear?
b. Why are the benzonitrile lines in a liquid crys lal mll ch sharper than those i'l solid
benzonilrile?
c. Compared to an nmr spectrum of bcnzonitrile in CCl
4
, why are so many lines
observed in the liquid crystal I1mr speclrllm ofbcnzonitrile 'l
8. The speclrum and structure of pyrogal lol is given below. Th OH prot ons are nOI
H
H
HO*
-
- -
HO
H
OH
,
I
-
,

111
l .
8. 0 7. 0 6.0 5. 0 4.0 3.0 2.0 1.0 oppm
ph.
11. a. I
b.
d
C. i\
th
\\'J
\1
!h.
Exe rcises 355
coupl ed loany ol hernuc\ei.Whydon'l lhethree phenyl protonsgi ve ri se to adoublel
and a tri plel? (The group orpeakscentered abour 6.7 ppm areexpanded in theolTsel
sweep.)
9. 57Ft: has anextremelysmall magneti c momen!. and il sabundance isonl y2. 2%. The
magndi c moment is nol known to ve ry good aecuracy, and almost no inrormatio n
exi sts a boul chemical shirts or 5 7 "c nuclei. Even though lhe resonance signal was
expecled lo covn onl y a very small frequency range, and lhus a low passage sean
thro ughlheabso rpli onsignalwould notlake erymuch longe rto observe thanwo uld
arreeinducti on decaysigna!, thisex pcrimenl was notreporled unl ilFouriertransrorm
nmr became available.
a. Why was Fouri er lranSrorm nmr adva nt ageous ro r lhisexperiment ?
b. Why was n' t any 57Fe_1 3C spin-spin splitting observed io the natural-abundance
sampl e'l
10. Suppose that a sampl e has lwo siles with differeol chemieal shirts. lo lhe continuous
wave (CW)experimen t, wc expecl a separale signalror eaeh sil C.
es
Coosi der a kinel lc process that seis in as Ihe t mperal ure is raised,whi eh exchanges
lhe nu lcihelween Ihe lwo 'il es Aand B.(1 ngeneral, lhe problcm is compl cx,since
nI
lhe (li lTe renli alcljuations,one ror each sile,are couplcd by the dynami c procesoand
the indi vidual componenl magnet izat ions begin to lose their identitics.) Consider the
limi lingcas in whi ch the kineti cproec's bcgins to havc an obscr ableeffect. yet one
can slill eonsider lhe indi vidual M magneti:r.at ion. Argll e on a physica l ba is what
H
effect exchange will have on the widt h 01" lhe A-type rcsonance. (Hint: Reeall the
H physica lpr ces' parametrized by T:2 ).
11. a. Let the resonance rrequency or a wat er sampl e be WH , O' Show h w one can
determine the pul se duration T and a fi eld strenglh Il ror an osei ll alor tllned to
(I) H,O that will invert lhe H
2
0 magnetizati on.
b. llppose 111a1 at a later li me a 3rr/ 2 pulse was appl ied and Ihat no fr e indllction
decay curve was (lb erved.Whal explains (hi s? o rwh.1use i, this xp riment?
c. 1\ . olute HX is added to the sample. and proton ex hall ge oceurs at arate slIch
that separate but broadened reso nances are observed for H
2
0 and HX. Oiscuss
what effcct iscxpectcd on solute si nal intensit y observed in a CW experimcnt ir,
while scanning through iL one st rongly irradiales lhe sample of( Il , O' sa lurating
lhe H
2
0 spin systcm.
12. [n the experiment described in the text for measuring TI ' why must lhe 180
0
pulse
be followed by a 90
0
pulse?
13. In the slow passage nmr experiment, one frequently observes the following type of
patlern when sweeping the field from left lO right:
The wiggles to the right of the absorption peak are refcrred to as "ringing" and are
found only when the nucleus observed has a long T
2
. Explain ringing in terms ofthe
behaviorofthe bulk magnetizationofthesamplein thisexperiment. Be sureto speeify
your frame of referenee.
14. [n theseetionontheeffects ofnuclei with quadrupolemoments,therewas adiseussion
ofthewidth ofthe 19F resonancein thespectrumofNF3 asafunction 01'temperature.
a. Explain the quadrupole moment relaxation in terms of the conccpt of spectral
density.
b. Explain the resulting nmr spectrum in terms ofspectral density.
15. Consider a frame of rcference rotating at a frequency OJ
1
= 1.0000 X 10
8
Hz and a
sample of nuclei with a Larmor frequency ofOJo = 1.0001 X 10
8
Hz, with T = 100
sec and T
2
=0.01 seco At t = O, a 90 pulse is applied along the u axis using a strong
d. field offrequeney OJ l' in a negligible length of time. Using a uz or vs axis system
in each case,draw the net magnetization vector
a. just before the pulse.
b. just after the pulse.
C. at t = 2.5 x 10- 5 seco
d. at r=I seco
10
4
e. at = seco
16. The following DC T's have been determined by Freemen [1. Chem. Phys., 54, 3367
(1971)J on 3,5-dimethylcyclohex-2-ene-I-one:
17.
18.
b
19.
20
Exercises 357
T, (sec)
O
C, 37
H
H
C
3
3- Me
C
2
33
5.9
5.4
C
s
5.3
CH
3
C
6
C
4
3.[
3.1
5-Me 2.7
H
H
a. Whal appears lo be the dominant means of spin-Iattice relaxati on for these '3C
atoms?
b. In light ofyo ur explanation, why do C, and C) have such long T,'s?
17. Experimenls can be performed to determine the T, ofa specific atom in a molecul e.
The most commonly employed lechnique using FTNMR is to apply a 180
0
pulse,
del ay for a time r,followed by a 90 pulse and immedi ale acquisition. Tau is usually
varied from Osec lo many limes theexpected TI value.
a. Sketchageneri cversionofthispul sesequenceshowingthebulkmagneti zati onafter
eachstep in the experiment.
b. Consider the magnetization fo llowing the 90 pul se previ ously stated. Show whal
the spect ra l peaks (assume a singlet peak) would look like at the fol lowi ng times:
r = O, r = fraction of TI' r = T" r T, .
c. Would it be possible to perform this experiment to measure TI using only a 90
pul se, wai ling r, and then acquiring? xplain.
18. The proton-coupled "BCOSYspect rum ofdeca borane is shown as follows .
a. Draw Ihe "Bproton-decoupled nmrspectrum.
b. Assuming only directly bound borons are coupled, assign the resonances in Ihe
,'B nmr specl rum. Explain.
"
I I 1 I I
20 10 O -10 -20 - 30
("B)/pom
19. The 1H COSY spectrum ofa sample is shown below (Ietters correspond to thesame
' 3 nucleus throughout this pro blem).
358 Chapter 8 Dynamic and Fouri er Transform NMR
B e E AG FH
B
10 9 8 7 6 5 4 3 2
o('H)/pprn
3. Draw the prol on specl rum.
H
F
e
E
PI
e

J,.,---------- (J
.'
,
.
I
I
,
,
I
,
I
!
i
,
." :, 1) /j
-
I
I
"..------------- 0
: I
I I
I I
o
2
3
4
E
o.
5
:
..):
GQ
6
7
8
9
10
o
b. sing lhe leltcrs lI sed to label car bons, the couplcJ Jl c,:k\ by Ictt cr, e.y. , i\
is cou pled to R and C.
Thc tH/tJe HETeOR spectrum or lhe sample aboye is s hown next.
O
9
t
2
3
E
4
o.
:
5
-
I
6 ;;o
7
8
9
10
150 100 50
c. Draw the proton-decoupled De spect rum.
The heteronuelcar De2-1 , J-spcclrum is as rollows.
- 1
Exercises 359
o B e E G FA H

150 100 50
d. Describe how the J-spectra aid in peak assignment.
e. The molecul e is a partiall y lInsatllrat ed ester wi th empirica! formul a C
R
0
1
. H
I4
Dr:.w the strll cture.
20. The following spectra (:.cidic cond itions)wcrc taken for the mo!ecllle whose strll cture
is givcn below J-spectrllm is given in A ami the HETCOR in B. Assign the
nllmbercd peaks to the labeled ca rbons (ignore all llnlabcled carbons).
I
oHz
O
I
I
I
I
5
I
I
I
I
I
l O
I
1
E
a.
1
.9-

15
I
Ul

20
C') - ---- -
I
I E
(j)
I
:;:; ---=(3)
I e
(41 Jo 25
o
-T(51 -e
ro
I
I
U
I 30
I
I
I
I
35 I

I
1
40
I I
5 4 3 2 O
- 100 +100
Proton Shifts(ppm)
(B) (A)
'
l
IX
Introduction
Electron Paramagnetic
Resonance
Spectroscopy*
9-1 PRINCIPLES
Electron paramagnetic resonance is a branch of spectroscopy in which radiation
of microwave frequency is absorbed by molecules, ions, or atoms possessing
electrons with unpaired spins. This phenomenon has been designated by different
names: "electron paramagnetic resonance" (epr), "electron spin resonance " (esr),
and "electron magnetic resonance" (emr). These are equivalent and merely
emphasize different aspects of the same phenomenon. There are sorne simiJarities
between nmr and epr spectroscopy that are of help in understanding epr. In nmr
spectroscopy, the two different energy states (when 1 = 1/
2
)arise from the alignment
of the nuclear magnetic moments relative to the applied field, and a transition
between them occurs upon the application of radio-frequency radiation. In epr,
different energy states arise from the interaction of the unpaired electron spin
moment (given by m,= 1/
2
) with the magnetic field, the so-called electronic
Zeeman effect. The Zeeman Hamiltonian for the interaction of an electron with
the magnetic field is given by equation (9-1):
(9-1)
where 9 for a free electro n has the value 2.0023193, f3 is the electron Bohr
magneton, eh/2m
e
c, which has the value 9.274096 (0.000050) x 10-
21
erg
gauss -1 Sz is the spin operator; and H is the applied field strength. This
Hamiltonian operating on the electron spin functions rJ. and f3 corresponding to
m, = + 1/
2
and _1/
2
, respectively, produces the result illustrated in Fig. 9- 1. The
f3 spin state has its moment aligned with the field, in contrast to nmr, where the
lowest energy state corresponds to m
j
= + 1/2(rJ.
N
). The lowest energy state in
epr corresponds to ms = - 1/
2
beca use the sign of the charge on the electron is
opposite that on the proton.The transition energy is given by equation (9- 2):
t.E = gf3H (9-2)
The Additional References contain reviews o[ epr. The reference by J. E. Wertz and J. R. Bolton
is especially recommended.
H:
The
COIT
freq
can
wit
(i.e.
stre
con
free
OH
Q-t
Si n
res(
Iim
Q-t
I t i!
at t
sol
dec
sol,
ca
sp
sol
bes
Sy
fon
mel
360
9--1 Pri nciples 361
E = +(1/2)gf3H
a(m, = +1 / 2)
FIGURE 9-1 The removal 01
h, = gfJH
the degeneracy 01 the a and
Pelectron spin states by a
f3(m, = -1/2)* magnetic !ield. *Note the
difference in the ground state
E = -(1/2)g{3H !rom nmr.
H i n c ~
The energy difference between the a and f3 spin sta tes in magnetic fields of strengths
commonly used in the epr experiment (several thousand gauss) corresponds to
frequencies in the microwave region. For a field strength of 10,000 gauss, one
can calculate from equation (9-2) that .E is 28,026 MHz. This is to be contrasted
with the energy for the transition of the proton nuclear moment of 42.58 MHz
(i.e., radiation in the radio-frequency region) in a magnetic field of identical
strength. The magnetic moment for the electron is -9.2849 x 10-
21
erg gauss-
l
compared to 1.4106 x 10 -
23
erg guass-
l
for a proton nuclear moment.
The epr experiment is generally carried out at a fixed frequency. Two common
frequencies are in the X-band frequency range (about 9500 MHz or 9.5 gigahertz,
GHz,* where a field strength of about 3400 gauss is employed) and the so-called
Q-band frequency (35 GHz, where a field strength of about 12,500 gauss is used).
Since the sensitivity of the instrument increases roughly as v
2
and better spectral
resolution also results, the higher frequency is to be preferred. There are several
limitations on the use of the Q-band frequency. Smaller samples are required for
Q-band, so the sensitivity is not as much greater as one would predict from v
2
It is more difficult to attain the higher field homogeneity (Hj H) that is requ:red
at higher frequencies. Finally, for aqueous samples, dielectric absorption by the
solvent becomes more serious as the frequency increases and this results in
decreased sensitivity.
Water, alcohols, and other high dielectric constant solvents are not the
solvents of choice for epr beca use they strongly absorb microwave power. They
can be used when the sample has a strong resonance and is contained in a
specially designed cell (a very narrow sample tube). Epr measurements on gases,
solutions, powders, single crystals, and frozen solutions can be carried out. The
best frozen solution results are obtained when the solvent freezes to form a glass.
Symmetrical molecules or those that hydrogen bond extensively often do not
form good glasses. For example, cyclohexane does not form a good glass, but
methylcyclohexane does. Sorne solvents and mixtures that form good glasses are
listed in Table 9-1.
The sample tube employed is also important. If the signal-to-noise ratio is
low, a quartz sample tube is preferred, because Pyrex absorbs more of the
microwave power and also exhibits an epr signa!.
*The prefix mega indica les 10
6
, and giga indica tes 10
9
362 Chapler 9 Electron Paramagnetic Resonance Spectroscopy
TABLE 9-1 , Commonly Used Glasses'
Pure Substances
3-Melhylpenlane Sulfuric acid Sugar
Methylcyclopen tane Phosphoric acid T riel ha nolamine
Nuj ol (paraffin oil) Elhanol 2- Methyltelra hydrofu I'an
Iso penl ane Isopropa nol Di-n-propy l et her
Methylcyclohexane l-Propa nol cis-trans Decalin
ISOOClane I-Butanol Tri acelin
Boric acid Glycerol Toluene
Mixtures
Components RaNo AI B
3- Meth ylpentane/isopenlane 1/ 1
Isopentane/ met hyleyclohexane 1/ 6
M et h ylcylo pen ta ne/meth y Ieyclo hexa ne 1/ 1
Pen tene-2(cis)/pen tene- 2(t raJ1S)
Propane/propene 1/ 1
Isopropyl benzene/ propane/propene 2/9/9
Ethanol/ methanol 4/ 1, 5/ 2, 1/ 9
lsopropyl alcohol/isopenla ne 3/7
Ethanol/ iso pen tane/ diet hyl et her 2/ 5/ 5
Alphanol 79'/ mixt ure of primary aleo hols
I opentane/ YI-butyl alcohol 7/ 3
Isopentane/ iso propyl alcoh ol 8/2
Isopentane/ J1 -propyl alcohol 8/ 2
Diethyl ether/ isooctane/ isopropyl alco hol 3/ 3/ 1
Diethyl et her/ isooctane/et hyl alcohol 3j3/ [
d
Di ethyl el her/ iso propyl alco hol 3/ 1
DiethyJ ether, ethanol 3/ 1
Isooctane/ meth ylcyclo hexane/ sopropyl alco hol 3/ 3/ 1
D iet hyl ether/to lu ene/ethan ol 2/ 1/ 1
fsopropyl alcohol / isopentane 2/ 5/5 A
Propano l/ diethyl et her 2.' 5
th
Butanol/ die th yl et her 2{5
DiethyJ ether/isopentane/ dimethyJ formamide/ ethanol 12/ 10/ 6/ 1
Water/ propylene glycoJ 1/ 1
Ethylene glycoJ/ water 2/ 1
Trimethylamine/isopentane/diethyl ether 2/ 5/ 5
T riethylamine/ iso pentane 'diet hyl ether 3/ 1/3
Meth ylh yd razine/ met hy lam i ne/ t rimet h y lamine 2/4/4
Dieth yl ether/isopen tane/ethanol/ pyridi ne 12/ 10/6/ 1
Di-n-butyl ether/diiso propyl ether/dimelhyl ether 3/ 5/ 12
Diphenyl et her/ I,J -di phenylethane/trip henylmelhane 3/3/1
DiethyJ ether/iso pentane 1/ 1 to 1/ 2
Dip ropy l ether/ isopent ane 3/ 1
Dipropyl eth er/ methylcyJohexane 3/ 1
Diethyl ether 'pentene-2(cis)-pent ene- 2(traJ1S) 2/ 1
Ethy l iodide/ isopentane/ diethyl et her 1/ 2/ 2
Et h yl brom ide/ met h ylcyclo he xane/ iso pen tane/ mel h ylcyclo pen tane 1/4/ 7/ 7
Ethanoljmel hanol/ethyl iodide 16/4/ 1
Ethanoljmethanol / propyJ iodide 16/4/ 1
Ethanol / methano ljpropyl chloride 16; 4/ 1
Et hanol/ met hano ljpropyl bromide 16/4/ 1
Dicthyl ether/ iso pentane/ethanol/ I-ch loronaphtha lene 8/6/212
3- Met h y J pentane/ iso pen tane 1/2
PropyI alcohoJ/ propane/ rropene 2/ 9/ 9
Dilso propylamine/ propane/ propene 2/ 9/ 9
Dipropyl ether/ propane/ propene 2/4/4
9-2 The Hydrogen Atom 363
Mixtures
Components Ratio AIB
Toluene/methylene chloride 1/1 or exeess tolllene
Toluene/aeetone 1/ 1 or excess toluene
Toluene/ methanol or ethanol 1/ 1 or exeess toluene
Toluene/ aeetron itrile 1/ 1 or excess toluene
Toluene/ehlo roform
1/ 1 or exeess tolllene
2- M eth y ltet ra h ydro fu ran/ met ha n01 2/ 1
2- M ethy I tetrah yd rofu ra n/proprion i tri le 2/ 1
2- Methyl tetrahyd rofuran/met hyl ene eh loride 1/1
* Abslracted in part , with permission, fr om B. Meyer, " Low Temperature Speclroscopy,"
American Elsevie r Publi shing Ca., New York, J971
There a re many effects tha! modify the electron energy sta tes in a magnettc
field. \Ve shall consider these factors one at a time by discussing the epr spectra
of increasingly complex systems.
In the way of introduction, it will simply be mentioned tha t differences in
the energy of the epr transition for different molecules are described by changi ng
lhe value of 9 in equation (9-2). Thi s is to be contrasted with nmr, where one
customarily holds gN fixed and introduces the shielding constant to describe the
different resonance energies, i. e., for nmr,
(9-3)
As we proceed to more complex systems, we shall discuss the factors that influence
the magnitude of g.
Nuclear
Hyperfine
SpliHing
9-2 THE HVDROGEN ATOM
The first contribution to epr transition energies that will be introduced is the
electron-nuclear hyperfine interaction. The hydrogen atom (in free space) is a
simple system to discuss because, by virtue of its spherical syrnmetry, anisotropic
effects are absent . In the development of epr, we shall employ the Hamiltonian
to quantitatively describe the effects being considered. The full interpretation of
the esr spectrum of a sys tem is given in terms of an effective spin Hamiltonian .
This is a Hamiltonian that contains those effects, of the many to be described,
which are used to interpret the particular spectrum of the compound studied.
The complete spin Hamiltonian for the hyd rogen atom (in free space) is
f = gfJH ' S- gNfJ NH 1 + a7 .S
= gfJ( H);x + HySy+ I-/
z
SJ - gNfJN( H)x + H/
v
+ H)z) + a7
x
S
x
+ a7ySy+ a7
z
S
z
364 Chapter 9 Electron Paramagnetic Resonance Spectroscopy
For a spherical system in a magnetic field that is defined as the z-axis, this
simplifies* to
(9-4)
The first term of this Hamiltonian discussed earlier [equation (9-1)J, leads to the
energy-field relation shown in Fig. 9-1. The second term of the Hamiltonian is
familiar from our discussion of nmr ; it describes the interaction of the nuclear
moment of the hydrogen atom with a magnetic field. It is of opposite sign (the
state with m = + 1/ 2 is lowest) and sma ll er in magnitude than the first termo
The combined effect of the first two terms in equation (9-4) upon the energies
of the spin states of the hydrogen atom in a magnetic field is shown in Fig. 9-2(C).
The field strength is fixed in this figure, and the dashed lines simply show the
energy changes incurred by adding a new term in the Hamiltonian. In order to
determine the energy of the hydrogen atom in a magnetic field, we employ a
basis set for this Hamiltonian [equation (9-4)J that consists of the four possible
electron and nuclear spin functions. Such a basis set is ({J 1 = 1 rxerx
N
), ({J2 = 1 rx e{JN ) '
({J3 = 1 {JerxN) and ({J4 = 1 {Je{JN ) ' Let us begin by calculating the energies arising
from the first two terms in the Hamiltonian, Ho. We must solve the simultaneous
equations {JIII H01 ({Jm ) - E{J1l 1({JII ) = O, where n and m may or may not be
equal. Thus the 4 x 4 secular determinant in this basis set contains diagonal
terms of the type:
( rxe{J N1 gfJH5
z
- gNfJN H7 z 1 rxefJN ) - E( rxefJN 1 rxefJN )
= ( rxefJN 1 gfJH5
z
1 rxe) ' 1 {JN ) - ( rxe{JN 1 gNfJNH7 z 1 {JN ) ' I rx
e
) - E = O
Since for this problem the operators are 1z and 52' rx and fJ a re eigenfunctions ;
i.e., 5
z
1rx
e
) = 1/2rx. , 5
z
1{J .) = - "/2{Je, U rx
N
) = "/2rx N' and 7, 1{JN ) = - 1/
2
{JN'
Furthermore, 5 does not operate on the nuclear spin function and 7z does not
z
operate on the electron spin function, leading to:
It should now be clear that all the off-diagonal elements will be zero with this
Hamiltonian, for a l! of the off-diagonal elements are of the form
{Jn 1 Ho 1 ({Jm ) - {Jn 1 ((Jn) , which equals zero when n#- m. Since the Hamiltonian
matrix is diagonal, the determinant is already factored and we get the four energies
directly, as shown aboye for rxefJN ' They are indicated for El ' E
2
, E
3
, a nd E
4
, in
Fig 9-2(C). These results can be verified for practice. The usual selection rules
in epr are ~ m = Oand ~ m s = 1. It will be noticed !hat the two esr transitions
~ m = O) illustra ted in Fig 9-2(C) have the same energy. Considering only the
first two terms of the Hamiltonian, the epr spectrum of the hydrogen atom would
be the same as tha! of a free electron, i.e., one line at a field hu/ g {J or 9 = 2.0023.
Next, we mus! concern ourselves with the al 5term in the Hamiltonian. This
term describes the coupling of the electron and nuclear spin moments, which
H, and Hy are zero and H = H,. The effects of S" Sy, / " and Iv are not necessarily zero.
-
-
-
-
-
-
-
-
-
-
-
:
-
o

...,
r
r
.
(
I
J
-
-
:
-
-
'
t
r
.

:
:
r

0
'
.
;
,
-
:

r
r
.

e
n
-
-
-
-
-
-
.
-
-
-
-
-
-
-
-
1
Q
e
)

<
-
-
1

f
l
H

_
_
_
_
_
_
/
I

+
2
g
f
'

1
_
_
_
_
_
_

_
_

/
/
/
/
/
/
/

Q

-
-
"

/

"
"
"
"
,
"
"

1

-
-
-
-
-
-
"

"

_
_
-
-
"
-
-

_
_
.
_
_
_
_
_
_
_

1
Q
e
Q
N
)

E

_
_
_
_
1
_
_
_
_
1
Q
e
Q
N

)

2

1
'
-
1
,
/
.
/
,
,
/
/
l
E

,
.
.
.
.
.
.
.
.
.

I
-
.
/
'

"
,
-
-
-
I
Q
Q
N
)

.
/
.
/

'
-

-
-
-
-
-
-
e

E
,

"
E
2

t
l
m

=

E

_
_
_
_
1
_
_
_

-
-
1
-
-
-
-
4

I
E
4

-
-
I
E
3
-
_
_
_
.

I
"
.
N
)

I1
)
3

I
-
-
E

_
_
_
_
_
_
_
_

-
-
-
-
-
-
-
-
"
"
"
-
-
'
-
a
2

1
-
-
;
a
E
3

+
0
+

E
4

+
0
+

E
l

a
2
1
I

1

+
-
-
-
-
-
;
a
E
2

=

(
B
)
.
(
e
)
(
D
)
(
E
)
(
A
)
,
,
,
,
'
F
r
e
e
E
l
e
c
t
r
o
n
,
H

=

H

=

H
=

H

=

N
o
M
a
g
n
e
t
i
c
F
i
e
l
d
+

a
l
,

.
S
,

+

a
l
,

.
S
,

F
I
G
U
R
E

9
-
-
2

T
h
e
i
n
f
l
u
e
n
c
e
0
1
v
a
r
i
o
u
s
t
e
r
m
s
i
n
t
h
e
H
a
m
i
l
t
o
n
i
a
n
o
n
t
h
e
e
n
e
r
g
y
o
f
h
y
d
r
o
g
e
n
a
t
o
m
i
n
m
a
g
n
e
t
i
c
f
i
e
l
d
.
f
J
e
c
x
N

w
c
o
r
r
e
s
p
o
n
d
s
t
o
m
s
=

-
1
/
2

a
n
d
m
I

=

+
1
/
2
;

f
J
e
f
J
N

t
o
m
s
=

-
1
/
2

a
n
d
m
I

=

-
1
/
2
;

C
X
. f
J
N

t
o
m
s
=

+
1
/
2

a
n
d
m
I

=

-
1
/
2
;

a
n
d
c
x
.
c
x
N

t
o

m
s

=

+
1
/
2

a
n
d
m
,
=

+
1
/
2
.

/
classically corresponds to the dot product of these two vectorS. The quantity a
indicates the magnitude of the interaction and has the dimensions of energy. This
is referred to as the Fermi contact contribulion to the coupling, and ils magnitude
depends upon the amount of electro n density at the nucleus, lj!(o) 2, according to:
(9-5)
For a hydrogen atom, the Slater orbital function is lj! S = (1 /na
o
3
) exp (-r/a
o
)
where a
o
, the Bohr radius, equals h
2
/me
2
= 0.52918 . Substituting inlO equation
(9-5), the value of lj! for a hydrogen s-orbital at r = O yields a/h = 1422.74 MHz.
Since the nuclear hyperfine interaction we are talking about involves the do!
product of the nuclear and spin moments, it has X-, y-, and z-components, so
(9-6)
The elements generaled by the 7 s term operating on Ihe basis CX eCX
N
, elc., are
z z
again only diagonal elements because <ep" Ia7
z
S
z
Iepm> = O when m#- n; for
example, <cx./3
N
Ia7
z
Icx
N
> = O. T he following results are obtained for the diagonal
elemenls:
- - 1
<f3
e
cx
NIaSz]z If3
e
cx
N
> = - 4. a
1
<f3 ef3N IaSz]z If3ef3N > = 4. a
These have lO be added to Ihe energies in F ig. 9-2(C), modifying the energies as
shown in Fig. 9-2(D). The contributions of e/4)a to El ' E
2
, etc., from aiJz are
indicated al the bottom of (D). Now we see, looking al the arrows for the t\Vo
electron spin changes, that the transition energies are no longer equal. One
transition gives rise to a spectral peak at lower energy than that corresponding
to 9 = 2.0023 [see F ig. 9-2(D)] by e/2 )a, and the olher occurs at an energy tha!
is higher by e/ 2)a. The energy separation of the two peaks is a.
To complete the problem, we now have lO add the effecIs orixs
x
and }; \ ..
This is best done in terms of the raising and lowering operators, which work in
a similar fashion to 1 and _ that were discussed earher. For the electron spin
operators, we define:
S+=Sx+iSy
L = Sx - iSy
Thu!>
an
Co
The
L:
Allo
we ce
e/eme
,FIGURE
The mal
and
f a
his
,de
lo:
- 5)
(/0)
IOn

dot
9- 6)
are
for
onal
9-2 The Hydrogen Atom 367
and
Combining these equations, we see that:
The following results are obtained by analogy to our earlier discussion orI + and
L:
S+7 _ I {J.a
N
) = Ia.{JN )
s_7+ lae{JN ) = I{JeaN )
S_7 + Ia.a
N
) = O
All other operations of S_7 + or S+7_ upon the basis set produce zero. Thus, if
we consider the 4 x 4 matrix shown in Fig. 9-3, the only non-vanishing matrix
elements from S+ _ and S _ + are
( ae{JN IaS +L I{JeaN ) = a
( {JeaNIaS _7 + Iae{JN ) = a
as
z are
e two
. One
nding
y that
1\:5".
ork ;n
11 spm
- gNflNH) + - E
2 4
o o o
o
1 1
2(gflH + gNflNH) - a - E
1
-a
2
o
O
1
-a
2
1 1
- 2(gfl H + gNflNH) - a - E O
O O O
1 1
- 2(gflH - gNflNH) + a - E
FIGURE 9-3 Secular determinant lor the lield-Iree hydrogen atom.
The matrix element
and
j
We can summarize this entire section by completing the full determinant for
the original spin Hamiltonian equation (9--4), operating on the ([J basis set to give
energies <([Jm I HI ([J,,) = E< ([Jm I ([J,,). The determinant shown in Fig. 9-3 equals
zero. Note that it is block diagonal so that two of the energies, El and E
4
, are
obtained directly. We also see that 1};x and l/iy lead to off-diagonal elements
that mix ([Jz and ([J3. A perturbation theory solution* of the resulting 2 x 2
determinant gives (to second order):
l
We can see in Fig. 9-2(E), where the effects of these off-diagonal elements on the
energy levels are illustrated, that the energies of both transitions are increased
by the same amount. Since the off-diagonal elements are small compared to the
diagonal, effects arising from this part of the Hamiltonian are referred to as
second-order effects. Second-order effects thus have no infiuence on the value of
a read off the spectrum, but will change the value read off the spectrum for g. A
more interesting contribution to the spectral appearance is that the previously
forbidden transition E3 --+ Ez (the simultaneous electron and nuclear spin fiip),now
beco mes allowed because of the mixing of the basis seq
9-3 PRESENTATION OF THE SPECTRUM
As in nmr, the epr spectrum can be represented by plotting intensity, 1, against
the strength of the applied field; bu t epr spectra are commonly presen ted as
derivative curves, i.e., the first derivative (the slope) of the absorption curve is
plotted against the strength of the magnetic field. It is easier to discern features
in a derivative presentation if the absorption lines are broad. The two modes of
presentation are easily interconverted, and the relationship between the two kinds
of spectra is illustrated in Fig. 9-4. In (A), a single absorption peak with no fine
structure is represented; (B) is the derivative curve that corresponds to (A). The
derivative curve crosses the abscissa at a maximum in the absorption curve, for
the slope changes sign at a maximum. Curve (e) is the absorption counterpart
of curve (O). Note that the shoulders in (e) never pass through a maximum and
as a result the derivative peaks in (O) corresponding to these shoulders do not
cross the abscissa. The number of peaks and shoulders in the absorption curve
can be determined from the number of minima (marked with an asterisk in (O))
or ,maxima in the derivative curve.
* The exact solulon is E = -C/
4
) a ('/
2
) [(gil + gNIlN)2H
2
+ a
2
}'/2
t This allowedness is derived in Carrington and McLachlan (see Additional References) on
page 401.
fre.
un
fro
tha
st'
free
ass
9-3 Presentation 01 the Spectrum 369
1/\
9960 10000 10040 gauss
9995 10000 10005 gauss
(A)
(e)
gauss
gauss
(B)
The epr spectrum of the hydrogen atom is illustrated in Fig. 9-5. To a good
approximation, the g-value is measuredat x, which is midway between the two
solid cireles corresponding to absorption peak maxima. The hyperfine splitting,
a/gf3, is the separation between the solid cireles in gauss. The sign of a generally
cannot be obtained directly from the spectrum. The splitting in Fig. 9-2 implies a
positive value for a. If a were negative then m, = - Y2 and m[ = - 1/
2
; that is
(f3ef3N) would be the low energy state.
The epr spectrometer is designed to operate at a fixed microwave source
frequency. The magnetic field is swept, and the horizontal axis in Fig. 9-5 is in
units of gauss. One can set the field at any position using the field dial and sweep
from that place. For a fingerprint type of identification, greater accuracy is needed
than can be obtained using the instrument dials. For this purpose, an external
.S
:t
standard, diphenylpicrylhydrazide DPPH, is used together with a microwave
frequency counter. DPPH has a g-value of 2.0037 0.0002. The field sweep is
assumed to be linear, and the 9 values of other peaks are calculated relative to
IS
a
~
**
(D)
~ ~
H (gauss) ---+-
FIGURE 9-4 eomparison 01
spectral presentation as
absorption (A and e) and
derivative (B and D) curves.
FIGURE 9-5 The epr
spectrum 01 a hydrogen atom
({J has units 01 ergs/gauss) .
MI
m +--
2
In m ~ n
+1-
2
~ lrl m
1
2
III
3
2
FIGURE 9-6 Possible
nuclearspin arrangements 01
the protons in a methyl
radical.
this standard. The field axis is in units ofgauss, and the 9 value is reported as
a dimensionless quantity using
hv
9 = {3H
where v is the fixed frequency of the probe and H (which is being swept) is
obtained from the spectrum. A frequency countershould be used to measure the
probe frequency v.
Thevalue ofais sometimes reported in units ofgauss, MHz, orcm-l.Jt is
to beemphasized that theline separation in a spectrum in units ofgauss is given
by a/gf3 (where a has units ofergs and f3 has units ofergsjgauss-
1
) . When 9 #
2, it is incorrect to report this sepa ratio n as a in units ofgauss. One would have
to multiply the line separation by g{3 and divide by gef3 (where ge is the free
electron value of2.0023193) to report a correct value for a in gauss. Since a is
an energy, it is best to report its value as an energy. This is simply done by
multiplying the line separation in gauss by g{3, with {3 in units ofcm- 1jgauss-l .
There is no g-value dependencefor this unit. The valueofa in MHz is obtained
10
10 l
by multiplying a (cm-
1
) by e (3 x cm sec- ) and dividing by 10
6
9-4 HYPERFINE SPLlTTINGS IN ISOTROPIC SYSTEMS
INVOLVING MORE THAN ONE NUClEUS
Thefirst-orderenergies ofthe levels in the hydrogen atom are given by equation
(9-7), which ignores the small nuclear Zeeman interaction.
E = gf3Hm
s
+amsm (9-7)
Substitutingthe values ofms and m into this equation enables one to reproduce
the energies given in Fig. 9-2(0). For a nucleus with any nuclear spin, the
projection ofthe nuclear magnetic moment along the effective field direction at
the nucleus can take any of the 2/+1 values corresponding to the quantum
numbers -/,( -/+1), ..., (I - 1), I. These orientations give rise to 2/+1
different nuclearenergystates(one for every value ofmI); and when each ofthese
coupleswiththeelectron moment,2/+1lines result in theeprexperiment. Since
these energy differences are small, a11 levels with the same msvalue are equally
populated for practical purposes and the epr absorption lines wil! usually be of
"equal intensity and equal spacing. For example, three lines are expected for an
unpaired electron on 14N, whose1 = 1.
Weshall nextconsidertheeffecton thespectrumwhen theelectron interacts
with(i,e. is delocalized onto)severalnucJei. Forsimplicity,assumethatthespecies
is rotating very rapidly in al! directions, and that the 9 value is close to the free
electron value, As an example, the methyl radical will be discussed,(1,2) As
illustrated in Fig. 9-6,addition ofthe nuclearspin angularmomentum quantum
numbers of the individual protons results in four different values for the total
nuclearspinmoment,M, Asindicatedin Fig.9-7,thisgives risetofourtransitions
(I1M =0, I1ms= 1), Since there are three different possible ways to obtain a
total ofM, = +1j 2or - 1j 2(see Fig, 9- 6), butonly one possible way to obtain
s
e
IS
11
re
:e
is
ly
I
011
-7)
uce
9-4 Hyperfine Splittings in Isotropic Systems Involving More Than One Nucleus 371
m,

./
/// __ 1
/ ___ -2"
FIGURE 9-7 The four transitions that
+% occur in the epr spectrum 01 the methyl
radical (see Fig. 9--8 for the spectrum).
(As with the H atom, the + m, state is
lowestfor ms = - '/
2
and the - m, state
islowestfor ms = +'/
2
, fromthe. S term.)
MI = +3/
2
or - %, the former system is three times more proba ble than the
latter and the observed relative intensities for the corresponding transitions (Fi g.
9-7) are in the ratio 1: 3: 3: 1.
In general, when the absorption spectrum is split by n-equiualent nuclei of
equal spin 1
i
, the number of lines is given by 2nl +1. When the splitting is
caused by both a set of n-equivalent nuclei of spin 1; and a set of m-equivalent
nuclei ofspin I
j
, the number oflines is given by (2nl +1)(2ml
j
+1) The following
specific cases illustrate the use of these general rules.
1. Ifa radical contains n non-equivalent protons onto which the electron
is delocalized, a spectrum consisting of 2/1 lines will arise.
2. If the odd electro n is delocalized over a l1umber , n, of equivalent protons,
a total of n +1 lines, (2nl +1), will appear in the spectrum. This number is less
than the number of lines expected for non-equivalent protons (i.e., 2/1) because
several of the possible arrangements of the nuclear spins are degenerate (see Fig.
9-6). The spectrum of the methyl radical illustrated in Fig. 9-8 contains the four
peak s expected from these rules.
The spectra expected for differing numbers of equivalent protons can easily
be predicted by considering the splitting due to each proton in turn, as illustrated
in Fig. 9-9. When the signal is split by two equivalent protons, the total MI for
the three levels can have the values mI = +1, 0, and - 1. Since there are two
ways in which we can arrange the separate m's to give a total MI =
(namely +1/
2
, - 1/
2
, and - 1/
2
, +l/J, the center level is doubly degenerate. Three
peaks are observed in the spectrum (fJ. M = O,Mn, = 1), and the intensity ratio
is 1 : 2: 1. The case of three protons (e.g., the methyl radical) was discussed above,
and similar considerations are employed for the systems represented in Fig. 9-9
with more than three protons.
The relative intensities of the peaks are given by the coefficients of the
binomial expansiono Itshould be remembered in applying this formula that it is
restricted to equivalent protons or other nuclei having 1 = 1/
2
.
Ine. field strenglh_
FIGURE 9-8 The derivative
spectrum of the methyl
radical in a CH
4
matrix at 4.2
K.
FIGURE ~ 9 Hyperline
energy levels resulting Irom
interaction 01 an unpaired
electron with varying
numbers 01 equivalent
E
N
protons. (2) Each number in
E
parentheses gives the R
G
degeneracy 01 the level to
Y
which it relers, and hence
the relative peak intensities
lorthe corresponding
transitions.
:3 4 5 o 2
Number 01 protons
s
3. If theoddelectronis delocalizedovertwosetsofnon-equivalentprotons,
e
the number ofIines expected is the product ofthe numberexpected for each set
[(2n/ +1)(2m/
j
+1)]. The naphthalene negative ion, which can be prepared by
a
addingsodium to naphthalene,contains an odd electron that is delocalized over

le
the entire naphthalene ringoNaphthalene contains two different sets of four
il
equivalent protons. A total of n +1, or five peaks, is expected for an electron
delocalized on eitherset offour equivalent protons. In the naphthalene negative
ti
SI
ion, the two sets offour equivalent protons should give a total of25 Iines in the
f(
epr spectrum. This is found experimentally.
4. lf the electron is delocalized on nuclei with spin .greater than 1/
2
,
a procedure similar to that for protons can be applied to caJculate the number
of peaks expected. lfthe electron is delocalized over several equivalent nuclei
that have spins greater than 1/
2
,the number ofpeaks expected in the spectrum
fe
is predicted from the formula 2n/ +1. Forexample,five peaks are expected for
an electron delocali zed on two equivalent nitrogen atoms. A procedure similar
to that in Fig. 9-6shows that the intensities ofthe five peaks wilI be in the ratio
a
1:2:3:2:l.
~ 5. lfthe electron is delocalized over several non-equivalent atoms, the
I I
(A)
total number ofpeaksexpected is obtained by takingthe productofthe number
expected for each atom. The scheme illustrated in Fig. 9-10 for an electron
a'
delocalized onto two non-equivalent nuclei with / = 1 is often employed to
n
indicate thesplittingexpected. The three Iines in (A) representsplittingofanepr
111 111 111
(B)
peak by a nucleus with / = 1and a hyperfine couplingconstant a. Each ofthese
I
a
Iines is split into three components as a result ofdelocalization ofthe electron
onasecond,non-equivalentnucleuswith/ = 1,anda hyperfinecouplingconstant
FIGURE ~ 1 0 (A) Three
a', producing in (B) a total of nine Iines. In subsequent di scussions a scheme
lines expected Irom an
similar to that in Fig. 9- 10 wilI be employed for the interpretation ofspectra.
electron on a nucleus with
The shape of the spectrum and the separations ofthe peaks will depend upon
1= 1, and (B) nine lines
theresonantfield,g, andthecouplingconstantsa anda' . Frequentlythemeasured
resulting Irom the splitting by
a second non-equivalent
spectrum wilI not reveal aH the Iines expected, because the line widths are large
nucleus with I = 1. comparedtoa/g{J andtwocloselinesarenotresolved. Forexample,thespectrum
11
)
&
')
I

)

Ol
-
O)
-
5)
n
-
IS.
et
'Y
er
br
9-4 Hyperfine Splittings in IsotropicSystems Involving More Than One Nucleus 373
in Fig. 9-11 could result for the hypothetical radical H-)(+f->H-X+ where
1 =1for X. The two lines in (A) result from the protonsplitting.In (B) each line
in tum is split into threecomponents owing to interaction with nucleus X; thus
we would expect six lines, all ofequal intensity. However, it is possible to detect
only five lines, if the two innermost components are not resolved. They would
give rise to a single peak with twice the area ofthe other peaks (see Fig. 9-11). (Al
The epr spectrum(3) of bis-salicylaldimine copper(II) in Fig. 9-12 i::; an (B)
interesting example to summarize this discussion of nuclear coupling. This FIGURE 9-11 Hypothetical
spectrumwasobtainedona solidandis notisotropic;thisaspectwill bediscussed absorption spectrum lorthe
shortly. Four main groups of lines result from coupling of the 63CU nucleus
radical HX+ (1 = 1lor X).
(l =%) with the electron. The hyperfine structure in each of the four groups
consists of eleven peaks of intensity ratio 1:2:3:4:5:6:5:4:3:2:1. These
peaks result from splitting by the two equivalent nitrogens and two hydrogens,
H' in Fig. 9-12. The total number of peaks expected is fifteen;
(2nN1N +1)(2nH1H +1) = 5 x 3 = 15. Theeleven peaks found for eachsubgroup
in theactualspectrumresultfromoverlapofsomeofthefifteen peaksasindicated
in Fig. 9- 13. Theline for an electron not split by a nuc1eus is shown in (A). The
splittingsby thetwoequivalentnitrogensareindicated in(B) and thesubsequent
splitting by two equivalent protons is indicated in (C) The two nitrogens split
the resonance into five peaks ofrelative intensity 1:2:3:2:1. These values are
derwted in (B) by 4d, 4e, and 4fwhere the intensitiescorrespond to d = 1, e= 2,
andf = 3. The splitting by two equivalent protons will give rise to three lines
for each line in (B), with an intensity ratio of1:2:1. The intensities indicated by
letters undemeath the lines in (C) result from the summation of the expected
intensities. Since the relative intensities are d = 1, e = 2, and f = 3, the ratio of
the intensity ofthe bands in (C) is 1:2:3:4:5:6:5:4:3:2:1. The experimental
spectra agree with this interpretation, which is further substantiated by the
following results:
1. DeuterationoftheN-H"groups(see Fig. 9-12)produced a compound
which gave an identical spectrum.
2. WhentheH'hydrogenswerereplacedbymethylgroups,theeprspectrum
for this compound consisted offour maingroups,eachofwhich consisted offive
FIGURE 9-12
EPR-derivative spectrum 01
bis-salicylaldimine copper(lI)
with i.sotopically pure63CU.
Askerisk indicates calibration
peak Irom DPPH. From A. H.
Maki and B. R. McGarvey, J.
Chem. Phys., 29, 35 (1958).
Decreasing H--
FIGURE 9-13 Interpretation
01 the eprspectrum 01
bissalicylaldimine copper(II).
(A) An unsplit transition. (B)
Splitting by two equivalent
nitrogens, with d, e, and f
indicating relative intensities
01 1, 2, and 3. (C) Further
splitting by two equivalent
protons.
FIGURE 9-14 (A) Basic
molecular geometry 01 the
C03(CO)9Se complex. (B) The
epr spectrum 01 a single
crystal 01 FeC02(CO)9Se
doped with about0.5% 01
paramagneticC03(CO)9Se.
This spectrum containing 22
hyperline components was
recorded at77 K with the
molecularthreelold axis
parallel to the magneticlield
direction. [Reprinted with
permission lrom C. E.
Strouse and L. F. Dahl, J.
Amer. Chem. Soc., 93,6032
(1971).Copyright by the
(A) I
I I I I
(B)
4d 4e 4( 4e 4d
(C) 1 11 11 1 11 1I
d, 2d, d + e, 2e, e + (,2(, (+ e, 2e, e + d, 2d, d
lines resulting from nitrogen splitting only. The hyperfine splitting by the N-Hu
proton and that by the protons on the methyl group are too small to be detected.
This spectrum furnishes conclusive proof of the delocalization of the odd
electron in this complex onto the ligand. This can be interpreted only as covalence
in the metal-ligand interaction, for only bymixing the metal ion and ligand wave
functions can we get ligand contributions to the molecular orbital in the complex
that contains the unpaired electron.
Another interesting application of epr(4) involves the spectrum of
C0
3
(CO)gSe, whose structure and epr spectrum are shown in Fig. 9-14. The
22-line spectrum indicates that the one unpaired electron in this system is
completely delocalized over the three cobalt atoms (lco = 7/
2
), This ineffect gives
rise to an oxidation state of +2/3 for each cobalt atom.
(A)
(8)
9-5 CONTRIBUTIONSTO THE HYPERFINE
COUPLlNG CONSTANT IN ISOTROPIC SYSTEMS
In Equation (9-5), we saw that:
a = 3
8n
g{3gN{3N 11/1 0 1
2
In a molecule, the hyperfine splitting from delocalization of unpaired spin density
p(r
N
) onto a hydrogen atom of the molecule is given by equation (9-8):
(9-8)
where p(r
N
) can be crudely thought of as the difference in the average numbers
of el ectrons at the nucleus that have spin moments characterized by ms = +1/
2
and _1/
2
, When there is an excess of +1/
2
spin density (i.e., the electro n spin
s
9-5 Contributions to the Hyperfine Coupling Constant in Isotropic Systems 375
moment opposed to the field) at the nucleus, this nucleus is said to experience
negative spin density. An excess of electro n density with /TI
s
= - 1/
2
is called positive
spin density. Positive spin density is represented by an arrow that is aligned with
the external field, and negative spin density is represented by one opposed to the
field. To further complicate matters, positive spin density is often referred to as
IX spin in the literature, even though the wave function for evaluation of the matrix
elements for this electron is represented by Pe' Thus, the common convention
for labeling spin density is exactly the opposite of that used to label the electro n
spin wave functions. We wiU avoid the IX and Pla beis of spin density and use
these as symbols for the spin wave functions in this book.
We should also be careful to point out that the amount of unpaired spin
density on an atom in the molecule does not correspond directly to the atom
contributions in the molecular orbital containing the unpaired electron. We shall
refer to the lalter effect as unpaired electron density. An unpaired electro n in an
orbital of one atom in a molecule can polarize the paired spins in an orthogonal
sigma bond so that one of the electrons is more often in the vicinity of one atom
than in the vicinity of the other. This puts unpaired spin density at the nucleus
of the atom even though there is no unpaired electron density delocalized onto
it. We can make this more specific with the following example.
Sorne of the first altempts at interpreting hyperfine couplings involved
aromatic radicals with the unpaired spin in the n-system, e.g., C
6
H
s
N0
2
-. Hckei
ca\culations were carried out and the squares of the various carbon pz coefficients
in the m.o. containing the unpaired electron were employed to give the amount
ofunpaired electron density on the various carbon atoms. The hyperfine splittings
observed experimentally were from the ring hydrogens, which are orthogonal to
the n-system. No unpaired eJectron density can be delocalized directly onto them,
but unpaired spin' density is fel! at the hydrogen nucleus by the so-called
spin-polarization or indirect mechanism. We shall attempt to give a simplified
view of this effect using a valence bond formalismo Consider the two resonance
forms in Fig. 9-15 for a C-H bond in a system with an unpaired electron in a
carbon Pn orbital. In the absence of any interaction between the n and (J systems,
the so-called perfect pairing approximation, we can write a valence bond
description of the bonding and antibonding sigma orbital wave functions:
and
Here f; and f;II represent wave functions for structures 1 and JI in Fig. 9-15,
which we shalJ not attempt to specify in terms of an a.o. and spin basis se!. When
interaction of the n and (J systems is considered, we find that 1 is a more stable
structure than JI and, accordingly, it contributes to the ground state more than
does JI, resulting in valence bond functions:
(a> b)
"
and
FIGURE 9-15 Resonance
lorms lor a C-H sigma bond
f;* = a'f; - b'f;1l (a' < b')
fragment with an unpaired
electron on the carbono
This in effect polarizes the electrons in the C-H sigma bond, leaving spin density
on the hydrogen that is opposite to the unpaired spin density in the carbon p,
orbital. The stabilizing feature of structure 1 over structure II is the electron
exchange interaction. It is the same effect that causes the Jowes.t-energy excited
state for helium, 15
1
25
1
, to be a triplet instead of a singJet. If we label the two
electrons that are mainly on carbon in each of the structures in Fig. 9-15,
we see that they can be interchanged in structure 1, without changing the ms
value of the unpaired electron :
a1 b 1
C 1 l H C1 l H
b a
This interchange is not possible in structure 11. Thus, I is stabilized by a quantum
mechanical interaction analogous to resonance.
A more complete molecular orbital description of this effect is presented in
Dewar's text.(5) In treating the e
2
/rij interactions in a molecuJe, one type of integral
that is obtained describes a repulsive interaction and has the form
(9-9)
This represents the Coulomb repulsion of the electron density es f m *(i)fm(i)dT
is the density in iJ from electrons i and j in orbitals m and n, where m may or
may not equal n. There are other integrals that we shall label Kmn , which are
zero when the electro n spins are paired and are non-zero when the spins are
parallel. The Km/l integrals are :
(9-10)
This is called an exchange integral beca use it corresponds to an exchange of the
orbitals containing electrons i and j. When the spins of the two electrons are
parallel, the squares of these wave functions show that the two electrons have a
drastically reduced probability of being near each other when compared to two
electrons with opposite spins. Thus, the Coulomb repulsion is decreased when
the spins are parallel beca use the electrons stay away from each other. The
magnitude of the Kmn integral depends upon the overlap of the two orbitals m
and n. The quantity fm(j)fn(j) dT
j
was referred to earlier as the differential overlap.
The overlap integral of the differentiaJ overIap of two orthogonal orbitals is zero;
i.e.,
f f,nU)fn*(j)dTj = O
However, when the differential overlap in the volume element dT
j
is operated
upon by e
2
/ rj, multiplied by f m*(i)f n(i), and integrated over all volume elements
dT and dT
j
, the result is not zero, but is the exchange integral. These exchange
effects not only give rise to the spin polarization described aboye and cause the
first excited triplet state of helium to be lower than the first excited singlet, but
they also lead to Hund's rule.
Thespin densityexperienced atthe hydrogen atom ofthe e-Hbond when
there is unpaired electron density in the n-orbital (2p z) is expressed by equation
(9-11):
(9-11 )
where Pc is the unpaired electron density in the carbon 2pz orbital and Q is the
value ofaH when there is a fuI! electron on the carbono The spin density at the
proton is negative, so aH is negative and Q must be negative. In systems where
Pe is known, Qcan be calculated and is found experimentally to vary from - 22
to - 27 gauss. A rough value of - 23 gauss for aromatic radicals treated by
Hckel theorysuffices for most purposesthatwill concern uso When anextended
Hckel calculation is used, the overlapis notsetequal tozero and the molecular
orbital coefficients are normalized to include overlap. Accordingly, the value of
Q used depends on the m.o. calculation used, that is, on the definition ofPe-
When there is a node in the m.o. containing the unpaired electron at one
ofthecarbonatomsina n-system,similarexchangeinteractionswithlower-energy
filJed pi-molecularorbitals operateto place negativespin density on this carbono
We shall make this more specific in the discussion of the allyl radical beJow.
Resultingexchange interaction ofthis unpaired spin with thee-Hsigma bond
places positive spin density on the hydrogen. The Hckel , extended Hckel, or
any restricted m.o. calculation (i.e., one where two electrons are fed into each
molecular orbital) do not include these exchange interactions. They simply
indicate a node at the carbon atom or the hydrogen atom. One attempts to
correct for this shortcoming, for example, at a hydrogen directly bonded to a
carbon containing unpaired electron density in an orthogonal C
2P
orbital by
employing equation (9-11). Often other polarization effects in a molecule are H (4.06)
qualitatively discussed, and the protons orcarbons where these effects dominate
(13.93) H 6 H (13.93)
2

areignoredwhenoneattemptsaquantitativefit ofthecalculatedandex perimental
I I
couplingconstants in a molecule.This discussion can be made more specific by (14.98) H H (14.98)
considering the observed(6) proton hyperfine splittings in the allyl radical shown
in Fig. 9- 16. The radical contains three electrons in the n-systern whose wave FIGURE 9-16 Proton
functions are given by:
hyperfine splittings in the
allyl radical
(9-12)
(9-13)
(9-14)
The odd electron is placed in fJ 2' so one would predict the unpaired density at
el to be Pc = (1/fi)2= 0.5, where l / fi is the el coefficient in the m.o.
containing unpairedelectron.Usingequation(9-11) withQ= - 23,onewould
predict aH to be equal to - 11.5. Furthermore, there would be no unpaired
electron density ate
2
and, without sorne kind ofspin polarization involving the
carbon n electron density, one would predict a zero coupling constant for this
hydrogen or for a 13C at this position. This is not observed. Two polarizations
are needed to account for a hydrogen coupling constant from this middle
hydrogen. The qualitative explanation involves taking the filled orbital !/J I and
writing two separate spin orbitals for it, !/J la and !/J lb' Only one electron is placed
in each spin orbital. The wave functions in terms of the foregoing wave functions
for allyl become
V/l a = !/JI + Jc!/J 3
!/J
lb
= !/JI - )43 (where ), 1)
For spin aligned with the field in the lower energy !/J l a and opposed to the field
in !/J lb' there wiU be increased spin density aligned with the field on atoms 1 and
3 relative to that on atom 2. In !/J lb' with spin density opposed to the field, there
will be more negative spin density on atom 2 than on carbon atoms 1 and 3. By
this mechanism, we are not introducing any unpaired electrons into the old !/JI
orbital, but we simply are inftuencing the distribution of the paired spins over
the three atoms giving rise to negative (opposed to the applied field) spin density
on C
2
. This negative spin density then undergoes spin polarization with the
electron pair in the C-H bond [se e the discussion of equation (9- 11)J to place
spin density on the hydrogen. The exchange interaction of the unpaired electron
in !/J 2 (mainly on C 1 and C3) with the pair in !/J 1 is the effect that lowers the
energy of !/J la relative to !/J lb' The two hydrogens on one of the terminal carbons
are not equivalent by symmetry, but our discussion so far has not introduced
any effects that would make them non-equivalent from the standpoint of spin
distribution. Exchange polarization involving filled sigma molecul a r orbitals is
required.
The phenomena discussed aboye are all indirect mechanisms for placing
unpaired spin dcnsity on the hydrogen. When the free radical is a sigma radical ,
e.g., the vinyl radical H
2
C=C-H, the protons in the molecule make a
contribution to the sigma molecular orbital containing the unpaired electron.
Thus, the unpaired electron is delocalized directly onto the proton and aH is
proportional tO!/J2 Since H ckel calculations are inappropriate for sigma systems
of this sort, the initial work in this area utilized extended Hckel molecular
orbital calculations. Procedures have been reported(7) for evaluating !/J2 at the
nucleus from the wave function, and aH is calculated by:
aH (gauss) = 1887 !/J(H)2 (9-1 S)
Again, spin polariza tion is foreign to this calculation. Often the majority of the
unpaired electron density resides at a given atom in the radical. When this is the
case, spin polarization makes a large contribution at protons directly bound to
this atom. Poor agreement between calculated and experimental results can be
expected for this atom. Generally, for other protons in the molecule (with a few
exceptions), spin polarization effects make a relatively insignificant contribution
when direct delocalization is appreciable.
Semi-empirical quantitative approaches(8 .9) have been reported to incorpor-
ate the effects of spin-polarization. An unrestricted molecular orbital calculation,
i.e., one utilizing spin orbitals, yields the best results. The most common one at
present is the so-called INDO calculation,(9) which has been parametrized to
t
t
g
e
1
1
e
Q
a:
o
a
e
le
e:
~
1,
a
\.
IS
at
to
calculate spin densities on hydrogen. lt has not been extensively tested on atoms
for which spin polarization dominates, but is certainly the method of choice for
this calculation at present. The output(10) consists of one-electron orbitals, and
all the positive and negative spin densities at an atom in all the filled molecular
orbitals are summed to produce the net spin denslty at the atom.
The application of the results from molecular orbital calculations to the
hyperfine splittings from atoms other than hydrogen is considerably more
complexo In contrast to protons, which have only the direct and indirect
mechanisms described aboye, 13C hyperfine splittings have contributions from
other sources. (1) Unpaired electrons in a p(n) orbital can polarize the filled 2s
and the filled ls orbitals on the same atom. (2) There can be direct delocalization
of electron density into the 2s orbital in a sigma radical. (3) Spin density on a
neighbor carbon, by polarizing the C-C sigma bond, can place spin density into
the 2s and 2p orbitals of the carbon whose resonance is being interpreted. The
calcuJations(l0-13) of 14N, 33S, and 170 hyperfine coupling have been more
successful than those for 13C. Silicon-containing radicals have also been success-
fully treated.(13) The effects from spin densities on neighboring atoms are found
to be less important for these nuclei than for 13C.
The application of the results from molecular orbital calculations to the
assignment of the esr spectrum of an organic radical is an important application
of the foregoing discussion. Another application involves determining the
geometry of free radicals. For instance, is CH
3
' planar? Does the C-H bond of
the vinyl radical lie along the C-C bond axis? When the calculated hyperfine
coupling constants are found to vary considerably with geometry (i.e., a whole
series of molecular orbital calculations are performed for different geometries),
the fit of calculated and experimental results can be used to suggest the actual
geometry. (14) In several examples, molecular orbital calculations have provided
evidence about the structure of a radical produced in an experiment.(lla. 14) For
example, y irradiation of pyridine produced a radical believed to be the pyridine
cation; i.e., one of the lone pair electrons was removed. The results shown ID
Table 9- 2 indicate that the 2-pyridyl radical was actually formed(lla)
TABLE 9-2. Extended Hckel and Experimentallsotropic Hyperfine Coupling
Constants (Gauss)
Calculated IOr
Calculated lor 2-pyridyl
C H N ~ C
S
H
4
N Exper i mental
{l1\ 52.5 33.8 29.7
aH
27.0 (2,6 H)
53}
9.7 (3.5 H) 9.3
38.8 (4 H) 7.6 4.3
0.0
These calculations and esr experiments indicate the very extensive amount
of electro n delocaJization that occurs in the sigma system. For example, significant
amounts of unpaired electro n density are found on the methyl group protons of
CH
3
H
2
+ and C
2
H
s
H
2
+ . Thus, the Ion e pair molecular orbital is not a
localized nitrogen lone pair orbital, but is a delocalized molecular orbital. The
extent of delocalzation onto the protons varies in the different rotamers.(l 6)
'
Anisotropic
Effects
9---6 ANISOTROPY IN THE 9 VALUE
The next feature of esr spectroscopy can be introduced by describing the 9 values
for the N0
2
radical trapped(17) in a single crystal of KN0
3
. When the crystal
is mounted with the field parallel to the z-axis of N0
2
(the twofold rotation axis),
a 9 value of 2.006 is obtained. When the crystal is mounted with the x- or y-axis
(the plane of the molecule containing y) parallel to the field, a 9 value of 1.996
is obtained. The molecule is rapidly rotating about the z-axis in the solid, so the
same result is obtained for x or y parallel to the field . The differences in the 9
values with orientation are even more pronounced in transition metal ion
complexes (vide infra) and in compJexes of the lanthanides and actinides.
The treatment so far has involved so-called isotropic spectra. These are
obtained when the radical under consideration has spherical or cubic symmetry.
For radicals with lower symmetry, anisotropic effects are manifested in the solid
spectra for both the 9 values and the a values. Usually, for these lower symmetry
systems, the solution spectra appear as isotropic spectra because the anisotropic
effects are averaged to zero by the rapid rotation of the molecules. Our concern
he re is how these anisotropic effects arise and how they can be determined. Later
(Chapter 13), we shall see how the anisotropy in 9 and a can be used to provide
information about the electronic ground state of transition metal ion complexes.
Anisotropy in 9 arises from coupling of the spin angular momentum with the
orbital angular momenlum. The spin angular momentum is oriented with the field,
but the orbital angular momentum, which is associated with electrons moving
in molecular orbitals, is locked to the molecular wave function. Consider a case
where there is an orbital contribution to the moment from an electron in a
circular molecular orbit that can precess about the z-axis of the molecule. In Fig.
9-17, two different orientations of this molecular orbital relative to the field are
indicated by ellipses. In Fig. 9-17(A), JiL (the orbital magnetic moment vector*)
and Jis (the spin magnetic moment vector) are in the same direction. In Fig.
9-17(B), a different orientation of the molecule is shown. The electron moment
Jis has the same magnitude as before, but now the net moment, indicated by the
boldface arrow, results because JiL and Jis do not point in the same direction.
If it were not for the orbital contribution, the moment from the electron would
be isotropic. When the effects ofthe orbital moment are small, they are incorporated
into the g-value; and thi s g-value will be anisotropic. A tensor, equation (9-16), is
needed to describe it. The g-tensor than gives us an effective spin, i.e., g ' S = S eff'
For different orientations, the g-tensor lengthens and shortens S eff to incorporate
orbital effects. It should be emphasized that even when the ground state of a
molecule has no orbital angular momentum associated with it, field-induced
mixing in of an excited state that does have orbital angular momentum can lead
to anisotropy in g. The information that g-tensor anisotropy provides about the
electronic structure of the molecule will be discussed in Chapter 13 on the epr
of transition metal ion compJexes.
The direction of the orbital angular momentum given by the right-hand rule is opposite to
that of the magneti c moment vector of the electron.
01
in
Be
in
m
rel
an
in
giv
ala
the
an(
COI!
by
9
me
X,
the]
orie:
He
ax
of t
9-6 Anisotropy in the 9 Value 381
IlL
FIGURE 9-17 Coupling of
the projections of the spin
and orbital angular
momentum far two different
molecular orientations
relative to the applied field H.
\ ~
H
(A) (B)
For an isotropic system, we wrote our Hamiltonian to describe the interaction
of an electron spin moment with the magnetic field and with a magnetic nucleus
in equation (9-4) as:
Both g and a were scalar quantities. When an anisotropic free radical is
investigated in the sol id sta te, both g and a have to be replaced by tensors or
matrices. The g(3HSz term in the Hamiltonian becomes (3S ' g ' H, which can be
represented with matrices as:
(9-16)
and a in the al' S term is also replaced by a tensor. Here x, y and i are defined
in the laboratory frame; i.e., they are crystal axes. The off-diagonal element gzx
gives the contribution to g along the z-axis of the crystal when the field is applied
along the x-axis. This matrix is diagonal when the crystal axes are coincident with
the molecular coordinate system that diagonalizes g. When they are not coincident
and the crystal is studied along the x, y, and z crystal axes, we get off-diagonal
contributions, as we shall show subsequently. The g matrix can be made di agonal
by a suitable choice of coordinates.
If one studies the esr of a single crystal with anisotropy in g, the measured
g value is a function of the orientation of the crystal with the field because we
measure an effective g value oriented along the field. If we define molecular axes
X, y, and Z that diagonaJize the g-tensor and pick as an example a case in which
they are coincident with the crystal axes, the effective values of g for an arbitrary
orientation of the crystal is then given by
ger/ = (g2Lx cos
2
()Hx + (g\y cos
2
OHy + (g2)zz cos
2
GHZ
= (g2t)x 2 + (g2)y)y 2 + (g2).. Iz 2 (9-17)
Here G
Hx
, G
Hy
, and OHz are the angles between the field H and the X -, Y- , and Z-
axes, respectively. The symbols Ix, ly, and Iz are often used to represent the cosines
of these angles and are referred to as the direction cosines. From trigonometry,
Fe
tio
Ix 2 + Iy
2
+ IZ 2 = 1, so two parameters suffice to specify the direction. The aboye
equation can be indicated in matrix notation as
(9-18)
Since Sx' Sr and Sz as well as H
x
' Hy, and Hz are defined in terms ofthe molecular
coordinate x,y,z system, they can be replaced by the same direction cosines. The
molecular coordinate system that diagonalizes the g-tensor may not be coincident
with the arbitrary axes associated with the crystal morphology. Since this
experiment is carried out using the easily observed axes of the bulk crystal , the
aboye equation has to be rewritten in non-diagonal form as
(9-19)
Equation (9-19) can be used to evaluate al! the tensor components. The matrix
is symmetric [i.e. , (g2)yX = (g 2t
y
], so only six independent components need to
be evaluated. Since it is most convenient to orient the crystal in the magnetic
field relative to the observed crystal axes, the x, y, and z axes are defined in terms
of these observed axes of the bulk crystal. S"' Sy, and Sz> as well as Hx, H
y
, and
Hz , are defined in terms of these axes. Consider the first case where the crystaI
is mounted, as shown in Fig. 9-18, with the y-axis perpendicular to the field so
that the crystal can be rotated around y with H making different angles, e, to z
in the xzylane. Now, Iz equals cos eand Ix equals sin e, where eis the angle
between H and the z-axis. Substituting these quantities into equation (9-19) and
carrying out the matrix muItiplication yields
(9-20)
v
FIGURE 9-18 Mounti ng 01 a
crystal lor rotation i n the xz-plane. H
z
In
ob
its
in I
to
the
9-7 Anisotropy in the Hyperfine Coupling 383
For rotations in the yz-plane, we have Ix = O, Iy = sin e, and Iz = cos e. Substitu-
tion into (9-19) and matrix multiplication then yields
(9- 21)
In a similar fashion, rotation in the xy-plane yields
(9-22)
These equations thus tie our matrix in equation (9-19) to experimental
observables, gef/ ' In our experiment, a g-value is obtained, but we do not know
its sign, The measured g-value is squared and used in this analysis, For rotations
in any one plane, only three measurements of geff
2
need be made (corresponding
to three different ti-values) to sol ve for the three components of the g2-tensor in
the respective equations, F or the xz-plane, one measures (g2)zz at ti = Oand (g2) xx
at ti = 90. With these values and gef/ at e= 45, one can solve for (g 2)xz' In this
way, the six independen t components of the g2-tensor can be measured, 1 n practice,
many measurements are made and the data are analyzed by the least squares
method. One then solves for a transformation matrix that rotates the coordinate
system and diagonalizes the gl -tensor. This produces the molecular coordinate
system for diagonalizing the g2-tensor, and the square roots of the individual
diagonal g2 matrix elements produce gxx ' 9
yl
" and gz z in this special coordinate
system, In order for this procedure to work as described, it is necessary that all
the molecules in the unit cel! have the same orientation of their molecular axes
relative to the crystal axes. Thus, these measurements are often carried out in
conjunction with a single crystal x-ray determination.
9-7 ANISOTROPY IN THE HYPERFINE COUPLlNG
We introduced Section 6 by describing the anisotropy in 9 when a single crystal
of N0
2
in KN0
3
was examined at different orientations relative to the field, The
a-values of this system are also very anisotropic. When the molecular twofold
axis is paralleJ to the applied field, the observed nitrogen hyperfine coupling
constant is 176 MHz, while a value of 139 MHz is observed for the orientation
in which this axis is perpendicular to the field, In rigid systems, interactions
between the electron and nuclear dipoles give rise to anisotropic components in
the electron nuclear hyperfine interaction, The classicaJ expression for the
interaction of two dipoles was treated in Chapter 8, and the same basic
considerations apply he re, For the interaction of an electron moment and a
nuclear moment, the Hamiltonian is :
(9-23)
The sign is opposite that employed for the interaction of two nuclear dipoles,
which was the problem treated in the section on liquid crystal and solid nmr.
384 Chapter 9 Electron Paramagnetic Resonance Speclroscopy
Substituting S = Sx + Sy + Sz, 1= t + ly + lz, and r= x + y+ z, and expand-
ing these vectors, leads to
2 2
fIdiPOlar = -9{39N{3N{[r + [r + [r
2

- 7 (Sxly + Si) - 7 (S;Jz + SJx) - 7 (Sylz + SJy)
(9-24)
When this Hamiltonian is applied to an electron in an orbital, the quantities in
brackets must be replaced by average values; we employ angular brackets to
refer to the average value over the electronic wave function. In matrix notation,
we then have
fIdiPOlar =
1y (9-25)
This equation is abbreviated as
fI dipolar = hS .T 1 (9-26)
where T is the dipolar interaction tensor (in units ofHz) that gauges the anisotropic
nuclear hyperfine interaction. The Hamiltonian now beco mes
(9-27)
where the first terro on the right is the electron Zeeman terro, the second is the
nuclear Zeeman term, and the third is the hyperfine interaction termo The quantity
A in the third term includes both the isotropic and the anisotropic components
of the hyperfine interaction; i.e.,
A=T+a1 (9-28)
In the application of the Hamiltonian given in equation (9-27) to organic free
radicals, several simplifying assumptions can be introduced. First, 9N{3NH 1, the
nuclear Zeeman effect, usually gives rise to a small energy teTm compared to the
others. (Recall OUT earlier discussion about the energies of the esr and nmr
transitions). Second, 9-anisotropy is small, and we shall assume that 9 is isotropic
in treating the hyperfine interaction* (This would be a particularly bad
If g-tensor anisotropy is comparable to hyperfine anisotropy, this assumption cannal be made
The reader is rererred 10 Chapler 13 and lO A. Abragam and B. BJeany, " EPR or Transilion lons,"
p. 167, CJarendon Press, Oxrord , England, 1970 ror a discussion of Ihis stualion.
assumption for certain transltlon metal complexes, vide infra.) The electron
term is assumed to be the dominant energy term, so Sis quantized along
H, which we label as the z-axi s. We see in thi s example, as we shall see over a nd
over again, that ir is often convenientlO define the coordinate system to be consistent
with the largest energy pJfect. Next we have to worry about the orientation of
the nuclear moment relative to the z-field. Our discussion is general, but it may
help to consider an ethyl radical oriented as shown in Fig. 9-19, with the eH
3
group not undergoing rotation. To make this point, focus attention on nucleus
Ha involved in dipolar coupling to the electron. nuclear moment will not be
quantized along z, but an effective field, H
eff
, which is the vector sum of
the direct external field H (nuclear Zeeman) and the hyperfine field produced by
the nearby electron.lfthe hyperfine interaction is large gauss), the hyperfine
field a t thi s nucleus (i.e., the field from the electron magnetic moment felt at the
hydrogen nucleus) is about 11 ,700 gauss. (This is to be contrasted to the field of
gauss from the magnet and the field of 18 gauss relt at the electron
from the considerably smaller nuclear moment.) Thus, we may be somewhat
justified in ignoring the nuclear Zeema n term, gNfJNH ' 7, in equation (9-27). The
Hamiltonian for most organic free radicals (where 9 is isotropic) is then
considerably simplified from the form in equation (9- 27), and becomes
(9-29)
lhe terms on the far right give the z-component of the electron-nuclear hyperfine
interaction with contributions from 7x and 7" as well as from 7z' for the z-field
does not quantize 7, but does quantize S. When thi s Hamiltonian operates on
the I C( eC(N >a nd other wave functions , off-diagonal matrix elements in the secular
determinant result . When it is diagonali zed and solved for energy, the following
results are obtained:
The term containing the square root replaces the e/4)a obtained from the
evaluation of the al S term for the hydrogen atom. The energy for the hyperfine
coupling is thus given by
(9-30)
The quantity A contains both the isotropic, a, and ani sotropic, T, components
of the hyperfine interaction. Since in solution the anisotropic components are
averaged to zero, it becomes a simple matter to take one-third of the trace of A
to decompose A into T and a. (This assumes that the solvent or solid lattice has
no effect on the electronic structure.)
These expressions apply for any orientation of the molecule relative to the
applied field. In a single-crystal experiment, in which the crystal and molecular
axes are not aligned, we proceed as in the case of the evaluation of the g-tensor
FIGURE 9-19 The
orientation 01 the spin and
nuclear moments in an
applied lield.
l
to determine all of the components of the hyperfine tensor. The coordinate system
that diagonalizes the g-tensor need not be the same one that diagonalizes the
A-tensor, and neither one of these need be the apparent molecular coordinate
system.(17b
J
lf the molecule has overaJl symmetry (i.e. , the fullligand environment
included) such that it possesses an n-fold rotation axis, the same axis will be
diagonal for 9 and A, and it must be coincident with the molecular z-axis.
The angular dependence of the hyperfine interaction for the case where the
field from the hyperfine interaction is large, 1 = %, and the system has axial
symmetry can be expressed by substituting r cos efor z and r sin efor x and y
into equation (9-24). We are, in effect, resolving the nuclear moment in Fig. 9-19
into components parallel and perpendicular to the field. The Hamiltonian
including the electron Zeeman term (gf3HSz) becomes
The result of this Hamiltonian operating on the basis set produces the energies
given by
hM
E = gf3HM
s
T [(a - B)2 + 3B(2a + B) cos
2
e] 1/2 (9-32)
where a is the isotropic hyperfine coupling constant, B is the anisotropic hyperfine
coupling constant, and eis the angle that the z-axis of the molecule makes with
the field. The hyperfine coupling constant A observed experimentally is the
difference between the energies of the appropriate levels and is given (in cm -1) by
A = h[(a - B)2 + 3B(2a + B) cos
2
8] 1/2
One often sees the following equa tion presented in the \iterature to describe
the anisotropy of 9 and A for an axial system:
2
t.E = hv = Ggil + 91)f3
H
O + amI + D(gil - gl)f3Ho + BmIJ(3 cos 8- 1)
(9-33)
where 8 is the angle between the z-axis and the magnetic field, a is the isotropic
coupling constant, and B is the anisotropic coupling constant. The equation
results from equation (9-32) by adding the anisotropy in 9 and by assuming that
both the g- and A-tensors are diagonal in the same axis system.
Since in the analysis of the anisotropy in the hyperfine coupling we deal
with A 2 [see equation (9-30)], usually one cannot obtain the sign of the coupling
constant from the esr experiment. * However, it can be readily predicted for an
organic radical that contains an electron in a p-orbital (there is no anisotropic
contribution from unpaired electron density in a spherical 2s orbital). We shall
begin by returning to equation (9-25) to further explore its meaning. Assume
For certain systems, one can determine the sign of the coupling constant by using nmr, because
spin aligned with the field causes a downfield shift and spin opposed lo the field causes an upfield shift.
th
ve
be
sol
sin
ne
whe
(9-3
TheSl
com
l
oftb
the p
this s
appli
wher!
for tb
Accol
(9-34
.)

h
,y
)
,3)
)IC
on
lat
ti

,al!
me
alise

that the electron is in a hypothetical orbital that can be represented by a unit
vector. When this hypothetical orbital lies along z, we have z = r, x = O, and
y = O, and al! off-diagonal terms are zero. We observe, on substitution into
equation (9-25), that T = k( l /r
3
) , T = k(1l r
3
) , and = - k(2Ir
3
) t [The
xx yy
matrix elements as written in equation (9-25) have the opposite sign, but the
whole term is negative to describethe interactionofthe positive nuclearmoment
and the negative electron moment.] Note that the trace is zero.
To make the problem more reaJistic, we shal! next consider the electron to
be in a pz orbital. Jt is convenient to convert to spherical polar coordinates to
solve this problem by substituting z = l' cos e, x = l' sin e cos ep, and y= l' sin e
sin (p. The result for an electron at a specific (1' , e) (after consideration of the
negative sign) is
T
zz
= g{3gN{3N(3cos
2
e- 1)/1'3)
= - g{3gN{3N(3 cos
2
e- 1)/1'3) T
VY
The latter two matrix elements are readily obtained by substituting for x and y
in equation(9-25) and substituting ( cos
2
ep) = [/
2
for an axial system. Note that
the trace is zero. Now, consider that the electron can be located at any place in
the p orbital. Thus, we have to integrate over all possible angles for the radius
vector to the electron in this orbital and then overal! radii r . In doingso, we get
(9-34)
where ( 1/1'3 ) is the average value of the quantity l l r
3
. Abbreviating equation
(9-34) as T = 4/5 P , we have
zz p
and
Tyy = - 5
2
P
p
(9-35)
These considerations are valuable in predicting the signs of the anisotropic
components ofthe hyperfine couplingconstan!.
Jt is informativeto applytheseequations to theanisotropic hyperfine tensor
of the l3e nucleus, which depends mainly on the unpaired electron density in
the p orbital ofthis atom. We wish to consider the signs ofT
xx
, 'fyy, and T.. for
this system. Thethree orientationsofthep-orbital in the molecule relati e lo the
applied field are indicated in Fig. 9-20. The uotted lines indicate the regions
where the (3 cos
2
e- 1) function is zero. This corresponds)o plotting the signs
for the various regions ofthe lines offlux emanating from the nuclear momen!.
Accordingly, by visual inspection, we can teU whether T expressed in equation
zz
(9-34)will be positive or negative. For example, as we see in Fig. 9-20(A), when
tThe proportionality constant is g{JNgN{3/h.
:
I
l
388 Chapter 9 Electron Paramagneti c Resonance Spectroscopy
11
fi
c
le
(A) (B)
(e)
T
FIGURE ~ 2 Visual representation 01 dipolar averaging 01 the electron and
ra
nuclear moments: (A) p orbital oriented along the lield; (B) and (e) p orbital
perpendi cular to the lield.
the p z orbital is aligned with thefield almost the entireaveragingofthe dipolar
interaction ofthe nuclear moment over the p z orbital will occur in the positive
part ofthe cone. A large, positive Tzz- value is thusexpected.Forthe orientation
Sil
along the x-axis shown in Fig. 9-20(B), thedipolarinteraction, TXX' will be large
it
and negative; the same is true of T
yy
for the orientation shown in Fig. 9-20(C).
Analysis(18.19) ofthe 13C hyperfinestructureoftheisotopicallyenrichedmalonic
acid radical, H
13
C(COOH)2 ' produces a
c
= 92.6 MHz, T
xx
= -50.4 MHz,
T
yy
= - 59.8 MHz, and 4z= +120.1 MHz. After the hyperfine tensor is
diagonalized, the relative signs of Tu> T , and T are known (the trace must
yy z z
be zero), but the absolute signs are not ; i.e., al! those given aboye could be
Th
reversed,However,theargumentsbasedon Fig.9-20provideuswithgoodreason
the
to think that the signs presented aboye are correct.
ma
It is informative to predict the signs ofthe anisotropic hydrogen hyperfine
components ofa C-Hradical. By analogy to our discussion aboye, the three
cor
orientations ofthe p,,-orbital of this radical shown in Fig. 9-21 predict that T
iso
zz
is small, whereas T
vv
is positive and T
xx
is negative. Visual averaging of the
p orbital with our cone of magnetic nuclear flux also suggests that T
zz
will be
In
small. Note that the cones representing the nuclear moment Iines of flux are
infc
vah
drawn at the nucleus whose moment is causing the splitting via the dipolar
---
an:
For
whel
(A)
(B)
(e) the
the ,
FIGURE ~ 2 1 Visual representation 01 the dipolar averaging 01 the nuclear
IS ca
moment on the hydrogen with the electron moment in a p-orbital 01 carbon o(A) Ho
MH.
is parallel to the z-crystal axis ; (B) Ho is parallel to the y-crystal axis ; (e) Ho is
of31
parallel to the x-crystal axis, and we are looking down the axis 01 the p-orbital.
The
)
lar
[ve
on
'ge
ej.
mc
-Iz,
is
ust
be
50n
fine
lree
T
zz
the
I be
are
olar
Ha
interaction with the electron. If the x, y, and z axes are defined relative to the
fixed crystal axes (which are coincident with the molecular axesj as in Fig. 9-21 ,
calculation(20l shows that a full unpaired electron in the carbon p-orbital would
lead to an anisotropic hyperfine tensor of
+43
o
~ MHz
O -5
The experimental proton hyperfine tensor for the a proton of the malonic acid
radical was found to be .
O
29
~ MHz
O 58
Since the isotropic hyperfine coupling constant, a, is one-third the trace of AH'
it equals 59 MHz. Accordingly, the anisotropic hyperfine tensor T must be:
O O
-30 +30 or
~ MHz ~ 1MHz
O -1 O +1
The arguments presented in the discussion of Fig. 9-21 and comparison to the
theoretical tensor lead us to predict the tensor on the left to be correct. This
matrix arose from a = - 59 MHz. Since a positive a would have given tensor
components that correspond to values greater than that for a fuI! electron, the
isotropic hyperfine coupling constant must be negative.
Anisotropic and isotropic hyperfine coupling constants have been measured
in several organic and inorganic radicals and have provided considerable
information about the molecular orbital containing the unpaired electron. The
value of B for one electron in a p orbital of various atoms can be evaluated using
an SCF wave function from
B = 5"
2
h-
1
g{3gN{JN <r-
3
> (9-36)
For 13C, the anisotropic hyperfine coupling constants are given by
[ -B
- B 1
+2B
where B is calculated from SCF wave functions to be 91 MHz: For HC(COOH) 2'
the experimental value of T
zz
for 13C is found to be +120.1 MHz compared to
the value of 182 MHz for an electron localized in a C
2 p
orbital. Accordingly, it
is concluded that Pe is 0.66. From l3C enrichment, it is found that a
e
= +92.6
MHz. A full electron in an s-orbital has an isotropic hyperfine coupling constant
of 3110 MHz. The measured a corresponds to a value of 0.03 for C
2s
spin dcnsity.
e
The radical is expected to be nearly planar.
j

390 Chapler 9 Eleclron Paramagnelic Resonance Speclroscopy
The magnitude ol" the isotropic 13C hyperfine coupling constant supports a
planar(21) CH
3
radical, a = 38.5 gauss, but the value of a = 271.6 gauss in the
c c
CF3 radical indicates(21) that it is pyramidal with s-character in the orbital
containing the unpaired electron.
The isotropic 14N hyperfine coupling constant in N0
2
is 151 MHz, and the
maximum value for the anisotropic hyperfine coupling constant is 12 MHz. With
1540 MHz expected for one electron in a nitrogen 2s orbital and 48 MHz for
an electro n in a 2p orbital, Ps is calculated to be 0.10 and Pp is found to be 0.25,
for a 2p/2s ratio of 2.5. An Sp 2 orbital would have a ratio of 2.0, so this suggests
that more p-character is being used in the orbitals to bond oxygen and an angle
greater than 120
0
is predicted. Microwave results gave a value of 134 for N0
2
in the gas phase.
9-8 THE EPR OF TRIPLET STATES
The next complication we shall discuss arises when there is more than one
unpaired electron in the molecule. An example is provided by the triplet state
that is formed upon u. v. irradiation of naphthalene. The single crystal epr spectrurn
was studied for a sample doped into durene. The similar shapes of these two
molecules allowed the naphthalene to be trapped in the du rene lattice; dilution
of the naphthalene greatly increases the fetime of the triplet state. The spectrurn
consists of three peaks, which changes resooance fields drastically with orientation
ofthe crystal. The changes could not be fitted with the anisotropic g- and a-tensor
we have developed. The anisotropy in this system arises from electron-electron
spin interaction and is described by the spin Hamiltonian given in equation
(9-37). This Hamiltonian is seen to be vety similar to that for the dipolar
interaction of an electron and nuclear spin [equatioo (9-23)].
(9-37)
where r is the vector joining the two electrons labeled 1 and 2.
FIGURE 9-22 (A) Singlet ground
term; (8) ms = 1, 0, -1
components 01 the S = 1 state.
ms = O ms = O
(8) (A)
FI
No
the
Lar
axi
de
Co
mol
repl
grOl
beca
state
the t
are
xist
dege
this e
obse
betw
of S
remo
Whe
trans
that 1
oftn
dm
s
:
when
this il
that e
value
9--8 The EPR 01 Triplet States 391
1
)
rl
n
O
Ir
,o
In
ir
17)
-1
+1
T<-,
m
s
= +1, 0,-1 D
- - - <E'---- ---O
-72 <Ia'l) + l'la)
1_
-1 o
l'l'l)
1-- H increasing --- 1-- H increasing ~ 1-- H increasi ng -----+
o o o
(A) (8) (e)
FIGURE ~ 3 The effeets of zero-field splitting on the expeeted epr transitions. (A)
No zero-field effects. (B) Moderate zero-field splittings. The dashed arrows show
the fixed frequeney result, and the sol id arrows show the fixed field result. (C)
Large zero-field effeets. The magnetie field is assumed to be parallel to the dipolar
axis in the moleeule.
The magnitude of the contribution to the epr spectrum from these effects
depends upon the extent of the interaction of the two spins. We discussed the
Coulomb (1) and exchange (K) integraJs earlier in this chapter. When two
molecular orbitaJs are closer in energy than the difference between exchange and
replll sive energies, a stabJe triplet state arises. In the case of naphthalene, the
ground state is a singlet, and the excited triplet state has an appreciable lifetime
becallse of the forbidden nature of the triplet-singlet transition. For the ground
state S = Oand ms = O, and this configuration is illllstrated in Fig. 9-22(A). For
the triplet state we have S = 1 and ms = 1, O, - l. These electronic configurations
are illustrated in Fig. 9-22(8). If only exchange and electrostatic interactions
existed in the molecule, the three configurations ms = 1, O, and -1 would be
degenerate in the absence of a magnetic field. The magnetic field would remove
this degeneracy as shown in Fig. 9-23(A), and only a single transition would be
observed as was the case for S = 1/
2
, Howe.ver, magnetic dipole-dipole interaction
between the two unpaired electrons removes the degeneracy of the ms components
of S = 1 even in che absence of an excernal field, as shown in Fig. 9-23(8). This
removal of the degeneracy in the absence of the field is called zero-field splitting.
When a magnetic field is applied, the levels are split so that two t..m
s
= 1
transitions can be detected, as illustrated in Fig. 9-23(8). EarJier we mentioned
that three peaks were observed for the epr spectrum of triplet naphthalene. Two
of these are the t..m
s
= 1 transitions shown in Fig. 9-23(8); the third is the
/),m
s
= 2 (between ms = -1 and ms = +1) transition, which beco mes allowed
when the zero-field splitting is small compared to the microwave freqllency. When
this is the case, one cannot assign precise ms = +1, O, or -1 vallles to the states
that exist. When the zero-field spJit ting is very lrge, as in Fig. 9-23(C), the ms
vallles become valid qllantum numbers and the energies for the t..m
s
= 1 allowed
392 Chapter 9 Electron Paramagneti c Resonance Spectroscopy
transitions beco me too large to be observed in the microwave region ; accordingly,
no spectrum is seen.
Since the electron-electron interaction is dipolar [equation (9- 37)J, it is
expected to be described by a symmetric tensor, the so-called zero-field splitting
tensor, O.
(9-38)
The O-tensor elements have the same form as those for T given in equation (9-25).
This dipolar O-tensor accounts for the large anisotropy observed in the spectrum
of a bi-radical. In terms of the principal axes that diagonalize the zero-field
splitting tensor, we can write
where X is the Dxx e1ement in the diagonalized zero-field tensor. Since the tensor
is traceJess, (X + Y + Z = O), the zero-field Hamiltonian can be written in terms
of two independent constants, D and E:
Since X = Y in a system ofaxial symmetry, the last term disappears. If the
molecule has cubic symmetry, no splitting from this zero-field effect will be
observed.
Operating with this Hamiltonian on the triplet state wave functions, one
can calculate the energies as a function of field and orientation. The results
indicate substantial anisotropy in the spectrum. The spectrum for the naphthalene
triplet state is described by g (isotropic) = 2.0030, D/ hc = + 0.1012 cm - \ and
E/ hc = - 0.0141 cm -l. The magnitudes of D and E are related to how strongly
the two spins interact. These quantities beco me negligible as the two electrons
become locali zed in parts of the molecule that are very far apa rt.
In liquids, the traceless tensor O averages to zero. The large f1uctuating fields
arising from the large, rotating anisotropic spin-spin forces in moJecules with
appreciable zero-field splitting cause effective relaxation. The Iines in the spectra
are thus usually too broad to be detected. With sorne exceptions, the epr of triplet
sta tes cannot be observed in solution unless the two spins are far apart (i. e., D
and E are small).
9-9 NUCLEAR aUADRUPOLE INTERACTION
A nuc\eus that has 'a nuclear spin quantum number 1 1 also has an electric
moment, and the unpaired electron interacts with both the nuclear magnetic and
electric moments. The electric field gradient at the nuc\eus can interact with the
quadrupole moment as in nqr, and this interaction affects the electron spin energy
states via the nuc\ear-electronic magnetic coupling as a second-order perturbation.
The effect of quadrupole interaction is usually complicated because it is
le
le
le
1
Id
,1 y
ns
ds
.Ih
.ra
D
9-9 Nuclear Quadrupole Interaction 393
accompanied by a much Jarger magnetic hyperfine interaction. The orientation
of the nuclear moment is quantized with respect to both the electric field gradient
and the magnetic field axis. When the magnetic field and the crystal axes are
para11el, the only quadrupole effect is a sma11 displacement of all the energy levels
by a constant amount, which produces no change in the observed transitions.
However, when the two axes are not para11el, the effect is a competition between
the electric field and the magnetic field. This has two effects on the spacing of
the hyperfine lines: (1) a displacement of a11 energy levels by a constant amount
and (2) a change in the separation of the energy levels that causes the spacing
between adjacent epr lines to be greater at the ends of the spectrum than in the
middle.
This quadrupole effect can easily be distinguished from another second-order
effect that produces a gradual increase or decrease in the spacing from one end
of the spectrum to the other. The variation in the spacing from this other
second-order effect occurs when the magnetic field produced by the nucleus
becomes comparable in magnitude to the external field. In this case, the unequal
spacing can be eliminated by increasing the applied magnetic field.
A further effect of this competition between the quadrupolar electric field
and the magnetic field is the appearance of additional lines that are normally
forbidden by the selection rule I'lm = O. Both I'lrn = 1 and I'lm = 2
transitions are sometimes observed(22) An analysis of the forbidden lines gives
the nuclear quadrupole coupling constant(23) The approach involves a single-
crystal epr study of a compound doped into a diamagnetic host . A spectrum
containing these transitions is illustrated(24j in Fig. 9-24 for bis (2,4-pen-
tanedionato)copper(Il) [
63
Cu(acac)2], doped into Pd(acac)2' The forbidden tran-
sitions are marked in Fig. 9-24(A) with arrows and the other bands are the four
allowed transitions [I(
63
CU) = %J. The spacing and intensity of the forbidden
lines vary considerably with the angle e. The variation in the spacing is shown
in Fig. 9-24(B). By matrix diagonalization, the spectra could be compu ter-fitted(24)
to a spin Hamiltonian:
f = /3[gIlH};z + gJ.(HxSx + HyS
y
)] + AS)z + B(S..Ix + SJJ
+ f
1
/ - 1 (I + 1)] - 9N/3 N
H
. 1
The term Q'[Iz 2 - e/ )I(I + l)J accounts for the quadrupole effects, and a11 other
3
symbols have beendefined previously. A valueofQ'/hc = (3.4 0.2) + 1O-
4
cm-
fits -a11 the data; and for 1 = %, 4Q' is the quantity related to the field gradient
eZQq (see Chapter 14) at the copper nucleus, i.e., Q' = 3e
2
qQ/41(21 + 1). In similar
studies of Cu(bzac)2 doped into Pd(bzac)z and of bis-dithiocarbamato copper(II)
[CU(dtC)2J in diamagnetic Ni(dtc)2' Q' -values of (3.3 0.21) + 10-
4
cm-
t
and
(0.7 0.1) x 10 -
4
cm-
l
, respectively, were obtained. A Q'-value of about
l
16 x 10-
4
cm- is expected for a hole in a d,,_y' orbital ofa free copper ion,
and covalency should lower the value found (Q' measures the electric field gradient
in the direction of the symmetry axis). The charge distribution in the sulfur
complex is very c10se to symmetrical and was interpreted to indicate a very
considerable amount of covalency in the copper-ligand bond.
----
394 Chapler9 Electron Paramagnet ic Resonance Spectroscopy
FIGURE 9-24 (A) The
Q-band spectrum 01
Cu(acach at f) = ar.
Forbidden lines are
indicated by arrows. (B)
Angular dependence 01
(Al
thespacing between each
pai r 01 lorbidden lines
(11m, = 1) in the
spectrum in (A) . The
- - - - ~ ~ o 20
curves are calculated
- O ~
values using
Q' = 3.4 X 10-
4
cm-l. and
~ \
the symbols are
\
experimental values. The
15
\
letters /. m. and h
\ .
represent low-lield. <n
<n
::J \ :
medium-lield. and ro
2:
\ ;
high-lield pairs.
en
e
\" respectively. [Reprinted
u
10
ro
with permission Irom H.
(j)
Q.
m
So and R. L. Bellord. J.
Amer . Chem. Soc.. 91.
2392 (1969). Copyright by
5 ... ,
the American Chemical
h
Society.]
.
...
.
O ~ __~ ~ __~ ____L-__~ ____~ __~
.
O 15 30 45 75 90
Angle (degreesl
(BI
9-10 UNE WI OTHS IN EPR
In this section, we shalJ discuss briefly a number of factors that influence the epr
line width. Many of these are similar to effects we have discussed in nmr.
Broadening due to spin-lattice relaxation results from the interaction of the
paramagnetic ions with the thermal vibrations of the lattice. The variation in
spin-lattice relaxation times in different systems is quite large. For some
compounds it is sufficiently long to allow the observation of spectra at room
temperature, while for others this is not possible. Since relaxation times usually
increase as the temperature decreases, many salts of the transition metals need
to be cooled to liquid N
2
, H
2
, or He temperatures before well-resolved spectra
are observed.
Spin-spin interaction resul ts fr om the smalJ magnetic fields that exist on
neighboring paramagnetic ions. As a result of these fields, the total field at the
ions is slightly altered and the energy levels are shifted. A distribution of energies
9-10 UneWidths in EPR 395
..
v
I
!\
\
:\
.
.
results, which produces broadening of the signal. Since this elfect varies as
(1/r3)(1 - 3cos
2
e), wherer is thedistance betweenionsand eis theanglebetween
the field and the symmetry axis, this kind of broadening will show a marked
dependenceuponthedirectionofthefi eld.Theelfectcanbe reduced by increasing
thedistance betweenparamagneticions bydilutingthesaltwith an isomorphous
diamagnetic material; for example, small amounts ofCuS0
4
can be doped into
a diamagnetic host ZnS0
4
crystal.
As in nmr, rapid chemicaJ processes also influence the spectral line widths
and appearance. Resonances that areseparatein thestopped exchangemit will
broaden as the process rate increases, and they will then coaJesce to give a
weighted-average single resonance. With one-halfthe width at halfheight ofan
organicfree radicalbeingtypically ~ 0 . 1 gauss,significantlinebroadeningoccurs
1
for processes with first order rate constants of5 x 10
7
sec-
Electron spin exchange processes are very common in free radical systems,
and these elfects drastically influence line width and spectral appearance. In
solution, thisis generallya bimolecularprocessin which two radicalscollideand
exchange eJectrons. The elfects are similar to those observed in nmr and are
iHustrated in Fig. 9- 25 for solutions of varying concentrations of di-t-butyl
nitroxide, [(CH3hCJ2NO. As the concentration increases on going from (A) to
(C), the rate ofbimolecularexchangeincreases and the resonances broaden. The
rate constant for this process has been evaluated in the solvent N,N-dimethyl-
10
9 1
formamide and was found to be 7 x l mole-
1
sec - , a value corresponding
tothedilfusion controlled limit. As the solution whosespectrum is shown in Fig.
9- 25(C) becomes considerably more concentrated, the single line resonance
sharpens as in the ver y fast exchange limit in nmr. This sharpening is referred
to as exchange narrowing.
EJectron transferbetweena radicalanda diamagneticspeciescanalso occur
ataratethatcauses line broadeningoftheeprspectrum.Oneofthefi rstsystems
1 ~ t
(A)
(8)
l' 15G----l
(e)
FIGURE 9-25 EPR spectra of the di-t-butyl nitroxide radical in
C
2
H
5
0H at 25 C. (A) 10-
4
M; (B) 10-
2
M; (C) 10-
1
M.
investigated in volved the electron exchange between naphthalene and the
naphthalene negative ion. A second-order electro n transfer rate constant of
10
7 1
6 x l mole-
1
sec- was found(25a) in the solvent THF. This is a factor of
100 slower than the diffusion-controlled rate constant ; it is thought to be slower
beca use the positive counter-ion of the negative ion radical in the ion pair must
also be transferred with the electron.
Many effects cause the line widths of one band to differ from those of another
in a given spectrum. We mentioned earlier that the spin density in the eH
3
proton of ethylamine is conformation dependent. The time dependency of this
type of process can influence the line widths of different protons in a molecule
differently. Rapid interchange between various configurations of an ion pair with
an anion or cation radical can also lead to greater line broadening of certain
resonances than of others. (25b.26)
9-11 THE SPI N HAMILTONIAN
The spin Hamiltonian operates only on the spin variables and describes the
different interactions that exist in systems containing unpaired electrons. It can
be thought of as a shorthand way of representing the interactions described
aboye. The epr spin Hamiltonian for an ion in an axially symmetric field (e.g. ,
tetragonal or trigonal) is:
f =D[S/ - S(S + 1)J + gllfJHzSz + 91.fJ(HxSx + HySy)
(9-39)
+ A11S)z + A1.(S)x + SJy) + Q{7/ - 1(1 + 1)J - gNfJNHO' 7
(
The first term describes the zero-field splitting, the next two terms describe
the effect of the magnetic field on the spin degeneracy remaining after zero-field
splitting, the terms A 11 and A1. measure the hyperfine splitting paral!el and
perpendicular to the unique axis, and Q' measures the changes in the spectrum
produced by the quadrupole interaction. Al! of these effects have been discussed
previously. The final term takes into account the fact that the nuclear magnetic
moment IlN can interact directly with the external field IlNHO = 9NfJNHo1. This
interaction can affect the paramagnetic resonance only when the unpaired
electrons are coupled to the nucleus by nuclear hyperfine or quadrupole
interactions. Even when such coupling occurs, the effect is often negligible in
comparison with the other terms.
In the case of a distortion of lower symmetry, the principal g-values become
9x' 9 , and 9
z
; the hyperfine coupling constants become A
x
' Ay, and Az; and two
y
additional terms need to be included, i.e., E(Sx 2 - S/) as an additional zero-field
splitting and Q"(7/ - 7/) as a further quadrupole interaction. The symbols P
and P' are often employed for Q' and Q", respectively.
The importance of the spin Hamiltonian is that it provides a standard
phenomenological way in which the epr spectrum can be described in terms of
a smal! number of constants. O nce the values for the constants have been
determined from experiment, calculations relating these parameters back to the
electronic configurations and the energy states of the ion are possible. It should
1
9-12 Miscellaneous Applications 397
le
m
~
g.,
39)
be
cid
and
:um
.sed
Ictic
This
lired
.pole
le in
;ome
I two
-field
ols p
Ildard
ms of
been
to the
ihould
be pointed out that not all terms in eguation (9-39) are of importance for any
:given system. For a nucleus with no spin, all terms containing 1 are zero. In the
absence of zero-field splitting, the first term is egual to zero.
9-12 MISCELLANEOUS APPLlCATI ONS
When the epr spectrum for CuSiF6 6H 20, diluted with the corresponding
diamagnetic Zn salt, was obtained at 90 K, the spectrum was found to consist
of one band with partially resolved hyperfine structure and a nearly isotropic
g-value(2 7) In a cu bic field, the ground state of Cu 2+ is orbitally dou bly degenerate.
Although CuSiF
6
'6H
2
0 has trigonal rather than cubic symmetry, this orbital
degeneracy is not destroyed. Thus, Jahn-Teller distortion will occur. However,
there are three distortions with the same energy that will resolve the orbital
degeneracy. These are three tetragonal distortions with mutually perpendicular
axes (elongation along the three axes connecting trans ligands). As a result, three
epr transitions are expected, one for each species. Since only one transition was
found, it was proposed that the crystal field resonates among the three
distortions.(28) When the temperature is Jowered, the spectrum becomes aniso-
tropic and consists of three sets of lines corresponding to three different copper
ions distorted by three different tetragonal distortions(29) The transition takes
place between 50 and 12 K; the three perpendicular tetragonal axes form the
edges of a unit rectangular solid and the trigonal axis is the body diagonal.
Other mixed copper salts have been found to undergo similar transitions:
(Cu, MghLa2(N03)12'24D20 between 33 and 45 K, and (Zn, Cu)(Br0 3) 2'6H20,
incomplete below 7 K. The folJowing parameters were reported for
CuSiF '6H
2
0(30):
o
90 K 20 K
gil = 2.221 0.005 gz = 2.46 0.01
91 = 2.230 0.005 gx = 2.10 0.01
A = 0.0021 0.0005 cm - 1 gy = 2.10 0.01
I
B = 0.0028 0.0005 cm - 1 Az = 0.0110 0.0003 cm-
1
Ax} < 0.0030 cm-
Ay
No guadrupole interaction was resolved. A similar behavior (i.e., a resonating
crystal field at elevated temperatures) was detected in the spectra of sorne tris
complexes of copper(lI) with 2,2' -di pyridine and 1,1 O-phenan throline. (31)
The epr spectrum of the complex [(NH
3
)sCo-0-0-Co(NH
3
)sJ
5
+ is an
interesting example to demonstrate how structural information can be derived
from spin density information and from hyperfine splitting. This complex can be
formulated as: (1) two cobalt(IJI) atoms connected by an O
2
- bridge; (2) cobalt(IJI)
2
and cobalt(IV) atoms connected by a peroxy, 0
2
-, bridge; (3) two eguivalent
cobalt atoms, owing to egual interaction of one unpaired electron with both
cobalt atoms; (4) interaction of the electro n with both cobalt atoms, but more
with one than, the other.
If (1) were the structure, a single line would result, whereas (2) would give
rise to eight lines (1 = 7/
2
for Col. Structure (3) would result in 15 lines and (4)
,
in 64. It was found(32) that the spectrum consists of 15 lines, eliminating the
unlikely structures (2) and (4) and supporting structures (1) or (3) or a mixture
of both. An
17
0 hyperfine result would be required to determine the importance
of structure (1).
A studyC33) of the 1 : 1 adducts of cobalt(JI) complexes with dioxygen has led
to an internally consistent interpretation of the
17
0 and 59CO isotropic and
anisotropic hyperfine coupling constants. Depending on the ligands attached to
cobalt, the adducts are described as consisting of bound O
2
or O
2
-.
One of the advantages of epr is its extreme sensitivity to very small amounts
of paramagnetic materials. For example, under favorable conditions a signal for
12
diphenylpicrylhydrazyl (DPPH) radical can be detected if there is 10- gram
of material in the spectrometer. This great sensitivity has been exploited in a
study of the radicals formed by heating sulfur. When sulfur is heated, the
diamagnetic Ss ring is c!eaved to produce high molecular weight Sx chains that
have one unpaired electro n at each end. The chains are so long that the
concentration of radicals is low, and paramagnetism cannot be detected with a
Gouy balance. An epr signal was detected,(34) and the number of unpaired
electrons (which is proportional to the area under the absorption curve) was
determined by comparing the area of this peak with the area of a peak resulting
from a known concentration of added radicals from DPPH. The total number
of radicals in the system is thus determined, and since the total amount of sulfur
used is also known, the average molecular weight of the species SSxS can be
ca1culated. The radical concentration at 300C was 1.1 x 10- 3M, and the average
chain length at 171 C was 1.5 x 10
6
atoms. By studying the radical concentration
as a function of temperature, a heat of dissociation of the S-S bond of 33.4 kcal
mole - 1 per bond was o btained.
Copper(lI) forms complexes of varying geometries, which have similar
electronic spectra and magnetic susceptibilities. Thus, it is often difficult to infer
the geometries of these materials in solution or in media other than the solid,
where single crystal x-ray studies can be used. A recent 110 study of the
five-coordinate adducts formed by vanous Lewis bases and hexa-
fluoroacetylacetonate copper(JI) describes (35) a procedure for determining
whether apical or basal isomers of a square pyramid are formed.
This high sensitivity of epr measurements has been of great practical utility
in biological systems.(3.6) Many metalloproteins have been studied in order to
determine the metal's oxidation state, the coordination number of the metal, and
the kinds of ligands attached. The measurements are generally made on frozcn
solutions. The interpretation of the results is difficult, and conc!usions are based
upon analogies between these spectra and those of model compounds. These
applications are more appropriately considered in the chapter on the epr spectra
of transition metal ions.
There have been several studies reported in which epr has been employed
to identify and provide structural information about radicals generated with high
energy radiation( 37) The materials O
2
-, CIO, CIO
z
' PO/ -, and CI0
3
are among
the many interesting radicals produced by this technique.
Spin traps have been used(38) to detect radicals whose lifetimes or relaxation
times are too short to be seen by epr. In a typical experiment, a nitrone or nitroso
compound is added to the system in which the radicals are formed. The reactions
in equations (9-40) and (9-41) occur to generate a relatively stable nitroxide that
can be det ected in the epr.
1
p
r
ti
le
()
T
R
1
2
3
4
5
6
7
8
9.
10
11
12.
13.
14.
15.
16.
17.
18.
19.
20.
21
22
23
24.
25.
and
frOIY
fron'
V\/ HR'
(9-40)
+ R -------+ ~ '-
>O-H'
N N
I I
101 10
(9-41)
Theeproftheresultingnitroxidesshowthecharacteristi c1:1:1nitrogenhyperfine
pattcmlnlhe nitrone,(S,S-dirnethyl-l-pyrroline-l-oxide,equation(9-40)) further
splitting by the hydrogen labeled H' in equation (9-40) gives rise to a six-Iine
pattern.Splittingby Ihemethyl group of(CH3hCN(0)CH3 gives aTl overlapping
Iriplel ofquarlels. The magnilude ofthe AN and AH vaJues can be used to heIp
idcnlify Ihe radicals trapped. Table9-3li sts sornetypi caJ vaJues forspin adducts
of5,5-dimethyl-l-pyrroline-l-oxide.
TABLE 9-3. Hyperfine Splitting (in gauss) for Nitroxides Produced from
Radical Trapping by 5,5-Dimethyl-1-pyrroline-1-oxide
R
1. MClhyl
~ Elhyl
1 n-Bulyl
4.Bcnz)I
5. I-Phenylethyl
6. Phen)'1
l-Cyanobcnzyl
x.Phenoxymelhyl
9 I-Elhoxyelhyl
Itl. lClrahydrofuranyl
11. Hydroxymethyl
I ~ 1-Hydroxyethyl
11 I-Hydroxybutyl
I'.2-Hydr0xypropyl
1.Acelyl
lh.Bcnzoyl
11. Aminoformyl
IX. Dimclhylaminorormyl
19 Tnnuor mClh yl
2IJ MClhoxy
.1 Elhoxy
_ n-Butoy
_' e-Bulo,y
:. Bcnzoy1oxy
~ Supcroxide
G
N
14.31
14.20
14.24
14.16
14.20
13. 76
1439
13.79
14.20
14.12
14.66
15.03
14.89
14.58
14.03
13.99
15.23
14.30
13.22
13.58
13.22
13.61
13.11
12.24
12.9
aH
20.52
2049
2041
20.66
2049
19.22
20.63
19.56
2049
17.92
20.67
22.53
22.72
239{
17.87
15.57
18.56
17.37
15.54
7.61
6.96
6.83
7. 93
9.63
6.9
G,.
101(3F)
1.85(1 H)
189(1H)
2.06(1H)
1.97(1 H)
0.87(2H)
Thccouplingsare solvcnt depcndent. Oxidation of[he nitrone produces a radical with f} = 2.009
nJA, = 13gauss Ihat ca nbe confuscd with trappinga radical. Generali on and trappingofradical s
'msolventoxidation mustalso beconsidered.Ada ta base,compulercompil ation ofradical sformed
t mvarious traps in a variet yofsolvents is ava ilable.! 39)
le
re
ce

1d
to
ItS
or
1m
la
lhe
mt
the
na
red
,'as
ing
ber
lfur
1 be
age
lion

lilar
ofer
Dlid,
the
exa-
ning
li lity
to
and

(9-40)
+R ->/\ '-
N R
>(I-H'
N
I I
/01 /0
(9-41)
The epr of the resulting nitroxides show the characteristic 1: 1: 1 nitrogen hyperfine
pattern. In the nitrone, (5,5-dimethyl-l-pyrroline-l-oxide, equation (9-40))further
splitting by the hydrogen labeled H' in equation (9-40) gives rise to a six-line
pattero. Splitting by the methyl group of (CH3hCN(0)CH 1 gives an overlapping
triplet of quartets. The magnitude of the AN and AH values can be used to help
identify the radicals trapped. Table 9-3 lists some typical values for spin adducts
of 5,5-dimethyl-l-pyrroline-l-oxide.
TAB LE 9-3. Hyperfine Splitting (in gauss) for Nitroxides Produced from
Radical Trapping by 5,5-0imethyl-1-pyrroline-1-oxide
R
1. Methyl 14.31 20.52
2. Ethyl 14.20 20.49
3. n-Butyl 14.24 20.41
4. Benzyl 14.16 20.66
5. I-Phenylethyl 14.20 20.49
6. Phenyl 13.76 19.22
7. a-Cyanobenzyl 14.39 20.63
8. Phenoxymethyl 13.79 19.56
9. I-Ethoxyethyl 14.20 20.49
10. Tetrahydrofuranyl 14.12 17.92
11. Hydroxymethyl 1466 20.67
12. I-Hydroxyethyl 15.03 22.53
13. l-Hydroxybutyl 14.89 22.72
14. 2-Hydroxypropyl 14.58 23.9{
15. Acetyl 14.03 17.87
16. Benzoyl 13.99 15.57
17. AminoformyJ 15.23 18.56
18. Oimethylaminoformyl 1430 17.37
19. Triftuoromethyl 13.22 15.54 1.01(3F)
20. Methoxy 13.58 7.61 1.85(1 H)
21. Ethoxy 13.22 6.96 1.89(IH)
22. n-Butoxy 13.61 6.83 2.06(1 H)
23. t-Butoxy 13.11 7.93 1.97(1 H)
24. Benzoyloxy 12.24 963 0.87(21-1)
25. Superoxide 12.9 6.9
. The couplings are solvent dependen t. Oxidation of the nitrone produces a radical wilh 9 = 2.009
and AN = 13 gallss that can be confused with trapping a radical. Generation and trapping of radi ca ls
from solvent oxidation must also be considered. Adata base, computer compil at ion of radicals formed
from various traps in a variety of solvent s is available.rJQ)
REFERENCES
CITED
3
1. F. 1. Adrian el al., Adv. Chem. Ser., 36, 50 (1960).
2. A. Carrington, Quart. Rev., 17, 67 (1963).
3. A. H. Maki and B. R. McGarvey. 1. Chem. Phys., 29, 35 (1958).
4. C. E. Strouse and L. F. Dahl, 1. Amer. Chem. Soc., 93, 6032 (1971).
5. M.1. S. Dewar;"MolecularOrbitalTheoryofOrganicChemistry,"McGraw-Hill,New
York, 1969.
6. R. W. Fessenden and R. H. Schuler, J. Chem. Phys., 39, 2147 (1963).
7. R. S. Drago and H. Petersen, Jr., J. Amer. Chem. Soc., 89, 3978 (1967).
J.
8. A. D. McLachlan, Mol. Phys., 3, 233 (1960).
C.
9. J. A. Pop1e el al., J. Amer. Chem. Soc., 90 , 4201 (1968) and references therein; 1. A.
PopIe and D. L. Beveridge, "Approximate Molecul ar Orbital Theory," McGraw-
A.
Hill , New York, 1970.
10. M. Karplus and G. K. Fraenkel, 1. Chem. Phys., 35,1312(1961).
c.
11. a. R. E. Cramer and R. S. Drago, J. Amer. Chem. Soc., 90, 4790 (1968).
b. P. D. Sullivan, J. Amer. Chem. Soc., 90, 3618 (1968).
B.
12. M. Broze, Z. Luz and B. L. Silver,1. Chem. Phys., 46, 4891 (1967).
W.
13. I. Biddles and A. Hudson, Mol. Phys., 25, 707 (1973).
A.4
14. a. R.S. Drago and H. Petersen, Jr.,1. Amer. Chem. Soc., 89, 5774 (1967).
N. I
b. R. E. Cramer and R.S. Drago, J. Chem. Phys., 51, 464 (1969).
P.
15. R. W. Fessenden and P. Neta,Chem. Phys. Letters, 18, 14 (1973).
16. R. Fitzgerald and R. S. Drago, 1. Amer. Chem. Soc., 90, 2523 (1968).
C.
17. a. R. Livingston and H. Zeldes, 1. Chem. Phys. ,41, 4011 (1964).
R.
b. 1. C. W. Chien and L. C. Dickerson, Proc. Natl. Acad. Sci. USA, 69, 2783 (1972).
A.
18. H. M. McConnell and R. W. Fessenden,J. Chem Phys. ,31, 1688 (1959).
G.l
19. T. Cole and C. Heller, 1. Chem. Phys. ,34,1085 (1961).
20. H. M. McConnell el al., J. Amer. Chem. Soc. ,82, 766 (1960).
H. f
21. R. W. Fessenden and R. H. Schuler,1. Chem. Phys., 43,2704 (1965).
22. P. W. Atkins and M. C. R. Symons, 1. Chem. Soc., 4794 (1962).
23. N. Hirota, C. A. Hutchison, Jr. and P. Palmer, 1. Chem. Phys.,40, 3717 (1964) and
references therei n.
24. H. So and R. L. Belford, 1. Amer. Chem Soc., 91, 2392 (1969); R. L. Belford, D T.
Huangand H. So, Chem. Phys. Letters, 14, 592 (1972) and references therein.
25. a. R. L. Ward and S. 1. Weissman,1. Amer. Chem.Soc., 79, 2086 (1957); T. A. Mil1er
1. (
and R. N. Adams, J. Amer. Chem. Soc., 88,5713 (1966).
b. J. R. Bolton and A. Carringt on, Mol. Phys. ,5, 161 (1962).
26. 1. H. Freed and G. K. Fraenke1,J. Chem. Phys., 37, 1156 (1962).
27. B. Bleaney and D. J. E. Ingram, Proc. Phys. Soc., 63, 408 (1950).
28. A. Abragam and M. H. L. Pryce, Proc. Phys. Soc. ,63, 409 (1950).
29. B. Bleaney and K. D. Bowers, Proc. Phys. Soc., 65, 667 (1952).
30. B.Bl eaney, K.D.BowersandR. S.Trenam,Proc.Roy. Soco (London)A228, 157(1955).
31. H.C. Allen.Jr. ,G.F. KokoszkaandR.G.Inskeep,J. Amer.Chem.Soc. ,86, 1023(1964).
32. E. A. V. Ebeworth and J. A. Weil, 1. Phys. Chem., 63, 1890(1959).
33. B. Tovrog, D. Kitko and R.S. Drago,J. Amer. Chem Soc. , 98, 5144 (1976).
34. D. M. Gardner and G. K. Fraenkel, J. Amer. Chem. Soc., 78, 3279 (1956).
35. D. McMilJin, R. S. Drago and 1. A. Nusz,1. Amer. Chem. Soc., 98, 3120 (1976).
2. L
36. See, for example, C. S. Yang and F. M. Heuennekens, Bi ochemistry, 9, 2127 (1970).
37. P. W. Atkins and M. C. R. Symons, " The Structure ofInorganic Radicals," EIsevier
Publishing Co., Amsterdam, 1967.
b.
38. a. E. G. Janzen, Free Radicals Biol., 4, 115 (1980).
b. M. 1. Perkins, Adv. Phys. Org. Chem., 1-7, 1(1980).
C. E. Finkelstein,G. M. Rosenand E.J. Rauckman,J.Am.Chem.Soc.,102, 4994 (1980).
d. G. M. Rosen and E. 1. Rauckman, Proc. Nat!. Acad. Sci. U.S.A., 78, 7346 (1981).
e. E. G. Janzen,C. A. Evans and 1. l.- P. Liu, J. Mag. Res., 9,510(1973).
f. D. E. Hamilton, R. S. Drago and 1. Te1ser, J. Am. Chem. Soc., 106, 5353 (1984).
*'
Exercises 401
-
39. A. S. W. Li, A. H. de Haas, L. J. Park, M. S. Watson and e. F. Chignell, "Spin Trap
Data Base II (ST DBII )" MD 1703, LMB, P.O. Box 12233, Research Triangle Park,
N.e. 27709.
w
A.
w-
72).
,and
1. E. Wertzand1. R. Bolton,"ElectronSpin Resonance," McGraw-HJlI,New York, 1972. ADDITIONAL
C. P. Poo1e and H.A. Farach,"TheTheory ofMagneticResonance," Wiley-Interscience,
REFERENCES
New York, 1972.
A. Carrington and A. D. McLachlan, "Introduction to Magnetic Resonance," Harper &
Row, New York, 1967.
C. P. Poole,Jr., "ElectronSpin Resonance AComprehensiveTreatiseonExperimental
Techniques," Interscience Publishers, New York, 1967.
B. A. Goodman and 1. B.Raynor, Adv. Inorg. Chem. Radiochem., 13, 135 (1970).
W. Weltner, "Magnetic Atoms in Molecules: ' Dover Publications, Mineola, N.Y., 1989.
A. Carrington, Quart Rev., 17, 67 (1963).
N. .Atherton, "Electron Spin Resonance," Halsted Press, London, 1973.
P. W. Atkins and M. e. R. Symons, "The Structure of Inorganic Radicals," Elsevier
Publishing Co., Amsterdam, 1967.
C. P. Slichter, "PrincipIes ofMagnetic Resonance," Harper & Row, New York, 1963.
R. M. Golding, "Applied Wave Mechanics, " Van Nostrand Reinhold, New York 1964.
A. Abragam, "The Principies ofNuclear Magnetism," Clarendon Press, Oxford, 1961.
G. E. Pake abd T. L. Est1e, "Paramagnetic Resonance," 2nd ed., W. A. Bcnjamin, New
York,1973.
H. Fisher,"Magnetic Properties ofFree Radicals," Landolt-BernsteinTables,NewSeries
Group Il, Vol. 1, Springer-Verlag, Berlin, 1965.
D.T.
l4illcr
1955).
1964).
~
970).
Isevier
'1980).
1981).
94).
J. Convert the derivative curves below to absorption curves:
EXERCISES
(A) (B)
2. a. How many hyperfine peaks would be expected from delocalization of the odd
electron in dibenzene chromium cation onto the rings?
b. Using a procedure similar lo Ihat in Fig. 9-6, explain how Ihe number of peaks
arises and what the relative intensities would be.
For references heavily oriented loward the epr oftransition metal ions, see Chapter 13.
3. a. Copper( 11) acetate is a dimer, and the two copper atoms are strongly interacting.
The epr spectrum consiSIS of seven lines with intensi ty ratios 1:2 :3 :4 :3:2: 1.
Copper nuclei have an 1 value of3/
2
,and copperacetateconsis tsofa ground state
thatis asingletand anexcitedstate that isatriplet. Explain thenumberand relative
intensit yofthe lines in thespectrum. [Foranswer,see B. Bleaney and K. D. Bowers,
Proc. Roy. Soco (London), A214, 451 (1952).J
b. What would you expect to happen to the signal intensity as a sample of copper
acetate is cooled? Why?
4. Predict the eprspectrum for (S03hN02- .
S. The mono negative ion
a. How many lines are expected in the spectrum, and what would be the relative
intensities of these?
b. What evidence would you employ and what experiments could be carried out to
indicate electrondelocali zation onto the oxygen?
c. The magnitude ofaH in thi s material is 2.37 gauss. Compare the spin density on
hydrogen in this molecule with that on a hydrogen atom.
d. How would the sign of the proton hyperfine coupling constant indicate whether
the odd electron was in a sigma- or pi-molecular orbita l?
e. Using the valueofaH given aboye and the fact that the unpaired electron is in the
n-system, calculate the spin density on the nearest neighbor carbono
6. The 13C hyperfinecouplingin themethyl radical is41 gauss,and the proton hyperfine
coupli ng is 23 gauss. Sketch the spectrum expected for 13 'CH
3
radical. [For answer,
see T. Cole el al, Mol. Phys., 1,406 (1958). J
7. Assume that all hyperfine Iines can be resolved and sketch the spectrum for the
chlorobenzene anion radical.
8. Assumingall otherfactorsconstant,would[inebroadeningbegreaterfor a bimolecular
process with aratecons tant of 10
7
or with arateconstant of 10
10
.)
9. How many lines would you expect in the epr spectrum of (CN) sCo0
2
Co( NH
3
)s ?
bplain.
10. The spectrum below is obtained fo r the NH2 radical:
a. Convert it to an absorption spectrum.
b. Howcouldyou determinewhetherthelargerorsmaJl ersplittingis duetohydrogen?
c. Assume that the larger splitting is due to nitrogen. Construct a diagram similar to
Fig.9-10 to explain the spectrum.
13.
Exercises 403
) 1. a. How many lines would yo u expect in the speclru m of lhe hYPolhetical mo lecule
SCI] (l for S = Oand e l = 3/
2
)?
b. Using a procedure simi lar lO lhat in F ig. 9- 6 and Fig. 9-7, explain how t hi s number
arises and indi cate the lransitions with a rrows. State what lhe expected rel a live
intensilies would be.
12. Th e epr speclrum of the cycJopentadiene radical (e sHd rapidly rotating in a single
crystal of cyclopen ladi ene is given below.
~ 3 G-l
a. Writc lhe appropriale spin Hamill onian.
b. Interp rel the spectrum.
13. Int erpret lhe epr spcctrum of eH
2
0H given beJow.
f-----17.4 G ----1
115G- f-
14. The epr spectrum of C
6
H
s
Ge(CH
3
h - is given below. Interpret this spectrum, given
the faet that al! of the splittings a ri se from the phenyl ring protons. CalcLilate the
a-vaJues.
16
17
[-----3 G--i
15.
Writ e the spin HamiJtonian, interpret the spectrum, and report the a-values.
f---3 G-+j
Exercises 405
16. a. Int erpret the epr spectrum given below and calcul ate the a-value(s) for the
substi tuted nitrosyl nitroxide, 0 -
I
(CH
3
)2 N+
" e/
I C-C
6
H
5
C
(CH
3
)2/ ' N!
I
o 1---10G- --i
b. What can you conclude about the deJocalization ofthe unpaired eJectron?
17. The epr spectrum ofthe potassium salt ofthe biphenyl anion,
5' 6' 6 5
is given as follows. Interpret the spectrum and calculate the a-values.
18. Th"p"p,"cemofIh,"""0"0'00. fON1] . i,gi"",, folloM. 10",p,"
the spectrllm and calculate the a-valll e(s).
1---1O G--------"'i
21.
19. Below is the epr spectrum of a sample ofS2- that has 40% 32 S (I = O) nuclei and
60% 33S (I = %) nuclei. lnterpret the spectrum and determine a for 33S.
1850 1900 1950 2000 2050 gauss
20. McConnell's relation allowsa rough prediction ofthe magnitllde ofproton hyperfine
cOllpling constants on conjugated organic systems by performing a Hckel m.o.
calclllation on the system. The hyperfine constant for the ith proton, a, is given by
a = Qp, wherep = C
j
; 2 C
j
is thecoefficientofthevariouscarbon2pz-atomicorbitals
in themolecular orbital containing the unpaired electron.
a. Thecarbon 2pz atomic orbitals that make IIp the 1!-system are orthogonal to the
C-Hsp2-sigma bond. Why then, does any unpaired electron density reside on
the proton?
b. Themolecular orbital scheme for benzene is:
Exercises 407
In the benzene anion, the unpaired electron can be in either f;4 or f;5. A Hcke[
m.o. calculation for these wave functions gives
:0:
1
f;4 = -:jtfJl - tfJ3 +tfJs - tfJ6)
In p-xylene, the degeneracy ofthese two m.o.'s is lifted, with f;4 lower in energy. se
McConnell's relation and calculate the proton hyperfine coupling constants for the
p-xylene anion. Draw the eprspectrum.
21. In an anisotropic single crystal epr stud y at v= 9.520 GHz, the g-value was fOllnd
to change with rotation in the xz(_ _. - curve)-, yz( curve)-, and xy(- curve)-
planes shown as follows.

Q)
e
6
3205
4
/-",
, \
/ '
. \
/ .
, \
3 /
. \
2 / \
,
\
,
\
.. -..
.......
g> 3200

.
.
.
\
.A
:/i
::
9
8
7
.
.
.
.
.
.
\
,
. ,
\
.... /
.....\ /
',-",,'
__ ____-L____ __ __ __
O 60 90 120 150 180
e(degreesl
The field position for resonance, H, is given. Th is is converted to a g-vallle using
!Jv 6801.9
!lE =hv and equation (9- 2). O ne obtains geff =- =-- for a 9.520-GHl
microwave frequency. f3 H H
o
,
408 Chapter 9 Eleclron Paramagnelic Resonance Speclroscopy
a. Inlerpolale rrom the plol and evaluale aJl orIhe elemenls orIhe g2-lensor.
b. Whal would you learn by diagonalizing Ihe g2-lensor ?
c. Whal sleps are required lo diagonalize Ihe g2-lensor?
d. Whal sleps are required lo oblain Ihe direction cosine matrix?
e. Write Ihe spin Hamiltonian.
-
The
Her
10ns
of I
Tral
unp
com
com
inftu
disCI
slral
10-1
Theq
the fi
arisin
mom
grou
simpl
with
confi9
2
DI
In the
degen.
corres
ofthe
r.
The Electronic Structure
and Spectra of
Transition Metal lons
The subject of thi s chapter has also been Ihe topic of several textbooks. (1 - 121
Bere we shall present . n o erview of the electronic struct ure of transition met al
ions. In so doing, we wi ll develop ome important ideas for l he understanding
of the spectroscopy of transi tion metal ion complexes- -our main objective.
Transition metal ion systems are covered separately in this book because their
unpaired electrons introduce several complications. As is so often the case, [hese
complicating factors, when under tood, provide a wealth of inform ation. The
complicat ions invol ve electron-electron interactions, spin-orbit coupling, and the
influence that a magnetic fleld has on systems wit h unpaired eleclrons. We have
discussed many of these topics a rlier, but their fu U implicat ion is best d mon-
strated wilh examples from transition metal ion chemistry.
10-1 ELECTRON-ELECTRON INTERACTIONS ANO
TERM SYMBOLS
There are numerous ways in which one or more electrons can be arranged in
the five d orbitals of a gaseous metal ion. We can indicale the energy di fferences
arising from different interelectronic repulsions and different orbit al a ngular
momenta for these various arrangements with term symbols. Any one t rm symbol
groups together all of the degenera te arrangements in the gaseous ion. The
simplest case to consider first is di. There are five ways to arrange an electron
with ms = + 1/
2
in the five d orbitals. Each arrangement is called a microstate
configuration.
2 O -1 -2
In the absence of externa! electric and magnetic fi elds, Lhe five microstates are
degenerate, and there are five oth rs that are also degenera te with these,
corresponding to ms = - 1/
2
, These ten microstates comprise the tenfold degeneracy
of che so-called 2D lerm (vide infra).
Introduction
Free Ion
Electronic
States
409
410 Chapler 10 The Electranic Structure and Spectra af Transiti an Metat tans
The ground state term for any d" configuration can be dcduced byarranging
the electrons in the el orbitals. filting those with the largest mi values first and
not pairing up any electro ns until each orbital has at leasl one ; i. e.. Hund's rules
are obeyed. The mi valllcs ofthe orbitals containing electrons may be algcbraically
sllmmed to produce the L vallle for the termo More completcl y, the mi quan tum
number for an individual electron is relaled to a vector with component ml(h/ 2rr )
in the di rection of an appli ed field. The M L value is the sum of lhe one-electron
mi alues. Vector coupling rules demand that M L have values of L, (L - 1), ... ,
-L, so we deduce that the maximum MI. val ue is given by the value of L. T he
foJlowing letters are used to indicate the L values: S, P, D, F, G, //, J corresponding
to L = O, 1, 2, 3, 4, S, 6, res pect ivel y. The 2L + 1 arrangements refer to the orbital
degeneracy and are described by M L wi lh val ues of L, (L - 1), ... , - L. As
mentioned earlier, the 2D term symbol describes lhe di case. ft i ten fold
degenera te with a fivefold orbi tal degeneracy corres ponding to ML values of 2
J, O, - 1, -2. In the di ion, the ground 2D term is the only onc arising fro m the
3d orbitals.
The spi n mult iplicity of a state is d fi ned by 2S + 1 (S, n analogy wilh L,
is Ihe large. t po sible Ms' where Ms = r . m ~ and is indicated by the super crpt
to the upper left of the term symbol. The spin multiplicily r f rs to lhe number
of possble projecti ons of S along a magnetic field; e.g., when S = 1, lhe
multiplicity of three refers to Ms = 1, O, -1 (gi ving Ihe z-component of spin
angul ar momentum aligned with. perpendicular to, and opposed to the fi eld).
T/e total degeneracy o/ (/ lerm is given by (2 L + 1)(2S + 1). The value of the S
quantum number for lhe term (or slate) s given by Lhe maxi mum Ms, wruch
equals Ihe Sum of lhe ms va lues of all unpaired electrons. Complete subshells
cOllt ribute nothing to L 01' S, because the sum of the Ins and the m valHes is zera.
Nex t. con ide r the d
2
configuraton. There are 45 ways to ar range two
elcctrons w th ms = 1/
2
n Ihe fi ve d orbtal . Using [be procedures de ' cribed
aboye fo r the microst at e 11 \1 \ l. we see l bat L = 3 and S = 1. Thi
Icads to a 3F ground term that is 21-fold degenerate in the absence of spi n-orbit
cou pli ng. T he other 24 microstates comprise bi gher energy (excitcd) tates; i.e. ,
electron-electron rcpuls ons are largcr for these sta Les. All of the terms ror a d"
configuration can be found by construct ng atable like that shown in Table 10-1
for a d
2
ion. To be sy lematc, we can begin construction of the table wilh tbe
row M e = 4. This ML value can be obtaincd on ly by hav ing two clectrons in
mi = 2, and thi s ca n be done on ly ir lhe spins are paired up. T he re ull ing
microSlate is abbreviated a. 2 2 -. Thc microsta t is placed in the M s = col wnn .
Ncxt, way to obtai n M
l
. = 3 ar s11 0\ n. T he possibilities are 2 r 1 +, 2 + 1 - ,2 -1 ."
and r 1-, corre ponding lo Ms valllcs of +1, O 0, and -1, res pectivel, . The
procedure is repeated ror MI values of 2, 1, and O. The microslates corrcs ponding
to negat ve Al L values are not indicatcd in the tableo They are obtained by
multiplyi ng the M L. values aboye ror lhe posit ive !'vI L microstates by - 1; e.y., ror
M
c
= -3. tbe possibi lit ies are - 2 ' - 1+ , - 2 " -1 , - 2 - 1 t , and
- 2- - 1 . Note that, fo l' cxample, 2+1- is not distinct from 1- 2+ since the
orde r in which we list the eiectrons is rrelevant; but it is di slinct from r I '
becaus in Lhis latt r mi crosLaLe the electron wit b 111; = 2 no longer has ms = + 1/
2
,
Starting wt h the highe t M L value, we can concIude that thcre musl be a
lerm or state and tha! it has MI. components or 4, 3,2, 1, 0, - 1, -2, -3,
-4. A box ' wed to et these c nllgura tions apar!. The choice of the M
r
. = 3
TA
4
2
o
val
m i c ~
Mt
be '1
1 .. - ~
10-1 ElectronElectr on Interactions and Term Symbols 411
TABlE 10-1. Microstates for a d
2
Ion for Positive M
L
Values
(+ +) (+ - ) (- -)

+ 1 (111 o -1
4 12+d
3
(2 ' I
(r l +) (2 ' I- )

,
.,
2
(2+0+) 12+0- 1 (ro +)

e
(2' - 1 +) 12+- 1-1
(2- - 1+)
)(
[I+O+J
[I-O J
:r
le
in
:1).
S
eh
,lis
wo
led
'his
rbit
. e..
,ti"
ll- I
(he
in
by
for
and
lhe
1'
11
'2'
he a
- 3.,
= 3
(2+ - 2+) [1 + - 1+]
12+- 2-1
(2- - 2+)
O
1+]
8[1
-
0-0+
configLlfation fo r the 1G term i. < rbilrary beca use we are only bookke ping with
this procedure. The actual wave function for this component of the lGerm is a
linear combination* of (he two micros tates indicatcd for M L = 3. Rai 'i ng and
lowering operators can be employed
ll
) to produce the wave functi on for gi ven
values of L, M
L
, S, and Ms' The same is true whcnever !here is a choice of
micfosta tes. ow, we procccd to the next highes! lv! L value that remains. namely,
MI- = 3. With 'v/" = +1, 0, -1 component s. it can be deduccd that there must
be a 3F tcrm. This term will be 21 -fold dcgenerate; the 12 mi cros tales. \vith
non-negati ve M l. values, ar bitrarily assigned to it are enclosed with parent hese
in Ta ble 1 l. Next, we come to a ta te with L = 2, whieh must be a single! (i.e.,
S= O). The microstates arbitrarily assigned to thi s 1D lerm are circled. Next , we
enclose with brackets tho se microstate ' of the .1 P termo The remaining term is
1S. Each of these lerms conslilules o de(j merole sel O(SWICS. ([lid me/ lerm diJlers
in energyfrom any olher.t
Each of the microstatcs is rea ll y an abbre\'iati on for a determinanlal \\il\e func tion. ..<J ..
t0ue often Ilnds the individual eigenfunclio ns of a term ,errcd to a'i sta tes. The cnlire terrn
is also referr, d to as a statc. The di fTe rcnce is usually obvious. Hit is 110t, \Ve shall u,e l erlll or Ic,eI
to tht> entire collection of degcncratc , tates and COIIII'0l1m/ for the indi n dual ,tat es .
i
412 Chapter 10 The Electronic Structure and Spectra of Transition Metal Ion 5
The energies for al! of these terms can be calculated(l) and expressed with
the Condon-Shortley parameters Fo, F
I
, and F
4
. These parameters are abbrevi -
ations for the vari ous elect ron repulsion integrals of t he ion. The energy expression
for any term as a funct ion of these param ters is independent of the metal ion.
The magnit ude of the parameters, on the other hand, varies it h [he metal ion.
Forexample, Ee F ) = Fo - 8F
I
- 9F
4
and Ee p) = Fo + 7F
2
- 84F... The tran-
sit ion energy 3 P- 3 F is the di ftcrence between the eoergies of these t wo terms
of J5F1 - 75F4 ' Sim il ar expressi ns exist for all the other lransitions involving
terms of the gaseo u ion. The t:ntire spect r um can be ht with the parametcrs F 2
and F... This is lrue fo r an dI ion.
lo the V( III ) ion, tbe 3F_
3
p tran ition occurs al 13,000 cm-
1
and the JF_1 D
trao it ion occurs at 10,600 cm - l. Solving the tw simul taneou ' >qual ions
Ee p - 3F)= 15F
2
- 75F
4
= D,OOO cm -
l
(1 0--1)
Ee D - 3F) = 5F
2
+ 45F
4
= 10,600 cm -
l
(l 0--2)
,.QL1S
, one o btains F
2
= L310 cm-
l
and F
4
= 90 cm-
l
!2l1G
T he Racah parameter redefi ned the empi rica l Condon-Short ley parameters
so that the separati on belween states havi ng the maximum multipl icily is a
"
"
"
function of onl y a single parameter, B:
"
11 (9) 3p
" r--
,"
(10-3)
A second parameter, e, is needed to express the energy di ffe rence betwe n terms
of di fferent mult iplicity :
____J(::)::
(10-4)
No Electronic Elecl,onic
Interaclions Interactions Rearranging, we obtain F2 = B + C/ 7 and F4 = C/35. Substituting rhese into
d
a
t
d
h
o
s;
(5 degenera te
d orbitals)
FI GURE 10--1 The terms
arisi ng Irom the
electron-electron interactions
in a d
2
gaseous ion. The
number in parentheses
indicates the degeneracy of
each level (excluding any
spin-orbit coupling).
equat ion (1 0-1) and (1 0--2), we obtain:
Ee p - 3F) = 15B
Ee D - 3 ) = 5B + 2e
1
For V(IJI), we find B = 866 cm- and CjB = 3.6.
In summary, the results of the electron-electron int eractions in a dI ion give
rise to a 3 F gro und term and the excited statc, a ri si ng from the d orbitals shown
in Fig. 10-1. The degeneracy of each term is indi cated in parentheses.
TABLE 1 ~ 2 Free Ion Terms lor Various d
n
lons
n Terms
dI
d
9
2D
d
2
da 3F 3p IG 10 IS
d
3
d
7
4F 4p 2H 2G 2F 2D 2D 2p
cJ4
d
6
So 3H 3G Jp JF 3D 3p 3p 11 IG lG IF ID ID IS IS
d
S
6S 4G 4F 40 4p 21 2H 2G 2G 2F 2F 2D 2D 20 2p 2S
10-2 Spin-Orbit Coupling in Free lons 413
By using procedures similar to those employed in Table 10-1, we can
determine the terms arising from various d
ll
ions. The results for n = j to n = 9
are presented in Table 10--2.
The d
9
configuration is for many purposes considered to be equivalent to
the di case, if we think in terms of the degenerate states that would arise from
degeneracies associated with the positive hole that exists in the d
9
case. It may
help to think of d
9
as being a dio case with a positron that can annihilate any
one of the 10 electrons. This concept is referred to as the hole formalismo By the
same token, the following equivalences arise:
d
2
d
8

d
3
d
7

d
4
d
6

10-2 SPIN-ORBIT COUPLlNG IN FREE IONS
As discussed in Chapter 9 (Fig. 9-1 8), the coupling of the magnetic dipole from
Ihe electron spin momenl with the orbital moment, I . S, is spin-orbit coupling.
Variations in the amount of spin-orbit coupling in the different electronic
configurations also lead to splitting of the terms derived so far. Two schemes are
widely used to deal with this effect: the so-called Russell-Saunders or L . S coupling
scheme, and the j . j coupling scheme. When the electron-electron interacti ons
give rise to large energy splittings of the terms compared to the splittings from
spin-orbit coupling, the former scheme is used. With the L S scheme, we
essentially treat the effects of spin-orbit coupling as a perturbation on the
individual term energies. On the other hand, the j . j coupling scheme is used
when a large splitting results from spin-orbit coupling and the electron-electron
interactions are sufficiently small to be treated as a perturbation on the spin-orbit
levels. The j . j scheme is applied to the rare earth elements as well as the third
row transition metal ions. Briefly, in the j . j scheme the spin angular momentum
of an individual couples with its orbital give a resultant
angular momentum, j, for that electron. The indivdual j 's are coupled to
produce the resultant vector J for the system, labeling the overall angular
momentum for the atom. The L S coupling scheme is applicable to most first
give
row transition metal ions, and we shall discuss this scheme in more detail. We
previously mentioned that the individual orbital angular momenta of
electrons, mi, couple to produce a-.!esultant angular momentum indicated by L.
The spin moments couple lo S. The resultant angular momenlum including
spin-orbit coupling is given by J, and the corresponding quantum number J can
take on all consecutive integer values ranging from the absolute values of IL - SI
lo IL + SI . For the ground term, the minimum value of J refers to the lowest
energy state of the manifold if the subshell (e.g., the d orbitals) is less than half
filled; and the maximum value ofJ refers to the lowest energy state when the subshell
is more than halffilled. If the shell is half filled, there is only one J value because
L= O.
Our discussion in this section can be made clearer by working out sorne
examples. The box diagram for t he ground state of the carbon atom is:
414 Chapter 10 The Electronic Structure and Spectra 01 Transition Metal lons
2p
1s 2s +1 O - 1
lliJ
[TI] 11 11 1
T he value of lhe L quantum number, obtained by adding the mI valucs for all
the electrons in incomplete orbitals, is 1 for carbon: L = + J + O = 1. This L
value corresponds to a P state. The sum of t he pn quantum numbers (m
s
= 1/ 2)
for a l! unpaired electron , is 1 for carbon : S = 1/2 + 1/ 2 = 1. The multiplcity is
thr , and the term symbol for the ground sta te s J P. The values for J (given
by IL - SI, .. , 1 L + S 1) are 1L - SI = 1 - 1 = 0,1 L + SI = 1 + 1 = 2, so J = O,
1, 2 (one being the only integer needed to complete thc series). T he subshel!
involved is less than halffilled, so the state with minimum J has the lowest energy.
The term symbol for the ground s tate of carbon is 3 Po, wi th the zero subscript
referri ng to the J value.
The box diagram for the ground state of V
J
; IS
+2+10 - 1-2
11 11 1
with term symbol 3F
2
(L = 3, S = 1, J = 4,3,2). An excited state fo r thi s species
is represented by 11 1 1; thi s microstate belongs to the term with
term symbol 1
4
(L = 4, S = O, J = 4) For nitrogen wth a box diagram
11 11 11 1, L = O, S = 3/ 2, and J = 3/ 2 so the term symboJ 4S
3
/
2
results.
Note that with L = O there is only one J value becausc 1L + SI =
IL -S I=3/
2

For practice, one can determine the following term ymbols for the ground
' tate of the elements in parenthe es : 3P
1
(S), 2P3/2 (e l), 3F
1
(Ti), 5D
o
( r), .JF
4
(Ni ), 3Po (Si), 4S3/2 (As), and 4/ lJ 1 (Pr).
Two parametcrs, and A, arc commonly used to describe the magnitude of
the energy of the spin- orbit coupl ing interaction. The parameter is used lo
describe lhe spin-orbil coupling energies for a single eleclron. It measures the
strength of the interaction between the spin and orbit al angular momenta of a
single c1cctron of a particular microstate, and is lhus a property of the microstate
and not of the termo The operator is l' S. T hc vaJue of is given by
(l0- 5)
where <r -
3
>is the average value of r- J , m is the mass of the eJectron, c is the
speed of Iight, and Zcrr is the effective nuclear harge.
lhe parameler J. IS used Ca describe che Cerm [he operator now beco mes
J.L' S. The va lues of J, a nd are relaled by
A= (1 0-6)
0- 6)
10-2 Spin-Orbit Coupling in Free lons 415
Theparameter isfundamentally a positivequantty. rrtheshell is Icss than half
filled, lhe sign ofJ. is positive; if il is more than halr filled, J. is negative. This
makes sense irwe think in terms ofpositive holes requiring the sign ofequation
(J0--5) tocha ngefor theconfigurat ionsofmorethanhalf-tilled shells.1nsummary,
then,for a shell that is less than halffilled, the lowcst valueof} corresponds to
the lowest energy a nd le i positi e.
Anequivalentopera torform forLSisgiven by l ll(J2 - 13 - S2) when the
stales can be characterized by quantum numbers L, S, and }. The spin-orbit
contribution to the energy ofany le el is then given by:
v.[}(} +1) - L(L +1) - SeS +1)J (10--7a)
Theenergy difference between twoadjacentspin-orbitstatesin a term is given by
I'lEJ.J+I = j ,(}+ 1) (10--7b)
Forexample,theenergyseparation between the} = 3and } = 4statesofa term
is 4J.. Fur/hermore, in Ihe L .S scheme, spin-orbi/ splil/in{j occurs so as lo preserve
the cC' l// er o{ {j ravi/y ol /he energy ol lhe term, i.e., the average energy remains
the same. The ground statefor a d
2
system, JF, has } values of4,3,and 2,wit h
2 lowest since the shell is less than half fi lled.The complete gr lI nd stalt: term
symbol is 31-"2' The IDexcited state has only one possible } stat , equal to 2.
1S J2.2. ___..:.(.;..:1
J = O
. ___ _ J = 4
(5)
J = 2
Jp (9)

\', (3) - >-
\ '--:"""":""_- J =1
\ (1) -2>-
J = O
FIGURE 10-2 Spin-orbi t states from a
10R __ -,(--,5)__
d
2
configuration. The spli tting of the JF?
J = 2
state by a magnetic fl eld He is indicated
on the far lower rlght.
(9) 3>-
I
J = 4
I
I
I
I

\\
\ \
\ \
\ \
\ \ (7) - >-
\ J 3 =
\
\
\
\
,-- 2
/
\
\
\(5)- 4>-
J =2 /
/
--
O
\ '-- -1
,
' -- -2
e - e- >- L.S
He
416 Chapter 10 The Electronic Structure and Spectra of Transition Metal lons
For the excited state, 3 P, we have J = O, 1, and 2, whereas 1 G has only J = 4
and IS has only J = O.
Now, using equation (10--7a), we can calculate the spin-orbit contribution
to the energies of all the J states. For the ground leve! of 3 F where J = 2, we
obtain e/2)),[2(2 + 1) - 3(3 + 1) - 1(1 + I)J = -4X This result is summarized
in Fig. 10--2 along with the results of similar calculations of the effects of icl. S
on al! the states of a d
2
system. Not al! the degeneracy is removed by spin-orbit
coupling, and the remaining degeneracy, corresponding to integer va!ues of M
from J to -J, is indicated in parentheses over each leve!. Note that equation
(10--7b) is obeyed and the center of gravity is preserved. For example, in the 3p
term, the degeneracy times the energy change gives 5}, - 3), - (1) (2):t = O. The
degeneracy o/ the individual J states is removed by a magnetic fie/d. The splitting
into the M states is indicated only for the ground J = 2 term in Fig. 10-2.
Crystal Fields 10-3 EFFECTS OF LlGANDS ON THE d ORBI TAL
ENERGIES
We usually do not work with gaseous ions but with transltlOn metal ions in
complexes. There are two crystal field type approaches to determine the effects
that these ligands in a transition metal ion complex have on the energies of the
d orbitals. The metal ion electrons in a complex undergo interelectronic repulsions
and are also repelled by the electron density of the Lewis base (ligand). When
the repulsions between the metal electrons and the electron density of the ligands
is small compared to interelectronic repulsions, the so-called weak field approach
is employed. When the ligands are strong Lewis bases, the Iigand electron-metal
electron repulsions are larger than the interelectron repulsions and the slrong
field approach is employed.
The basis set used in these problems can be the orbitals represented by
complex wave functions whose angular dependences are given by the spherical
harmonics
Y2 0= (5/8)1 /2 (3 cos
2
e- 1)' (271r 1/2
Y2 1 = (15 / 4)1 /2 sin ecos e (2rr) - 1/2
e
i'P
Y 2 = (15/ 16)1 /2 sin
2
e. (2rr)-1/2
e

2i
'P
2
Alternatively, the real trigonometric wave functions, which are linear combina-
tions of the complex orbitals taken to eliminate i, can be employed. These are
given by:
d
z
' = 10)
d
yz
= (il 2)[1- 1) + 11)J
d
xz
= (1/ )2)[1- 1) -ll)J
d,y = -(if)2)[12) -1- 2) J
d(x' - Y' l = (l / }2)[12) + 1- 2) J
10-3 Effects of Ligands on the d Orbital Energies 417
rn the weak fi eld appr a h, lhe free-ion term sta le igenfunctions (which
take into account lhe inlerelectronic repulsions in the d-manifold) ar empl o ed
as the basis set. As an example, for lhe 3 F lerm, lhe wave functions corre ponding
lO MI.. = 3, 2, 1, O are lIsed. They are abbrevial d as 13 ) , 12) , etc. The
Hamiltoni an is given as :
where [a is lhe free- ion Hamiltonian and Vis takcn as a perlurbati on from the
ligand electr n density on Ha. The perturbal ion, V, ha a drastically si mpli !1 d
form incorporat ing only the electroslalic r pulsion fro m Ihe li ga nds, hich are
represented simpl y as poinl charges. For an octabedral compl ex, the pertu rbal ion
i given by:
(,
V= eL,/r;j (10-8)
i = l
where e is lhe charge on lhe electron, Z; is lhe effecl ive charge on the ith liga nd,
a.nd r
ij
is the dislance from the d-el eclron (l hi s i a di problem) to the ilh charge.
This is lo be compa red to the full Hamiltonian given in Chapt r 3. U ing the
implifi cd Ha miltonia n [equat ion (l0-8)J leads to crvstal .field theory. Ir i' 1 be
emphasized that this formulati on of the problem simply describes th electrostatic
repulsion betwe n the d- \ectr ns a nd the ligand elect ron density, and as such
can leH us directly ol1ly about relative cnergics of lhe d orbitals.
In order to evaluate the integrals ( M L 1 VI !vi L'), ,7 is written in a form that
facilita tes integration(2.31 When this is done, many quantit ics related lo lhe radial
part of the malrix elements appear in the secula r delerminant wilh lhe f rm
IMZe
2
r
z
- 4a ' ). Here, /" 2 - 4 corresponds to the mean fourth-power radi us of lhe
d-eleclrons of the central ion, a is the metal-ligand distance, and Ze has lhe same
units as e. This radial quanlity is rderred to as IOD q and has units of energy.
It is informative to write the secular determi nant for an oct ahedral complex
with this Hamiltonian acting tlpon a di configuration. Employing the complex
d-orbi lal basis set, we ob.tai n
12>
11 ) 10> 1-1 > 1-2>
12>
Dq - E SDq
- 4Dq - E
II>
=0
re
6Dq - '
1-1 )
10)
-4Dq - E
1- 2) SDq Dq - E
This givcs roots
E( l l ) = -4Dq
E( I -1 ) = - 4Dq
E(I O) = 6Dq
418 Chapter10 The Electronic Structure and Spectra of Transit ion Metal Ions
60q
E
N
E
R
G
Y
- 40q
FIGURE 10-3 Splitting 01
the one-electron d orbitals by
an Ohcrystal lield.
and the det erminantaleguation
12) 1 - 2)
12) I Dq- E
5Dq 1=0
1- 2) 5Dq Dq - E
Thi sdetermina ntis solved to produce two energies:oneat - 4Dq andoneat6Dq.
As in a Hckel calculation, the energies can be substituted into the secular
eguations writl en from the secular determinant, and lhe wavc functions thus
obtained. The resll lts are
t/l4 = - ir 1/2(12) - 1- 2)
and
These are the wave functions ror the d
xy
and d
x
' _ y' orbitals, l he Jatt r potnt rng
at th ligands a nd th former in belween the ligands. Note that the octahedral
crystalfield mixes the 12) and1- 2) wave/ul/ctionsamimakesit moreconvenient
toemploy the real d<y andd",- ,r' orbitals in the description o/the complexo Since
lhe deg neracy of11 ) and 1- 1) is not removed lhe wave runclions t/IIto "'3
can be considered as the real or imaginary combinalion as is convenicnt. These
results are summarized in Fig. 10- 3, where it can be seen lhal lwo degen rate
sets of orbitals resll lt which are sepa raled by 10Dq. Thus, wc cxpect one d-d
el ectronic transit ion ror a dI systcm with an energy corre ponding to 10Dq. In
Oh symmetr , t he th r degeneratedc'd
y
:,and d
x
. orbitl ls lransform as t29 and
v
lead to the 7 ~ g ground state,whi l d:, a nd d,,'_\' . lead to the 2Egexcited state.
Thefollowinginformat ionisconvey d byt he esymbols : (1)thesymbolTindicates
tha l the state i orbitall y triply degen rate and E doubly degenerate ; (2) the
.uperscri pt 2 indicatesa ' pnmulti pli ty oftwo. i.e. ,one unpaired elect ron ;and
(3) t he 9 indicates a gerade orsymmetricstale.
Ncxt, weshall treata weak field, octahcdral d
2
complexo Oll rinitalconc rn
wiJl be with the 3F term described by the basis set 13) ... lO) ...1-3).Si nce
our bass set ror 3F consistsofall Ms = 1fll ncti ons, this has been dropped from
the symbol and only ML is indicated; i.e., 13, 1),etc., would be a more complete
de. cription. We shall not present the wave functi ons for the e basis functi ons.
Procedu res for obtaini ng lhe e wave functi ons llsing the raising and lowering
opera tor arepr sented by B llhausen.(l )Tbeseculardeterminanti gven below:
13) 12) 11 ) 10) 1-1 ) 1-2) 1-3)
01
- 30q- E 15
1
!20q
<21
70'1 - p; 50q
<I 1
- Oq - E 15
1
/2 Dq
-60q - E =0
<- 11
<1
15
1
/
2
Oq - Oq - p;
50q 70q - E
<- 31
<- 21
151/
2
Dq
- 30'1 - E
TI
r
E
N
E
R
G
Y
~
10-4 Symmetry Aspects 01 the d Orbital Splitting by Ligands 419
The solulions are
El = -6Dq Es = 2Dq
E
2
= -6Dq E = 2Dq
E3 = -6Dq E7 =12Dq
E4 = 2Dq
The energies* and wave functions for the respective levels are indicated in Fig.
10-4.
120q [2-
1
/2 (12) + 1-2)]
/
2
[24-
1
/
2
(313) + 15
'
1-1)]
[24-
1
/2 (31-3) + 15
'
/
2
11)]
2Dq [2-
1
/
2
(12) - 1-2)]
-6Dq [24-
1
/
2
(1 5
1
/
2
1- 3) -311)]
[10)
/
2
[24-
1
(15
1
/
2
13) -31-1)]
FIGURE 10-4 Splitting of the JFterm 01 a d
2
ion by an Oh
crystal l ield .
In this analysis, we have ignored any coval ency in the mctal-liga nd bond.
As a result,if we were to attempt a quantitati vecalcul at ia n ofDq, il would diITe r
consid rably from t hat fo und experimentall y. Liyand field theory admits to
coval encyin thebondandtreatsDq (andolherparameterslobedi cussedsho rtly)
as an empirica l parameter that is obtained from l he lectronic spectrum. The
formulation 01' lhe probJem in all other respects is ident ical.
10-4 SYMMETRY ASPECTS OF THE d-ORBITAL SPLlTTING
BY LIGANOS
As is usually the case when a vast ly simplifi ed Hamilt onian is employcd. the
correct predict ions fr om the melhod aresymmetry determined. Forexampl e. we
men ti oned in Chapt r 2 that appropriate combinat ions or the binary products
orthe x, y, and z veclors gave the irreducible represenl at ions ror the d orbitals
and their degcneracies. Wc can use princi pies already covered (Chapter 2) to
illustratea procedure ror derivi ngall orthestate arisi ng[romone-elcctron levels.
This procedurecan then beextended ina traightforward wa lo deriveallorthe
states arising ror variou. mullielectron confi gura ti ns in various geomelries.
We begi n by xamin ing tbe effect of an octahedral field o n l he t tal
repre " nt ati onforwhich th etord wa efunctions for msl he basis.Todetermine
this total representat ion, we must find Ihe elements ofmatrices that express the
* Dq is deftncd for a onc-clectron system. For a polyeleclron systcm, une should employ a
difIerent D4 valuc for each st at e. (C 1. Ballhausen and H. B. Gray, " Chemis try of Coordinati on
Compounds," Volume 1, ed. A. E. Martell, Van os trand Reinhold, Princeton, .J ., 1960.) Thls is
seldom done in practice because ofthe er ude nature ofthis f1l odel.
420 Chapter 10 The Electroni c Str uctur e and Spectra of Transi tion Metal lons
effect upon Our basis set ofd orbitals ofeach ofthe syrnrnet ry opera tions in the
group. Thecha racters ofthese matriceswill cornprise the representation we seek.
Since a ll of t he d orbitals are gcrade, i. e. syrnmetric to inversion, no new
informalion wi ll result as a conseq uence ofthe inversion ymmetry opera ti on.
T hus, we can work wil h the simpler pure rotal ional subgroup O in t ad ofOh'
Ir you need to convince you rselfofthis, note that in any groupcont aini ng i (e.g. ,
D411 or e311)' the corre po nding rotati on group (e.g ., D4 or 3) has the same
irreduci bler presentat ionfor lhebina ry productsexceptforl heu andg subscri pts
in the former group. Recall that lhe d wave functi ons consist ofradial. spin,and
angular(e ane! q;) pa rts.The radial part is neglected, fo r it is nondirectional a nd
hence unchanged byany yrnrnetryoperation. Weshall assume thatthe pi n part
is independen! of the orbita l par! a nd ignore it for now. The a ngle Uis defined
relative to the princi pal axis (i .e. , lhe rotation ax is). so it is uncha nged by a ny
rotation and ca n be ignored. Only q; will change; lh forrn of thi s pa rl of lh
wave functi on i giv n by e il/l /; ,. (Forthe l orbital .! = 2 a nd 11'11 has values 2 1,
O, - 1, - 2.) Towork ou l lheeffects ofa rotation by rx on e
inl
,,,,. we note lhals uch
a rotat ion causes t he followi ng cha nges:
2 i rp
e
e
i
",
O
e
e-
irp
e - 2irp
e 2'(", f

rOl a re
---------->
e
O
by a
- 1(",+.)
e- 2i (rr+ 2)
The rnat rix that operates on our d-orbital ba is set is
O
O
O
O
O
O
O
O
L.l
A general forrn ofl hi matrix for the rotation ofany set ofor bilals is givcn by:
O O
O
[r
O
O O
When'X =O,eachelernentisobviouslyone.We givelhe traceofthis la tlerrnatrix
wi thout proof* as:
sin (t
(10-9)
X( rx ) =
The quantitics summed rorm a geometri c progrcssi on.
j
d
.(
d
.y
le
l.
:h
by:
ltrix
10-9)
10--4 Symmetry Aspects of the d Orbital Splitting by Ligands 421
where rx =1- O. From the trace determined with this formula, \Ve have the character
of the representation for any rotation operation. Substituting directly into this
formula, we find that the total character for the C
3
rotation of the five el orbitals
is given by
-1
Characters for other rotations can be worked out in a similar way. To obtain
the characters when rx = O and rx = 2n, one must evaluate the limit of an
indeterminate form, e.g.,
sin (t + (2n)
O
--> -
SIn n O
Using I'Hopital's rule, one obtains
x(O) = 2t + 1
x(2n) = 2t + 1 for integer t or
-(2t + 1) for half-integer t
Thus,.for the identity, rx = Oand X(E) is given by 2t + 1. Referring to the character
table for the point group and using the aboye formula to determine the
characters for the various operations on the five d orbitals, we have:
E
5
Using the decomposition formula, we obtain the result XT = E + T
2
. Since the d
orbital s are gerade, we can write this as
This was the result of our crystal field analysis. By a similar symmetry analysis,
the results summarized in Table 10-3 can be obtained.
We could work out the effect of other symmetries on the one-electron leveIs
in a similar way. AlternativeJy, one can use a correlation table that shows how
the representations of the group Oh are changed or decomposed into those of its
sub-groups when the symmetry is altered. TabJe 10-4 contains such information
for sorne 01" the symmetries commonly encountered in transition metal ion
complexes.
With the irreducible representations given in Table 10-3 for various atomic
orbitals in Oh symmetry and with the correlation table given in Table 10-4, we
can ascertain the irreducible representations of the various orbitals in different
symmetry environments. The results for single eJectrons in various orbitals apply
422 Chapler 10 The Electronic Structure and Spectra 01 Transition Metal lons
TABLE 10- 3. Representations lor Var ious Orbitals
in Oh Symmetry
Type 01
Orbital Value Irreducible Representation
D
s o
alg
P
1 t) u
d 2 eg + e2g
f a2"+e l "+t Z"
3
g 4 a
l9
+ eg + t19 + t
29
h 5
e" + 2e 1" + t 2u
6 Cl
l g
+ Cl 2g + e
g
+ (19 + 2t
l g
a he sub, criplS 9 and 11 are dClcrmincu by Ihe 9 or 11 nalure of
Ihe alomie orbital s invol"cd When I is even, lhe orbital is gcrade ;
when I is odd, lhe orbil a I is ungerade.
TABLE 10-4. Correlation Table for the Oh Point Group
Oh T
d O ... l d C., C .
0-",
O, C. Io

"
A 19 Al Al A 19 Al Al Al Al g
A, Ay
A29
A
2
A
2 Bl9 B l B l
A
2 Al 9 Al By
E9
E E
Al9 + Bl 9 Al + Bl Al + Bl Al + A
2 E9
E Ay + B.
T
l9
TI TI A29 + E.
A
2
+ F. A, + E A2+ B l+ B2 A 29 + Ey A l + E Ay + 2By

T
2
T
2 B29 + E9
B
2
+ E B; + E A,+B
l
+ B
2 A 19 + E. Al + E 21'1" + By
Alu Al A
2 Alu Bl
A
2
A
2 Alu A l Au
A
2 rl
A
2
Al B
lu
A, B
2
Al
A2"
/ 1
2 B"
tu
E F:
Alu + B l" Al + Bl A
2
+ B
2 Al
A
2
Eu E Ay + Bu
TI .. TI
T
2
A
zu
+ Eu B
2
+ E Al + E Al + B l+ B2
A 2 " +f "
A, + E
A" + 2Bu
T
2 ..
T
2 TI B2u + E" Al + E Bl + E A
2
+ 8
1
+ B
2 Alu + E"
A; + E 2..1" + Bu
to the terms arising from multielcctron systems. For exampl e, we can take
the 3F, 3p, tG, ID, and lS terms of the d
2
configurati on and treat them likef,
p, g, d. and s orbitals. The 9 or u subscripts given in Tabl e 10--3 \Vil! no! apply,
but wi II depend upon the 9 or u nature of the atomic orbitals in olved. Thus,
Table 10--3 appli es to tcrms as well as orbi tal s. The D term, for example, is fivefol d
degenera te like the uve d orbital s, the former bei ng described by a wave functio n
fo r each of the five M L val ue . These wave func t ions have l <I> part gi ven by
Combi ning Tables 10--3 and 10--4, we can sec that the D slate of (he free ion
splits nto E9 + states in an octahedral fi eld and int o A
1g
+ B 19 + Eg + B 29
states in a tet ragonal D
4 h
fi ell! . Simila rl y, l he 3 F term gives rise lo A29 + '[19 +
in an octahedral fi eld and B 1 + Al + 2E + 8
2
in a e4" ield.
11l--4 Symmetry Aspects of the d Orbi tal Splitti ng by Li gands 423
Next, we shall consider the states l ha t ari se fr om a d
2
confi gurat ion when
the crystal field is la rge compa red to the interelcctronic repulsi ons* T he
interelectronic repulsi ons are treated as pcrturba ti ons 011 the strong fi eld
d-eJectron configu rali ons. In other wo rd , the a ri ous crys tal lield sta tes a re
identified, eigcnfunctions are constructed and el/rij is used as a perlurba ti on.
The terms are readily wri tten for t he vari ous d" configurations. For dI , l he two
terms a re 2T
2g
and 2 E g . The lemlS t hat a ri se from a conn.guration with an
additi onal electron, d"+ 1, are given by lhe direcl product of the d" tcr m ymmelries
and thal ofthe added el ct ron. For d
2
, we have 1
1
/ , t
2g
l eg 1, a nd e/ a rrangements.
Accordingly, for t
2g
2, we ha ve
(2=)'
q!(2! - qj'
For" 1
1
/ conliguration, we have :
(2 x 3) I _

2 1(6 - 2)! .
[
61 -![ 4
1
]
2 . (6 - 2)! 11 (4- 1) ! = [1 5] ' [4J =60
t
2g
x e
9
whieh leads to T
l 9
+
and for e
y
2, we have
e
g
x e
g
which leads to Ea + A 19 + A
29
ext we have to dctennine lhe multipl icity of these lerms and show the
connecti n of these slrong terms to lhose of the gaseous ions. The multipLicities
are detem1i ned by the method o[ descending sYlnmetries( I.2l By considering the
e/ confi oura tion, we can show Ihal whcn w low r lhe symmelry fro m O" lo
D
4 h
tu remove l he dcgcneracy, lhe el terminati on of l he spi n degeneracy becomes
straighl forwa rd. T hc correlal io n lable (Table 10-4) shows
*The 10t al t hal ex ist s ror a systcl11 or q filling a subshcll wi th zdegenerate
(l rbitals (each occupied by lWO electrons wi th opposi tc spin) is gi ven by:
./
424 Chapter 10 The Electronic Structure and Spectra of Transi ti on Metal lons
In addition to the orbital correlation shown aboye, it is important to
remember that sta tes behave in the same way. In D
4
/ , a
1g
2 must be 5inglet because
1
of the Pauli principIe. For example, a
1
/ leads to a
1g
x a
1g
which leads to 1 A l y'
while b 1/ leads to b Ig X which leads to 1A Ig' and a
1g
l b 19 1 leads to b Ig X b
19
a
19
which leads to lB
19
or 3B
10
. The states in octahedral symmetry (A
1g
, A
2g
, and
E g) must change to those in D
4h
symmetry as shown in the group correlation
table (Table 10-4) and as summarized below:
Oh D
4h
-----+
A
A1 9
19
A
29
---+
B19
Eg
---+
AlU
~
Bg
We have determined the multiplicity ofthe D
4h
states; since low ring the symmetry
cannot cha nge the spi n d generacies, we can work backwards to determine the
spin degeneracy of the O h states. T he 1 AIg slate in D4 h must correspond to a
singlet lA in O h. T he other l A must a rise from E , requiring that this be l E
1g
.
19 19 g
The B Ig state in D
4h
arising from 1 E I g must also be a singlct. We are left wi th
the fact that 3B
19
in D
4h
is associated wi th A
29
, req uiring this to be 3A
2o
.
O h D
4h
1 A ---->
A
1g
eA
1g
)
19
3B
1g
---+ A
2g
eA
29
)
lA
---+
19
Ei
1
Eg)
~
lB
1g
The t
2g
2 confi guration gives rise to A Ig + ~ g + T
1y
+ T
29
states. We must
examine the correlation lable ror these states in Oh symmetry and find a lower
symmetry that converts t hese states to one-dimensional representations or a sum
of one-dimen ional representations. Table 10-4 shows that C
2h
and e
2
" sati sfy
this requirement. The results for C
2
/
1
a re summarized as
Oh
C
2h
----> A g A
19
~
E g Ag + By
Tg
---->
Ag + By + B g
T
29
--> Ag + Ag + B y
10--4 Symmetry Aspec ts of the d Or bi tal Splitting by Ligands 425
lo
Since1
2g
inOh gives rise toa
g
+ a
g
+ b
g
orbitalsin e2h' thepossibl configurations
are {9 12 , Clg l l ag2 1, ay ,'bg' , (/ g/' <1Q2Ibg' , b/ . As pr vi oll sl y:
(/y I X a
g
I to A g
a
g1
x a
g2
leads to Ag
a ! x by lead:. to B
g
"
x Cl'l2 lcads to A,) a
92
x b leads to By a
9 2 g
by X b
g
leads to A9
Thesllbscripts 1 and 2 on the a
g
orbital ar used lo distinguish lhe two different
ay represent at i ns that result fr om t
2g
in this lower symm try. Since lh fi rsl,
fourt h and sixth blIl ary products It sted correspond lo both eleetrons oceupylllg
thesameorbital *(a
y
, a
9 2
, andb
g
, respecti vely),t hesemust be singletsta tcs: A
g
,
lAg . and l Ag,re pectivcly.T hesecond,thi rd,and nfthbinaryprodll ctscorrespond
to lectronsin r ntorbital a ndgi verisetosingletandtripletstate :l Ag + 3A"
and 2 1B9 + 2 3B
g
. The resu[t in C
2h
is slI rnrnarized in t he left colurnn
10--5. In the right-hand column, we c nnect up the corre!ating sla tes in 0
1
, from
Table 10--4. Si nce we have three triplel ta tes in e211 of Bg. Bg, a nd Ag yrnrnetry,
these musl ariserrom 3 T g. Al! ofthe ot her _tatesfrom 1
2
/ aresinglets. Nool her
possible correspondence eists. One can work wi t h the t lglegl conngura t ion in
a si milar manner.
Summarizing the aboye procedur we note that \Ve have u d the method
ofdescent in symmetry as foll ows:
1. The orbi t als in tbe highersymmctry are eorrelated with the orbit a l in
the lower symmetry.
2. Thc required number ofelectrons are added to Ihese lower symmetry
orbit als.
3. T he el etronic states resulting from the elect ron configura ti ons in the
lower symmetry are detem1ined.
4. The lower symmet ry el ect ronic state , including spi n multiplicity, a re
correlated with the electronic states ofthe higher symmel ry case. (This
is, in effect, an aseent in symmet ry.)
The terms ofthed
3
l rongfield eonnguration a re given by taking the direct
product ofthe terms for d
2
wit h t
2g
and e for the added electron.
g
Next,we have to show h w t h term Ihat arise in a st rong fi el d are related
to those in a weak fi eld, fo r there must be a continuous cha nge fr om one to the
other as a fu nction of the li ga nd ficJd st renglh in a series of complexes that a
givenmeta lforms.Wecanillustratet hi swithad
2
ion byemployingtwo princi pIes:
L A one-to-one cor respondence exists between the sta tes of the same
symmetry and pin multpli city at the weak field and st rong field
extremes.
[f \Ve label the orbitals 1,2,and 3,we havc 1x 1, 1x 2, 1x 3,2x 2,2 x 3, and 3 x 3. For
1x 1,2x 2, and 3 x 3, we have lwo elcctrons in lhe sa me orbil al.
TABLE 10-5. Relation
of the Mu lti pliciti es in
C h and Oh
o"
- --- --
---
426 Chapler 10 The Electranic Structure and Spectra af Transitian Metal lans
FIGURE 10--5 Correlation 01
the strong and weak field
states of a d
2
ion.
2. States of the same symmetry and spin degeneracy cannot cross as the
Ii gand field strength is varied.
Figure 10--5 contains the free ion and corresponding weak field states on
the left and the strongfield st ates on the right. The configurations in an infinitel y
strong field are indicated on the far right.
'5
',:' 1 e
2
----- - ---- ----;;:-- ---
Free Weak
Ion Field
If we begin with the infi nilely strong fi eld e
2
configuration, we note a ! A
statc.Thereisalso a ! Al stat int /.Only irtheconnections are madeasshown
can we avoid cros'ing.The same is lmeror ! E. Sinee there is only one J A
2
state
in the weak field, this connection is straightforward. Proceeding to lhe other
stales from /2e and t/, only the connecti onsshown will lead to non-crossing of
states wit h the same symmet ry and multiplicity.
The resul ts oftheevaluation ofenergies ofthe va ri ousleveIs in going from
weak fi eld to strong fi eld cases are presented in graphical fo rm in the Tanabe
and Sugano diagrams(!J1 contained in Appendix e fo r variolI sd" conflgurations.
The energies are plottcd as E/ B versus Dq/ B, where B is the Racah parameter.
Thequantities E/ B and Dq/ B are plotted because they enableone to convert the
equalionforthe nergyintoaconveruentfor mfor plott ing. Sincestatesofdifferent
mult iplicities areinvolved, they area function 01' theRacah parametereas well
as B. Therefore, the diagram can be consl rucled onl y for a givcn ratio of C/ B.
The 1 wesl term is taken as lhezero ofenergy in these diagrams.
SIrong Inllnltely
Field Strong
Feld
1G--5 Double Groups 427
e/B.
The Orgel diagrams a re used to present some of the information in the more
complete Tanabe and Sugano diagrams. Orgel diagrams contain only t hose terms
that have the same multiplicity as the ground state. Accordingly, they suffice ror
the interpretation of the electronic spectra of multiplicity-allowed transi tions and
will be employed often in the rest or the chapter (e.g., f ig. 10-9).
10-5 DOUBLE GROUPS
We have previously shown how to use the character tables to find the character
or the represent ati on for which the p a nd d orbitals form a basis in various
symmetries. In the preceding section, we showed that for any sym metry operation
corresponding to a rotation by an a ngle a on an orbital or state wave fun ctio n
having an angular momentum quantum number 1, or L, the character x(a ) for
which this forms a basis is given by equation (J O- ):
sin (t + Da
x(a) = - Sin ( :: 2 - '----:--:'
This equati on can also be appli ed to those states characterized by total
angular momentum J (where J = L + S) by si mply substil uting J for t . W hen
there are an even number of electrons and J is an integer valuc, the total
representation in a ny ymmetry ca n be decompo d into the irreducible rcpre-
entations of the point group as done in the prcvious section. However, whcn J
is half-integral (i .e., S is odd), a rotati on by 2n (which is rhe identity operation)
does not prod uce the identi ty for the character:
sin (J + + 2n)
x(a + 2n) = . [(IX + 2n)]
Sin 2

- ---' S-i - = - X( a)
It can be sho 11 that rotation by 4n is needed to produce t he idcntity. To
avoi d Ihis difficulty. rota tion by 2n in this instance is treated as a symmct r
operation t hat we shall label R. T he ord inary rota ti on group is ex panded by
taking the product of R wi th all existing rotations. The new group is called a
double group . U ' ing equat ion (10-9), t he cha racter rOY the rotat ions can be
worked out. T he characters of E a nd R (i .e., a = Oand rJ. = 2n) require evaluation
of t he mit of the indeterminate form
428 Chapter 10 The Electroni c Structure and Spectra 01 Transit ion Metal lons
*S. Sugano. y. Tanabe, and H. K amimura, "Multipl ets of Transiti on M etal f ons in Crys l a[s."
Academi c Press. New York;-1970.
I
an
leading to X(O) = 2J + 1 and x(2n) = 2J + 1 r r int eger J or -(2J + 1) for
half-i ntegerJ, as men tioned bef re. The character tables for the r tati n do uble
groups D4' nd O' are gi ven in Appcndix B. Those for othcr groups have been
reporlcd. * Two commonly encountered sysl ms for labehng l he irreducible
representations are gi ven. One ti es a seria ll y indexed sel of 1:5, a nd the other
usespri medsymbolssimil ar toIhoseweha ebecnemploying. hed irectproducts
ofr pre entations ofdou ble groups can be taken as before and r duc d lo sums
ofirreducible r pr sentations.
The a boye d iscussion ca n be c1arified by consideri ng some examples. We
need t errlpl oy double groups to determine t he efli cts of spin-orbit coupling
when J 15 hal f-integral. Si n spi n-orbit effect s ari se from coupl ing of pin and
orbital momcnta of electrons, we are concerned wi t h the direct product repre-
entat ion of t hese t wo effects. As an example, we shall work out the efTect ofan
oelahedral fi eld and spin-orbit coupling on the 4F free ion state ofa d
7
ion. As
in Ihe previous section, we can work out th total represcnla tion in the O point
group and factor it to obtain
,
\
\
\
,
\ 4F (2 8)
~
I
/
/
/
/
/
/
/
/
J =%//
Free
Ion > AL S
:::::; AL S
Oh l e / ~ Oh Fl-elt!., Free
Ion
(G)
(A)
(B) (C) (O)
AL S >
Oh Fleld
(E)
FI GURE 1(Hi (A) The gaseous ion , (B) split by a strong Oh lield, (e ) lol lowed by
smaller I.L S On the r ight, (G) Iree ion, (F) spli t by large spin-o rb i t coupling, (E)
l ol l owed by a weaker li gand lield. Part (O) i ndi cates the correl at ion 01 states in the
i ntermediate region . For convenience, none 01 the states are shown to cross . States
01 different double-group symmetr ies may cross. States 01 the same double-group
symmetry wi II undergo conliguration i nteraction.
e
s
H
sI
as
b'
is
el l
th
.8)
ay
te)
Ihe
Slales
oup
10-6
A d
7
ion in a weak O" field leads, as shown in the Tanabe and Sugano diagram,
to a 4Tg ground state and 4T
2g
and 4A 29 excited states. In the O' double group,
these correspond to TI ' (r4)' T
2
'(r s), and A 2' (r 2)' respectively. Using S = 3/
2
and substituting S for t in equation (10-9), we generate in the O' point group
an irreducible representation of 1G(ra), i.e., one 0f the new irred ucible represen-
tations of the double group. Now, we take the direct products of the spin and
orbital parts and decompose them as before, leading to
r
2
x r a = r a
r
4
x r a = r
6
+ r
7
+ 2r
a
rS x r 8 =r6+ r 7+ 2rs
As we se e, spinorbit effects do not split r
2
, but the split 4 into four sta tes
and r s into four sta tes. \Ve coul d have con verted L and S to J ancl employed
equation (10-9) on J values of % 7/
2
, %. and 3/
2
to obtain the double group
representations. This procedure would have been folJowed if spin-orbit coupling
were comparable to or greater than the crystal field. U ing the approach empl oyed
aboye, we have assumed a large crystal field and a smalJ pin-orbit perturbat ion
on il. \Ve can summarize the rcsults with the diagram in Fig. 1 6.
T t is important to remember that whenever one is cOl1cerned with the effects
of spin-orbit coupling (as we shaJl often be in subsequent chapters) in a system
wilh half-inlegral J values. the doub/e group should be emp/oyed
1 ~ THE JAHN-TELLER EFFECT
T here is one other effect that inftuences the electronic structure of a complex,
which we should consider before discussing electronic spcct ra. Consider a
molecule with an unpaired electron in a doubly degenerate orbital, e.g., an
octahedral Cu(II) system. Note that by distorting the molecule fr om its most
symmetrical geometry (O h) to, say, D
4
/" it is possible to lower its energy:
e
g
lb +
+
bg
a
l g
t
2g
*1l -rr
~
1+
*
b
2 g
-lt-
tt-
e
g
Oh
~
D
4h
Aere the e set splits into b a nd a g components. Since two electrons are in the
9 9
stabilized a
l g
orbital and only one is in the destabili zed b
l g
orbit al , the molecule
as a whole is stabilized. It is easy to see how this happens by remem be ring the
basis of simple electrostatic cryst al field theory: a n orbital pointing at a ligand
is destabilized. The c10ser the Iigand is, Ihe higher the energy. A tetragonal
elongation (a lengt hening of two M- L bonds on the z-axis and shortening of
the othe!" four on t he x- and y-axes) deslabi li zes the d" _ y2 (bg) orbital and
stabilizes the dl (a 9) orbital. Simi la rl y, a tet ragonal compress ion would raise d=,
and lower d
x
' _ J'. Jahn a nd Tell r fi r t pointed out that , for a non-linear molecule,
The Jahn-Teller Eff ect 429
J
i
430 Chapter 10 The Electronic Structure and Spectra of Transiti on Metal lons
when such a dist o rt ion can occur to lower the energ it will. We thus expect
that Ihere will be a Jah n-Teller distortion any time we have an orbit ally degenerate
(E o r T) stat e and when a proper symmetry vibrational mode exists which enables
the molecule to move from one geometry to the other. One unpaired electron in
a doubly degenerate pair of e o rbitals gives rise to an E state and one or two
unpaired el ect rons in three triply degencrate t orbitals gives rise to a Tsta te.
Note that this criterion is very similar to the criterion for spin-orbit coupling.
A simple one-elect ron picture can be used to pred ict when orbital angul a r
momentum contri butions are expected and when they are not. To obtain o rbital
angular momentum the electron must be in a set of degenerate orbitals that
permit it to move freel y fr oIn one degenerate orbital to the next and, in so doing,
eircul a te around an axis. Consider, for example the d
xz
and d
p
orbi lals of a
metallocene. Degeneracy ofthis pair permi ts cireula tion and a ngul ar momenl llm
a bout the z-axis. All E and T states will have spin-orbit eoupling, xcepl for E
stat es in the Oh and ~ point groups. In t hese la tt erca e ,the E state a re composed
of d. l _ y' and do' so degeneracy does not allow ci rculat ion about an axi s.
Some peo ple, induding Teller, a rgue that, if a state is splil for a ny reason,
there is no Jahn-Teller effect. Ot hers talk about a Jahn-Teller dist ortion combini ng
wi th other factors that remove degeneracy. T his latt er a pproach brings up an
interesting di lemma: When a degenerate state spl ilS. is Ihis d ue t o a Jahn-Teller
distortion, distortion from lower symmet ry components in the struct ure, or
spin-orbil co upli ng? Since lhe magnit ude of these elfects is often comparable (200
to 2000 cm - 1), il may only be possi ble to say tha t the splitt ing is due lO some
unspecified combinat ion of these elfects. O n guideline is thal Ja hn-Teller
distortions are generally larger in E states tha n in T tates, so spin-orbi t coupli ng
is gene rally the dominant effect in T states.
10-7 MAGNETIC COUPLlNG IN METAL ION CLUSTERS
In metal clusters containing t wo or more paramagnetic meta l centers, l he elcclron
spins of the indi vidual metal ions SI' S2 '" S,,, interact. T he int eractiOll between
a pair of spi ns i and j is descri bed by lh Hamiltonian op ralor:
(10-10)
where J in energy units is called the exchange coupling constant or exchange
para meter. It is to be di stinguished fro m lhe J quant um number. With trus
Hamiltonian, t he exchange parameter J is negat ive for a n antiferromagnel ic
interaction, which leads t o a pairing of electrons, and is positive for a fe rromagnetic
int eraction. T he literat ure is confusing in t his a rea, for the aboye Hami ltonian
has be n wri tlen wi t h J replaced by 21, -J o r - 21.
Dimeric copper(IT) acetate di hydra te is the d a sic example of thi s type of
system. T he structure of this molecule is shown in Fig. 1 7, and the metal-metal
ax is is laken as the z-axis. The copper(lI) ions have a d
9
co nfiguration. At 10\V
tempera tures the compollnd is found to be diamagnetic, a nd at eleval ed
lcmpcratures it is para magueti c. We can view thi s system as one in which lwo
molecul a r orbitals exist t ha l are largel y metal d, z_y 1 (wilh a signlfican t contri-
bution from the bridging acetatc). A simpli fi ed representation of this part of the
CH
CH
rnoJ(
t he r
triplt
the l:
pai ri
afl ar
exam
but t
eleva1
. tudie
I
S = 1
slale
When
obtain
W
Acco rdl
wbich u
*Thi
con lrover";
of the two
10-7 Magnet ic Coupling in Metal Ion Clusters 431
FI GURE 10-7 The struclure 01
CU2( CH3C02)4 2H20 The Cu-Cu
dislance is 2.6 .
molecular orbital diagram of the complex is shown in Fig. 10- 8* (Ir necessary,
the reade r is referred back to the chapter on epr to review the discussion on the
tri plet state and exchange interactions.) With ,1 as the energy separatio n between
the bonding and a ntibonding molecul ar orbital s (Fig. 10-8) and K as t he spin
pairing energy, we obtain, when ,1 < K a ferromagneti c system. When ,1 > K,
an antiferromagnetic coupled system result s. T he copper( II) acetate dimer is a n
FIGURE ~ A simplilied
example of the latt er. In Cu
2
(CH3C02)4 2H20. the ground state is diamagnetic,
represenl al ion 01 the
but the excited triplet st ate is c10se by in energy and is thennall y popula ted a t
i nteraction 01 two metal d.>-y>
elevated temperat ures. The value of J is found (1 4) from magneti c susceptibil ity
orbitals in Cu
2
. (CH
3
CO)4 2Hp
st udies (vide infra) to be 284 cm - l.
lo produce two nondegenerate
In the discussion of the epr spectra of diradical s, new states with S = Oand levels.
S = 1 were shown to a ri se (see Fig. 9-22). The general expression for Ihe new
states ari sing fr om the exchange coupling of SI a nd S2 centers is given by:
(10- 11)
When SI = S2 = 1/
2
we obtain S = Oand S = 1. \Vhen SI = 3/
2
and S2 = 1/
2
we
obtai n S = 4,3, 2 and l .
\Ve defi ne a total spin quantum number for the sys tem, S, as
Accordingly
which upon rearra nging defines 8
1
' S2 as
(10-12)
This is rerer red to as a super exchang': pat hw<ty involvi ng 1he bridging acctates. There is
controversy rega rding the amollnt or a dircct exchange cOl1tribution, which in vo lves a direct overlap
of lhe IWO orbital s on each copper.
g
n
r
e
cr
ng
on
'en
lO)
ngc
thi s
eti c
e of
f ctal
tt low
lvated
t\Vo
l1ltri-
orthc
432 Chapter 10 The Electronic Structure and Spectra 01 Transi tion Metal lons
mJ
1
// -- 1 E=+ 4" J+g{3H, J+g{3H,
5=1 /' ,
--f-- --- -- O E= + - J J
'''' ' , 4
" 1
' -- 1 E= + 4" J - g{3H, J- g{3H,
,
,
,
,
, 3
,------ -.-- OE=- - J
o
5=0 4
Energy Separaton
JS,'S2 H
FIGURE 10-9 Energies 01 the levels in a dimeric d
9
system.
Recalling that S21/1 = S(S +1)1/1 , we have the following result:
For dimeric copper(lI) acetate dihydrate, we have
and S=O or S = l
For S = O, we obtain
whereas for S = 1, we obtain
By adding gfJSJI : to equation (10-10) the Hamiltonian becomes
H= gf3SzHz + JS l ' S2 which produces the results shown in Fig. 10-9. Calli ng
the ground state energy zero, we calculate the energy separation to the excited
states by subtracting the ground state energy.
In a similar fashion the reader' is left to show that when a S = 5/
2
center is
magnetically coupled to an S = 3/
2
center, equation (10-11) leads to states 4, 3,
2, and 1with energies from equation (10-14) of 9J, 5J, 2J,and Q. In a magnetic
field, each state will be split into t he Ms components given by S, (S - 1) '" - S.
The wave functions IS, M,) are expressed as li near combinations of l he two
centers ISI' S2' M" M./
2
>weighted by their appropriate coefficients C 1.2 '
o
r
n
rI
ti
ti
d
l1i
t Q
SI
n
rr
a
v.I
p
re
F
e
t '
tr
01
t
10--8 Survey 01 the Electronic Spectra 01 0" Complexes 433
3)
-s.
two
10-8 SURVEY OF THE ELECTRONIC SPECTRA OF Oh
COMPLEXES
The electronic spectra of transition metal complexes can be interpreted wi th the
aid of crystal Ci el d theory. In our discussion of Oh complexes in t his section, our
concern will be with syslems in which t he local symmetry is Oh' though the
overall molecular symmetry may not be. Throughout the remainder of this
chapter, we shall use t he symmetry terms very loosely to describe the type and
arrangements of donor atoms direct ly bonded to the met al, with the rest of the
li gand atoms bei ng ignored. Jt should be reali zed that this ass umption is not
always justified. Upon completion of t his secti oo, we shall be in a position lo
assign and predict t he elect ronic spectrum as well as rat ionali ze the magnitudes
of the d-orbital splitt ings observed. The treatment here wi ll not be encyclopedic;
selected topics will be covered. The aim is to give an appreciation for a very
powerful tool in coordinati on chemistry : the uti lization of electronic spectra in
the solution of structural problems. More advanced trea tments contai ning
references to the spectra of many complexes are available.( 1.2,4.5.9.1 0.t2)
The discussion in Chapter 5 of selection rules for electronic transiti ons should
be reviewed if necessary. Here we shall apply these rul es to sorne transition metal
ion systems. We begin by di scu sing high spin, octahedral complexes of Mn(ll),
a d
5
case.. here there are no spi n-allowed d-d t ran il ions. AII d-d transit ions io
this case are both multiplicity and La porte forbidden. lf it were not for vi bronic
coupling and charge transfer tran iljons, Mn(H) complexes would be colorless.
Hexaquomanganese(I1) ion is very pale pink, with aIl absorpt ion peaks in the
visible region bei ng of very low ioten ity.
The fact that mult iplici ty-all owed lransitions are usually broad, while
multiplicity-forbidden t ransitions are usually sharp, aids in making band assi gn-
ments. M ultipli city-aJlowed t
2g
-4 e
g
transitjons lead to an excited stat e in which
[he equilibrium internuclear distance between the metal ion a nd ligand is larger
than in the ground state. In the course of l he electronic t ransition no change in
distance can occur (Franck-Condon princi pie), so the electronicall y excited
molecules are in vi bra tionally excited sta te. with bond distances corresponding
to t he conCiguration of he ground sta te. The interaction of an excited state with
sol ent molecules not in the prima ry coordination sphere is variable beca use
neighboring sol vent rnolecules are vanous distances away when the excited
molecule is produced. Since the solvenl cannot rearrange in the transiti on time,
a given exci ted vibrational state in dilferent molecules wiII undergo interactions
with solvent molecules located at varying distances. Varying sol vat ion eoergies
produce a range of variable energy, vi brationally exci ted slates and a broad band
results.
In sorne spi n-forbtdden t rans itions, rearrangement occurs in a given leve!.
For example, in Cr(JII) complexes a trans ition occurs from a ground state
containing three uopaired el ectrons in t
2g
to an excited state io which t
2g
has
two pai red electrons and one unpaired electron. In these multiplicity-forbi dden
transitions there is often little dilference in (he equili brium internuclear distances
of the excited aod ground electronic states. Sharp lines result from these transitions
to a low energy vibrationallevel of an excited state whose potential energy curve
Applications
is simil ar in both shape and in equilibrium internuclear distance to that of the
grou nd state.
As discussed earlier, there is no center of symmetry in a tetrahedral molecule,
so somewhat more intense .:bsorptions (e = 100 to 1000) than those in octahedral
complexes are often obtained for d-d transitions in ~ complexes.
dI and d
9
Complexes
The simplest case with which to illustrale the relation between Dq and the color of
a transition metal ion complex resulting fr om a d-d traositi on is d I e.g. , Ti(TIl)
in an oct ahedral field. The ground state of the fr ee ion is deseribed by th' term
symbol 2D and, as indicated earlier, the degenerate d levels a re plit in the presence
of a n octahedral fie1d into a triply degenerate 2T
29
and doubly degenera te 2Ea
seL The splitting is equa! to 10D(1- This is repre ented graphicalty in Fig. 1 10.
~
FIGURE 1 ~ 1 Splitting of d levels for a
d' case, Oh field.
ce
w
Z
W
I
I
I
E
GASEOUS:
..
ION ! }E
- ---- -----------t--
T
29
o INCREASING Dq
"
<l
a
u
2
u
d
As Dq increa ' es, !lE, the energy (hence the frequency) of the transition increases.
The slope of t he T
2g
line is - 4Dq and that of Eg is +6Dq. T be value of t:.. (in
units of cm-
1
) can be obtai ned directly from the frequency of the absorpt ion
peak. For example, Ti(H 20)63+ has an absorption maximum at about 5000
(20,000 cm- 1). The t:.. val ue for \ ater altached to Ti 3+ i, about 20,000 cm - 1 (Dq
is 2000 cm - 1). Since thi t ransition occur with the absorption of the yeltow-green
component of visible light , the color transmitted is purp\e (blue + red). As the
ligand is changed, Dq varies a nd the color of lhe complex changes. The col or of
the sol ution is the complement of the color or c I rs absorbed, beca use the
transmitted bands deter mine the color. Caution should be exercised in inferring
absorption bands from visual observations ; e.g., violet and purple are often
confused.
For a d
9
complex in <ln octahedral field, lhe energy level diagram is obtained
by inverl ing thal of the di complex (see Fig. I 11). The inver ion applies because
the ground state of a d
9
configu ra tion is doubly degenerate [t l/e9
3
can
be t
2
/(d,,_ ,,1 )2(d:,)! or t2/(d" _ I. , )1(d
z
l)2] and Ihe excited st ate is tri ply
degenerate [e
2
/e/ can be (d y(d
y
, )2(d
x
=)1(e
r
l or (dx)2(dyz)1(dxzf(eq)4 or
(dx'y (d
y
,)2(d.<z f(e
g
)4]. Therefore, the transition is 2 Eg 2 T
2
(J' In elfect, t he
electronic transit ion cau es the motion of a posit ive hole from the e
g
level in the
grou nd state to lhe leve! in the excited sta te, and the appropriate energy
x
t
2g
n
:e
o.
lses.
~ (in
10--8 Survey of th e Electronic Spectra of OhCompl exes 435
>-
CJ
a:
w
FIGURE 10-11 Splitting 01 the d levels
z
w
in a d
9
complex, Oh lield.
o INCREASING Dq
diagram results by inverting that for the electronic lransi tion for a dI cas In
order to preserve the center of gravity, the slopes of the li nes in Fig. 10-1 J must
be -60(j for Eand +40q for T
2
.
The res ult s described above are often summarized by a n Orgel di agram as
in Fig. 10-12. For dI, t he tetrahedral plitting is just the oppo ile of that for
octahed ral spli tting so dI tetrahedral a nd d
9
octahedral complexes have similar
Orgel diagrams, as indicaled in Fig. 10- 12. The spl tting of Ihe sta res as a function
or Oq for oclahedral complexes wirh elect ron confi gurati ons dI and d
6
and fOl"
telrahed ral complexes wil h d
4
and d
9
elcclron confi gurations is described by t he
right half of Fig. 10-12. Only one band arises in the spect ra from d-d t ransi ti ons,
and thi s is assigned as 2T
29
-> 2Ey. The left-ha nd side of l he Orgel diagram appli cs
to octahedral d
4
and d
9
as well as tetrahedral dI and d
6
complex s. The single
d-d t ra nsi tion that occurs is assigned as l E -> I T
2
.
d'd
6
0
h
d
T
d'd
6
T
d
d
9
d
4
0
h
d
4
d
9
T E
FIGURE 10-12 Orgel diagram for high
spin d\ d
4
, d
6
, and d
9
compl exes. (The g
subscript would be added l o the
symmetry designation lor an Ohcomplex.)
2
E
+-- INC Dq o INC q ~
The two triplet states for a dI gaseous ion were earlier shown to be JF and 'P.
r urt hermore, we showed t hat an octahedral fi eld split lhe J F terms into the
triple! sta tes ]T
l g
JT
2g
, a nd JA
zg
; lhe JA
Ig
state arises fr om e/, t he 3T
I 9
states
ari e from t
2
/ , a nd (t hough no! worked out earlier) anolhcr JT
2 y
stale ari ses
from t2/e
9
l . ln underslanding the lcct ronic spcctra, only the tliplet states ne d
be considered, for the ground state is triplel. A simpli fi ed, one-electron orbital
description of t hese triple! states will be presented. The foll owing: degenerate
arrangemenls are possible for lhe ground stale of the octahedral d2 complex :
d
xy
1, dxzl, d
yz
O; d
xy
O, d
x
l
, d
yz
1; d,.,l , dxzo, d
I
The ground sla te is orbitall y triply
YZ
3
436 Chapter 10 The Electronic Structure and Spectra 01 Transiti on Metal lons
FIGURE 10-13 Possible
electron arrangements lor
tlg1eg'.
degenerate and the symbol JT
I9
(F) is used to describe this state; the (F) indicates
that the state arose from the gaseous ion F termo In addition to the 3I'liF)
ground sta te, an excited state exists correspondi ng to the configuration in Vvhich
the two electrons are paired in the 129 leve!. T ransitions to these states are
multiplicity fo r bidden, but sometimes weak absorpt ion bands assigned to these
transitions are observed.
The t ri plet excited state 12/e/ will be considered next. rr an electron is
excited out of dxz or dl'z so that t he remaining electron is in d,y ' the excited
electro n will encounter less electron-eJectron repulsion from the elect ro n in d
XY
if it is placed in d
z
" The d, ,_y' orbital is les s favo rable because of the proximity
of an electron in thi s orbital to the electron remaining in d
xy
' This gives rise to
arrangement (A) in Fig. 10-13. Similarly, if l he electron is excited out of d
xy
it
E d, , d, d, , d, d, , d,
x -v z x - v % -y z Z
N
-4- -4-
E
--1- -+-
R
d
xv
d .. dyZ
d
ru
dxz dyZ
d
zu
d
zz dyZ
G
y (A)
(8) (e)
will be m st stabJe in d<, _r" The remaining eJectron can be in either d : or d,,=,
x
giving rise to (B) and (q. T his set [Fig. 10-13(A, B, a nd )] gi ves ri se to the 3 1'
2
9
state, which is orbitally triply deg nerate and has a spi n multi plicity of three.
The arrangements (d
x
./, d
x
' _ 1', 1; d
xz
1, d:, I; d).z 1, d:, I) are higher in cnergy and
also produ e a n orbitally triply degenerate state, JT1g(P). O ther possi ble arra nge-
ments correspondi ng to t z/e / involve reversing one of lhe elect ron spins to
f
produce states with singlet multiplicity. Transitions to lhe e states from t he t riplet
ground state are mul tiplicity forbidden. Fi nally, a two-electro n transition produc-
ing the excited state e/ or dz , l , d,'_ / gives rise to a si ngl y degenerate 3 A 2y
state. lt is instructive to indicate how these states rel a te to t he gaseous ion. A'
iUustrated in the section on term symbols (Section 10-1), th ground state for
the gaseous ion V(III) (a d
2
ion) is 3F. The ligand field in the c mplex removes
l he sevenfold orbital degeneracy of this state (i.e., M L = 3, 2, 1, O, - L, - 2, - 3)
into two threefold degenerate states, and 3T
29
, and one non-degcnerate
state, J A 2g' This is indicated in the Orgel diagram (Fig. 10-14) for a d
2
, Oh complexo
>
O
FIGURE 10-14 Orgel diagram lor high a:
spin d
1
, d
3
, d
7
, and d
8
complexes.
w
z
w
+--INC Dq O INC Dq
TAE
(V
m al
H
2
0
H,
( H-
HC(I
eH
Asj
oft/]
triple

occur
10-8 Survey 01 the Electronic Spectra 01 Oh Complexes 437
TABLE 1G-6. Absorption Maxima of Octahedral NI" Complexes
1
(v
max
in cm- )
Ligand
) A
2q
---+ 3 T
lg
3A,..... 3 T'9(F) 3A, .... 3 T,glP)
H
2
0 8500 15,400 26,000
NH
3
10,750 17,500 28,200
(CH
3
l
2
SO 7730 12,970 24,040
HC(OlN(CH
3
l
2
8500 13,605 (14,900) 25,000
CH
3
C(O)N(CH
3
)2 7575 12,740 (14,285) 23,810
)'
y
o
il
Iy: '
T
29
ce.
Lnd
.ge-
,lO
piel
luc-
2a
. As
, for
oves
-3)
:rale
plex.
1, (F)
For zero Dq (i.e., the gaseous ion), only two triplet states, 3 F and 3 P, exist.
As Dq increases, 3 F is split into the 3 Tg(F), 3 T
2g
, and 3A 2g states. The degeneracy
of the 3P state is not removed by the ligand field, and this state becomes the
triplet 3T(g(P) state in an octahedral complex. The (P) indicates that this state
arises from the gaseous ion 3 P state. The energies of these states as a function
of Dq are presented in the OrgeJ diagrams as well as the Tanabe and Sugano
diagrams
l13
) (Appendix D). Use of the Orgel diagrams in predicting spectra and
making assignments will be demonstrated by considering V(III) and Ni(II)
complexes.
For V(III), three transitions involving the states shown in ig. 10-14 could
occur: 3Tg(F)--> 3T
29
, 3TiF)--> 3Tg(P), and 3TiF)--> 3A
2g
. The transition to
3 A
2g
in V(III) is a two-electron transition. Such transitions are re1atively
improbable, and hence have low intensities. This transition has nol been observed
experimentally. The spectra obtained for octahedral V(III) complexes consist of
two absorption bands assigned to 3Tg(f) --> 3T
2g
(F) and 3Ti F) --> 3TiP). In
V(H
2
0)63+ these occur at about 17,000 and 24,000 cm - \ respectively.
For octahedral nickeJ(II) complexes, the Orgel diagram (left-hand side of
Fig. 10-14, d
8
) indicates three expected transitions: 3 A
29
--> 3T
2g
, 3A
29
--> 3Tg(F),
and 3 A
29
--> 3Tg(P). (A similar result is obtained from the use of the Tanabe and
Sugano diagram in Appendix D.) Experimental absorption maxima correspond-
ing to these transitions are summarized in Table 10-6 for octahedral Ni(lI)
complexes. (Numbers in parentheses correspond to shoulders on the main band.)
Spectra of the octahedraJ NH
3
, HC(O)N(CH
3
)2' and CH
3
C(O)N(CH
3
)2 com-
plexes are given(l4) in Fig. 10-15. These complexes are colored purple, green, and
yellow, respectively.
10-9 CALCULATION OF Oq ANO FOR Oh Ni(lI)
COMPLEXES
The graphical information contained in the Orgel diagrams is more accurately
represented by the series of equations that relates the energies of these various
states to the Dq value of t he ligando These energies were derived in Section 10-3.
For Ni(I1) in an octahedral field, the energies, E, of the states relative lo the
sphericaJ field are given by the following equations.
for 3T
1g
: E = -2Dq (10-14a)
for 3 A
2g
: E = - 12Dq (10-14b)
for 3Tg(F) and 3T
1
/ P):
[6Dqp - 16(Dq)2] +[- 6Dq - pJ E +E
2
= O (10-14c)
Energy (cm-
I
)
25,000 12,500 10,000 8000
FI GURE 10--15 Molar
absorptivity, , lor some
nickel(ll) complexes in
CH
3
N0
2
solution ---,
Ni(NH
3
)(CI 0l2; ---,
Ni[HC(0)N(CH
3
)216(CI0
4
l2 ; -'-,
Ni[CH
3
C( O)N(CH
3
)216( C10
4
)2 '
14
12
~
;;
E.
10
.D
o
'"

8
...
o
(5
~
6
4
2
400 600 800 1000 1200 1400
Wovelength (mp)
where p is the energy of the 3 P sta te. There are two roots to the last equation
cor responding to the nergies of t he states 3T/F) a nd 3T
1Q
(P).
F rom the equations it is se n tha t the energies of both 3T
29
and 3 A ~ arc
linear functions of Dq. For any ligand that produces a spin-free octa hedral ni ckel
complex, the difference in energy between the 3T
19
sla te and the 3A 2g state in the
complex is lODq. As can be seen from the Orgel or Tanabe and Sugano diagrams,
lhe lowest energy transition is 3 A
2g
-7 3 T
2g
. Since l his trans ition is a di rect measure
ofthe energy difference of these states,!! (or IODq) can be equated to lhe transiti on
energy, i. e., Ihe freq uency of this band (cm - 1).
Equation (10-14c) can be solved for the energies ofthe other states. However,
the a bo e eq uations have been derived by assuming lhat the Iigands a re point
charges or point dipoles a nd thal there is no covalence in t he metal-l igand bond.
Ifthi were true, the value for Dq jusl determined could be substit uled into
equation (10-14c), Ih energy of 3p obtained from the a tomic spectrum of the
gaseous on,( 1O) and t he energy of the other two levels in the compiex caJculated
from equation (lO-14c). The frequenci of l he expected spectral transilions are
calculaled for one band orresponding (o the difti rence b I ween the energies of
the levels JTI9( F) - 3 A
2
<1 and fo r t he ot her band from the energy differenee
3T
1q
(P) - J A
2g
. The experimental energies obta ined from the spectra are almos t
a1ways lower than Ihe alues calculated in this way. Th devi ali on is altri bu(ed
to covaJency in the bonding.
16-9 Calculation of Oq and 1I for Oh Ni (ll) Complexes 439
The effect of covalency is to r duce the positi ve charge on the metal ion, as
a consequence of elect ron donation by t he ligands. With reduced positive charge,
he radial extension of he d orbit als increa es; this decreases the electron-electron
repulsions, lowering the energy of the 3 Psta le. Covalency is fore ign to the crystal
field approach and is incorporated into the ligand tield approach by providing
an additional parameter, as we shall di scuss next.
The d ifference in energy between the 3 P and 3F sta tes in the compl ex relativc
to Ihat in the gaseous ion is decreased by covalency a nd, as a result, t he gas
phase val ue cannot be used for p [in equa tion (10---14c)J; rather, p mus t be
experimentallyc al uated fo r each complex. Equalion (10---1 4c) can be employed
for thi' calcul a tion by using the Dq value from the 3 A
2g
--> JT
29
transiti on and
the experimental energy, /l E, for the 3 A
2g
--> 3Tg(P) transition. T h only unknown
remaini ng in equation (l 0-14c) is p. T he lowering of 3 P is a meaSll re of covalency,
among other effects. It is rererred to as the nephelauxetic effect a nd is sometimes
ex pressed by a parameter r- , a percentage lowcring of the energy of the 3 P stat'
in lhe complex compa red to t he energy of 3p in lhe free, gaseous ion.<l3) It is
caIculalcd by usi ng the equat ion:
IJ" = [ (B - B' )/ B] x 100
where B i t he Racah parameter discussed earlier for the free gaseous ion and
B' is the same parameter for the complex. It should be noted that p of equation
(10-14c) is proport ional lo B. In the case of nickel( lI), the energy of 3p in l he
complex can be subst ituted along Wilh Dq into equat ion (10-14c) and the ot her
root calclllated. The difference in the energy bet ween thi s root and [he energy of
3A
29
gi ves the frcq uency of the middle band [3 A 29 --> 3Tg(E)]. The agreement of
the calculated and experimental val ues for this band is good evidence for 0
1
,
symmet ry. The aboye discllssion will be made c1earer by referring to Appendix
E, where a ample calcula tion of Dq, {J , and the frequency of t he 3 A 2q --> 3Tg( E)
transitioll is presented for Ni [( 'H 3hSO]6(CJ04h.
Most often the qua ntity {J is ll sed instead of {J where {J is defined as:
B'
{J = - (1 0- 15)
B
The Iwo quant it ies are easily related if equation (1 0---13) is rewrittelJ as
{Jo = (1 - {J) x 100.
With many other ion the pectral data cannot h sol ved casily for Dq and
f3 be ause of complications introduced by pin-orbit coupli ng. T he cons quences
of this effect on a (e ion are illustra ted in Fig. 10-1 6. The tripl y deg nerate T
2g
state is plit by spin-orbit (s.o. ) coupling as indicated in Fig. 1O- 16(B). Coupli ng
lowers lhe energy of the gro und state and the extent of lowering depend upon
the magni t ude of the coupling. When the ground state is lowered by spi n-orbit
coupli ng, t he energies of al1 the bands in the spectrum have contri butions from
thi s lowering, /l, .o. ' When the cont ribut ion to lhe total energy from /l, .o. canno!
be determined, t he eval uation of /l and {J is not very accurale. Spin-orbit coupling
in an excited state is not as seri us a problem bccause lransiti ons to both of the
split levels often occur and the energies ca n be averaged. When l he ground state
is spli t, only the lower level is poplllalcd. Thus accurale values for Dq and {J
without corrections for spin-orbit coupling can be obtained onl y for ions iD which
E
FIGURE 10-16 Conlribulion lo
N
Irom spin-orbil coupling. (A)
E
d-Level splitting wilh no
R
spin-orbit coupling. (B) Splitting
G
01 T
29
level by spin-orbil coupling. y
the ground state is A or E (e.g., Ni(Il)) . A further complication is introduced by
the effect that Jahn-Teller distortions have on the energies of the Jevels.
Ni(II), Mn(II) (weak field), Co(III) (strong field), and Cr(III) form many
octahedral complexes whose spectra permit accurate calculation of Dq and f3
without significant complications from spin-orbit coupling or Jahn-Teller distor-
tions. Ti(III) has only minor contributions from these complicating effects. In the
case of tetrahedral complexes, the magnitude of the splitting by spin-orbit
interactions more nearly approaches that of crystal field splitting (Dq', the splitting
in a tetrahedral field, is about 4/9 Dq). As a result, spin-orbit coupling makes
appreciable contributions to the energies of the observed bands. A procedure has
been described(14) that permits evaluation of Dq and f3 for tetrahedral Co(III). A
sample ca\culation is contained in Appendix E.
Both (J and n bonding of the ligand with the metal ion contr i bu te to the
quantity Dq. When n bonding occurs, the metal ion t
2g
orbitals will be involved,
for they have the proper directional and symmetry properties. If n bonding occurs
with empty ligand orbitals (e.g., d in Et
2
S or p in CN-), Dq will be larger than
in the absence of this effect. If n bonding occurs between fil'led Iigand orbitals
and filled t
2g
orbitals (as in the case with the ligand OH- and Co(I1Il), the net
result of this interaction is antibonding and Dq is decreased. These effects are
illustrated with the aid of Fig. 10--17. In Fig. 10--17(A), the d electrons in t
2g
interact with the empty ligand orbitals, lowering the energy of t
2g
and raising
the energy of the mainly ligand n orbitals in the complexo An empty n* orbital
of the ligand could be in volved in this type of interaction. Since t
2g
is lowered
in energy and e
g
is not affected (the e
g
orbitals point toward (J electron pairs on
the ligands), Dq will increase. In the second case [Fig. 10--17(B)], filled Iigand n
orbitals interact with higher energy filled metal d orbitals, raising the energy of
t
2g
and lowering Dq.
It is informative to relate the energies of the observed d-d transitions to the
energy levels associated with the molecular orbital descri ption of octahedral
complexes. The scheme for an Oh complex is iJlustrated in Fig. 10-18 (which
neglects n bonding). The difference between T
2g
and Eg* is lODq. As metal-ligand
(J bond strength increases, Eg is lowered, Eg* is raised by the same amount, and
Dq increases. If T
2g
metal electrons form n bonds with empty p or d orbitals of
the Iigand, the energy of the T
29
level in the complex is lowered and Dq is increased.
Electron-electron repulsions of the T
2g
electrons and the metal nonbonding
eJectrons raise the energy of the T
29
set and decrease ,0\,. The aboye ideas have
been employed in the interpretation of the spectra of sorne transition metal
acetylacetonates.( 15. 16.1 7)
E
N
E
R
G
Y
E '
NI
E
R
G
Y
elec
the
Ade
obt
10--9 Calculation 01 Oq and fJ lor Oh Ni(ll ) Complexes 441
E
N
E
R
FIGURE 10-17 Effect 01 11: bonding
G
on the energy 01 a 129 orbital and on
Y
Oq. (A) Filled metal orbitals, empty
ligand orbitals. (6) Filled metal
eg--
orbitals, lilled ligand orbitals.
11
1 ~
2g \
\
\
\
\
\
\ 7T
'- 1l
(6)
Complex, Complex, Ligand
no 7T includlng 7T 7T orbital
bondlng bonding
FIGURE 10-18 Molecular
orbital description 01 an
octahedral complex (11:
bonding ellects and
electrons are not
included).
The magnitude of Dq s detennined by maoy fact ors: interactions from an
electrostatic perturbation, the metal-Iigand (J bond, the metal to lgand n- bond,
the ligand to metal n bond, and metal electron-ligand electron repulsions.
Additonal references( 9. 10.181 on the material presented io this section are available.
Much useful information regarding the metal ion-ligand interaetion can be
obtained from an cvaluation of Dq and ~ . For a series of amides or the type
R,
R,C(O)N/ . it was found lhal whenev r R, and R} are both alkyl groups, lower
R]
valut:S fo r Dq and f3 re ult for lhe six-coordinate niekel complexes than when
eilher R, or bolh R
2
and R] are hydrogens. T hi s is nOI in agreement with the
observati n that t owa rd phenol and iodinc the donor strengths of these amides
are fo und t inerease wit h the number of alkyl groups. l t was pr posed that a
sterie effect cxists between neighboring eoordi nated amide molecul cs( (4) in the
metal complexes. A st udy of the niekcl(U) eomplexes of sorne primary alkyl ami ne'
indieated lhat even Ihough water replaees Ihe amines in the eompl xes, the ami nes
inleraet mo re strongly with ni ckel t han do s water, and almos t as strongly as
amm nia.(19) A large Dq i also reported for the niekel compl ex of
et hylenei mine.(ZO) These results are int erprel d and an expla naton involving
solvation energies is proposed for the instability of the alkylamine complexes in
wat r.( 19)
Thc magnitude of IO Dq ror va rious metal ions generally va rics in the following
arder:
Mn(Il) < Ni(Il) < Co(I1) < Fe(I1) < V(II) < Fe(Tm < Cr(lTl ) < V(III)
< Co(lIl) < Mn(l V) < Mo(lII) < Rh(llI) < Pd(IV) < Ir(TII) < R (IV)
< Pt( IV)
Reprel entati ve li gands glve n c to the fol low:ng order, refcrred to as lhe
spectroehemical series:
1- < Br- < - SCN- < F- < urea < OH- < CH
3
C0
2
- < CzO} - <
H10 < - NCS- < glycine < C
S
H
5
N - H3 < et bylencdiamine <
S03
2
< o-phenanthrolin < NO
z
- < N
TABlE 10-7. Empirical Parame ters for Predicting 10Dq and Bwith Equations
(1Q-16a) and (1Q-16ba
Llgands h Metal Ions g(10
J
cm-' ) k
6F-
0. 9 0.8 V(Il) 12.3 0.08
6H
z
O 1.00 1.0 r(J1 r) 1704 0.2 1
6 urea 0.91 1.2 Mn(ll) 8.0 0.07
6 H3
l.25 lA Mn(I V) 23 0.5
3 en 1.28 1.5 Fe(lIl) 14.0 0.24
30x
2
-
6C1-
0.98
0.80
1.5
2.0
Co(lJI)
(JI )
19.0
8.9
0.35
0.12
6CN - 1.7 2.0 Mo(JIl) 24 0.1 5
68r- 0.76 2.3 Rh( lII) 27 OJ O
3dtp- 0. 86 2.8 Re(IV) 35 0.2
C
S
H
5
N 1.25 Ir(lII) 32 0.3
Pt(lV) 36 0.5
JI
to pr
empiri
and (1
Bo is ti
10-10
Since 01
splitting
d -.. d Ir
provide
be with
This i n ~
eomplex
The
or rhoml
repre. enl
trigonal
are comn
in Fig. I
E
N
E
R
20 /
~
\
G
Y
Gaseou
ion
stale can
tetragonal
A mu t oc
electron- lig
orbi lals j ~
lower in en
, From C. K. J0rgensen. "Abso rption Spectra and Chemical Bonding in Complexes," Pergamon
be observec
Press, el'. Yo rk, 1962.
the octahed
ns
le
10-10 Elfect 01 Distortions on the d-Orbital Energy levels 443
J0rgen en(4a.b) has reported a remarkable set of parameters that enable one
to predict 10Dq and f3 for various transi ti on metal ion complexes. When the
empirical parameters given in Table 10-7 are substituted into equat ions (1 0-16a)
and (10-16b) the values of lODq and Bfor the complex result.
lODq=fg(cm -
I
x 10-
3
)
B = Bo{1 - hk)
Bo is the free ion interelectronic repulsion parameter.
1(}-10 EFFECT OF DISTORTIONS ON THE d-ORBITAL
ENERGY LEVELS
Since octahedral , square planar, and tetrahedral crys tal fields ca use differen t
splitti ngs of the fi ve d orbital, geomet ry will have a pronounced elfect upon the
d--> dtrans itions in a metal ion complexo Spe tral data for t b e transit ions should
provide informal ion about lhe structure of complexes. Our initial concern will
be with how struclure affects the energies of the various sta les in a metal ion.
Thi informati on wi ll Ihen be applied lo determi ne lhe structures of various
com pl xes.
The structures of six-coordinate complcxes can be cI a sifi ed as cubic, axial,
or rhombic, if lhe equivalences of the ligaods al ng lhe x, y, and z axes are
represented by x = y = z, x = y i= z, or x i= y i= z, re p clivel y. Tel ragonal and
trigonal dist ortions O_e., an elongalion or compression al ong lhe threefold axis)
are commom axial examples. The spl itt ing of the ta tes for a di case is reprcsented
in Fig. 10-19. Since d-d el ctron repul ' ions are no! presenl in lhe di case, the
E
N
E
FIGURE 10-19 Orbital splitti ng tor d'
complexes in octahedr al and tetragonal
R
tields.
Y
G
states can be correlatcd wi-lh the d or bitals as indicated. For the splitt ing in a
34
tetragonal complex, trans-TiA
4
B
2
, lo arise as indicaled in Fig. 1 18, ligand
A must occupy a higher position in lhe pectrochcmical series lhan B. Metal
electron- liga nd el ectron repulsions areless for sta tes consisting of electron ' in
orbi tals directed toward the Iigands, B, located 011 the z-axis. As a resul4 d
z
' is
lower in energy than d
x
' -1", a nd d,,:and d
y
: are lower than d<\,. More band wi ll
be observed in lhe pectrum of the tetragonal complex lhan in the spect rum of
the oct ahedral complex.
,
444 Chapler10 The ElectronicStructure and Spectra 01 Transition Melal lons
'B
1 ~
~
E
~ = =
N
E
FIGURE 10-20 Splitting 01 the
'Eg
R
various states lorcobalt(llI) in
'r ~ t ~ ~
G
---.!L....., - - - !lE
Y
octahedral, tetragonal , and
--- 1t
rhombic fields.
' A
2g
~ ~
Oh Tetragonal Rhombic
The energies and spJi tt ings of the various sta tes for a spin-paired Co(I1I )
complex are indicated in Fig. 10-20. Since this is an ion wi tb more than one d
eleclron, we musl concern oll rselves with sta tes a nd not orbita!s. The l T, gexciled
state of t he octa hedral complex plits into l A 2g and 1Eg states in a tetragonal
field, while splits into l Eg and ! B2g' The splitting thal occurs in a rhombic l T
29
field is also indicated. Hydra t d tris(glyeinalo)cobalt(IIT) exi sls as a vi olet a isorner
and a red p isomer. On isomer must be cubic (where x = y = z), a nd the other
isomer must be rhombic. The spect mm( 18) of Ihe f3 isomer consisls of (wo ba nds.
The a isomer al so gi ves rise to two bands, one of which is a ymmet ric and must
consist of two or more absorption bands thal are nol r olved. Therefore, Ihe a
isomer must be the rhombic isomer and the f3 i ' omer lhe cllbic i omer.
Both cis- a nd trans-CoA
4
B
2
+.isomers a re tetragonal. Howcver, lhe differ nce
in energy betwecn t he ! A
2g
and l Eg stales (/lE, in Fig. 10-20) is usual ly abollt
twice as large in trans complexes as it is in cis compl xes(21.22)
[Ll E.(cis) = - C(Ll
A
- Ll
B
) and /lE,(trans) = 2C(Ll
A
- Ll
B
), where e is a constanl
usually less than one, Ll
A
and /lB represent the crystal field spl itt ings of ligands
A and B (i.e., lheir positions in the spectrochemieal series), and the minus sign
aeeounts for lhe faet thal the cnergies of l E y and 'A29 are interchanged in cis
and trans complexes]. Usually, when Ll
A
and Llo di ffer appreciably, the IA
lg
and
l Eg spJitting gives rise lo a doublet for the l Al u---> 1 T
l9
peak in the trans compound,
while this band is simply broadened in the cis compound(22) It also found thal
Gis isomers often have la rger molar absorptivi ty values for d ---> d transitions than
trans isomers. Typical spectra(23) are illust rated in Fig. 10-21. When Ll
A
and Ll o
are similar, this criterion cannot be employed. T he ultraviolet charge transfer
band can also be used to distinguish between cis- and trans-cobalt (lll) eomplexes
when both isomers are available. The frequency of Ihe band is usually higher in
the Gis than the lra/lS compollnd. The benzoylacetonates of Co( IIT) and Cr(III)
are examples in which Ll
A
and Ll
B
are nearly equal and the meri di onal (trans)
complex has a larger ; value Ihan the facial (cis) complex(24)
Ifcer tain assumptions are made concerning the metal-Iigand di sta nce, the
di poI e moment of the ligand, and the effective charge of the nickel nucleus, it is
possi ble to calculate(25) the change in energy that occurs for the various states
as the Iigand arrangement is varied from Oh to D
4
/. This corresponds to
lengthening lhe metal-ligand distance along do , lO infinity. The change in energy
for the various levels as a function of the distort ion is illustraled in Fig. 1 22.
T he percentages on the abscissa indicate progressive weakening of two tran s
!TI
TI
ni
pr
di
co
Ni
E
N
E
R
G
Y
-----------
1)
el
10-10 Effect 01 Distortions on the d-Orbital Energy Levels 445
Co(enl;'
IAI
cm-
1
FIGURE 10--21 Spectra 01
(A) octahedral
trisethylenediamine Co(III),
(BI
(B) the cis dilluoro
compound, and (C) the trans
difluoro compound. AII
spectra are taken in water .
(el
100 f
' o
10,000 15,000 20,000 25,000 30,000 35,000
cm-
1
metal-ligand bonds (e,g" 100 % weakening represents a square planar complex).
It is thus easy to see why the spectrum of a square planar or tetragonally distorted
nickel complex should differ from that of a regular octahedral complexo
As indicated in Fig, 10-22, there will be a continuous change in spect ral
properties as the amount of tetragonal distortion increases, Eventuall y, for highly
distorted tetragonal complexes, the spectra wiU resemble those of square planar
complexes. With large distortion, the multiplicity of the lowest energy state for
Ni(II) becomes singlet and a diamagnetic complex results, The diamagnetic
E
N
E
R
G
Y
D
41h
Oh
100 80 50 20 O
Percent from Oh symmetry
FIGURE 10--22 Elfect 01 tetragonal
distortion on the energy levels 01
nickel(II). [From C. Furlani and G.
Sartori, J. Inorg. Nucl. Chem., 8,
126 (1958).]
446 Chapler 10 The Electronic Slructure and Spectra of Transition Metal lons
tetragonal or squarc planar complexes have high intensity absorption bands
(8 = 100 to 350) with maxima in the 14,000 to 18,000 cm - 1 region. T he spectra
may contain on , two, or three peaks,126.27) and band ass ignments are often
di ffi cult. Howcver, by using spectral and magnetic data, square planar or highly
dist orted tetragonal nickel(I1) complexes can be easily dis tinguished from nea rly
octahedral or tetrahed ral complexes.
Just as di st ortion from Oh and D
4h
changes the energies and properties of
the various levels, so does distortion from D
4h
(planar) to D
2d
to J; (Fig. 10-23) .
..
E
FIGURE 10-23 Energy
N
levels tor T
d
, O'h' and 02d
E
complexes. [From C. Furlani
R
and G. Sartori, J. Inorg. Nucl.
G
Chem, 8, 126 (1958).]
Y
(Al )
E g _ ~ ~ ~ ~ ~
B29
-------T
d
Figure 10-24 contains spectra for O h ' D
4h
, D
2d
, and J; complex S. 12UR-JOI T he
transitions of the J; nickel complex NiCI/ - have large 6 values beca use the
complex does not have a eenter of symmetry. In thi case, the d and p orbitals
can m.ix in a molecular orbital description. The p orbital contribulion of the
ground and excited states gives some allowed d -> p character to the l ransition,
and the in!cnsily increases. Mi xing in non-cenl rosymmetric ligand m leeular
orbital s will also cnhance lhe intensity. Accordingly, [;/ 5 is plotted in Fig. 10-24.
As can be seen, different spectra are obtained for di fferen t structures. T he spectrum
for a J; complex is expected (see Fig. lO- 23) to contain three ba nds VI' V
2
, and
corresponding to the thr e-spi n-allowed transitions : JTI(F) -> JT
2
, \'1; v
J
3T
1
(F) -+ 3 A
2
, v
2
: a nd ]T(F) -+ 3T
I
(P), v] (se e Fig. 10-24). The VI band occurs in
lhe range be!ween 3000 and 5000 cm - I and is oflen masked by absorption by
eitller the organic par! of the molecule or the solvent. lt has been obser ved for
Ni( Il ) in silicate glasses and in iCl/ -. The V
z
band occurs in the 6500 lo tO,OOO
cm - I region and has small molar absorptivi ty (8 = 15 to 50). T he v] band is
found in lhe visibl e region (12,000 to 17,000 cm - 1) and shows moderate absorption
(8 = tOO to 200).
Tt is proposed(
28
) that the complex Ni[OP(C
6
H
5
h J4(CI0
4
iz has a Du
configuration. Absorpt ion peaks occur in t he spectr um al 24 300, 14,800, and
13,100 cm- with 8 values of approximately 24, 8, and 9, respectively.
3
~
1
T
t ~
al
In
111
SI
01
In
pt
x-
lal
Tr
en
IS
eo
co
di ,
th,
SP\
gn
a v
Ihr
19,
up'
bel
9
Ig
The
the
itals
f lhe
trum
2' and
and is
rplion
a Dld
,OO. anu
1G-l1
j , .'\
35
1 l'
l . \
>- 1 I \
\ I
~
\ i
\
a
I
\, \
~
el jg 20
I
..
e
e
/ \ O
/ "

\
/ -
10
//\B
/
I i i
/
\ / "
/
\ / .
j
- j
=-==-;......-.- ....:'- .. _. _.-
Slruclural Evidence from Ihe Eleclronic Speclrum 447
FIGURE 10- 24 Electronic
absorption spectra 01 sorne
nickel cornplexes . (A)
Ni(03PO).(CIO.)2 in CH
3
N0
2
(D
2d
); (B) Ni[(CH3)2S0l 6(eI04)2
in (CH
3
h SO ( Oh); (e) Ni CI/-
in CH
3
N0
2
(T
d
); (D). Ni(ll)
(dirnethylglyoxinateh in
e HCI
3
(D
4h
). Curve C is a plot
01 e/5.
400 500 600 700 800
Wavelenglh (mil)
10-11 STRUCTURAL EVIDENCE FROM THE ElECTRONIC
SPECTRUM
Theelect ronic spectrumcan orten provide qui ck and rel iable informat ion about
theIigandarrangementin tran ition metal ion complex s.Tetrahedralcompl xcs
are often readily dist inguishecl from six-coordi nate ones on the bao i of lhe
intensit y of the bands. The spectra of nickel (Il) and cobalt(T1) are par ticul arly
informat ive.The complcx Ni{OP[N(CH
3
)z]3} 4 1
2
coul d ll ave tetrahedral, D
2d
,
square planar,tet ragonal,orotherdis torted octahedralgeomel ries. Thesi mil arity
oflhe e1cclronicspectrum ofthiscomplex lo that of iCI/ - [see ig. 10--24( )]
implied(30J that this was the fi rst cationic, lelrahcdral ni ckel(I1) complex ever
prepared. Furtherconfirmal ion ofthesl ruclure comes from lhesimilarity ofthe
x-ray powder diffraction palterns of the nickel(H) anu zinc(I1) complexe.. The
3d
LO
latt er, with a configurati on. i expected to be telrahcdral. The Orgel or
Tanabe-Sugano diagram fora T, , d
8
complex is the ~ a m e as that for octahedral
cobalt (lI)(Ohd7) with a low Dq value. Accordingly, the high energy isi ble band
is assigned to 4T(F)-+4T( P) and the low energy band to 4T(F)-+4A
2
The
commonly observcd splitting of tbe visi ble band is att ri but cd to spin- or bit
coupling, which li ft s the deg neracy of4T(?) state. 11 is recommended that any
di scussiol1 of ba nd assignments in this section be accompanied by reference to
the Ta nabc and Suga no (01' Orgel) diagrams.
I n anol h r complexo i( 0
3
)4
2
- . it was shown(3J that the electronic
speclrllm of the nickel is that ofa si x-coordinate complex. ome of the nit rate
groups must be bidentate. The color ofa transition metal ion complex is often
a very poor indicatorofstruct lll'e. Octahedral nickeI(II) complex s usuall y have
three absorpt ion bands in lhe regionsfrom 8000 to 13,000cm- , from 15,000 to
19,000 cm- , and from 25,000 to 29,000 cm- l. The exact position will d pend
upon thequantities\ and{3. Themolarabsorptivitiesofthesebandsaregenc rally
beJow 20. The Iigand field fi t ofthe cakulated and experimenta l frequencies of
448 Chapter 10 The Electronic Structure and Spectra 01 Transiti on Metal lons
the middle peak has been proposed as confirmatory evidence for the existence
of an Oh complex.
Spin-free tetragonal nickel(lI) complexes, in which the two Iigands occupying
either cis or trans positions have Dq values that are similar to the other four,
will give spectra that wil! be very much like those of the Oh complexes. In general,
molar absorptivities will be higher for tetragonal than for octahedral comp1exes.
A rule of average environment relates the band maxima in these slightly distorted
tetragonal complexes to the Dq values of the ligands. The band position is
determined by a Dq value that is an average of all the surrounding ligands.<4.3 2)
Nickel(I1) forms a large number of five-coordinate comp1exes.(33) Geometries
based on both the trigonal bipyramid and the tetragonal (square) pyramid are
known. Many of the complexes are distorted significantly from this geometry.< 35)
The electronic spectra have been analyzed in detail by Ciampolini,(35) and the
interested reader is referred to his account. It is often difficult to detect the
difference between tetrahedral and certain five-coordinate geometries on the basis
of their electronic spectra.
The electronic spectra of cobalt(lI) complexes can often provide reliable
structural information. Most six-coordinate complexes are high spin. The Orgel
diagram is given in Fig. 10-14. The ground state is 4Tg and a substantial amount
of spin-orbit coupling is expected. Three transitions are predicted, 4TiF) -+ 4T
29
,
4Tg(F) -+ 4A
2g
, and 4T g(F) -+ 4T g(?). The 4Tg(F) -+ 4A
2g
transition is a two-
electro n transition and is not observed. The electronic spectrum of octahedral
Co(H20) 62+ and tetrahedral CoCI/ - are shown in Fig. 10-25. The band in the
octahedral complex at ~ 20,000 cm - is assigned as the 4T g(F) -+ 4T g(?)
transition. The shoulder results because spin-orbit coupling in the excited 4T g(?)
state causes the degeneracy to be lifted. The other absorption band, at 8350 cm - ,
is assigned to 4Tg(F) -+ 4T
2g
.
Tetrahedral complexes of Co(I1) have an energy level diagram like that for
Cr(IIJ). The complexes will always be high spin (see the Tanabe and Sugano
diagrams in Appendix D). The absorption band at ~ 15,000 cm - is assigned to
4A
2
-+ 4T(?). The fine structure is attributed to spin-orbit coupling of the T
state. The existence of spin-orbit coupling also allows sorne quartet -+ doublet
spin transitions to occur. The other band shown is assigned to 4A
2
-+ 4T (F). The
expected 4 A
2
-+ 4T
2
transition is predicted to occur at 3000 to 4500 cm -) ; this
is outside the range of most u.v.-visible instruments and is often overlapped by
Iigand infrared bands. Several five-coordinate complexes of cobalt(I1) have been
05a
) prepared and their spectra reported and interpreted .
Copper(JI) complexes(3 5b) take on a wide range of geometries, often with
low symmetry. One generally finds, for most geometries, one very broad band
with a maximum around 15,000 5,000 cm - , which is thought to contain all
of the expected transitions. It is possible, however, that the highest-energy
transition occurs farther out in the ultraviolet region under charge transfer bands.
Thus, the electronic spectrum of copper(lI) is of little value in structure assignment.
The band position can be correlated roughly with the Iigand field strength of the
bonding groups.
Spectral data are avaiJable to enable similar conclusions to be drawn
concerning the structures of other transition metal ions. The salient differences
between spectra for various structures have been summarized.(O) Infrared and
magnetic data should be used in conjunction with electronic spectral data to aid
IJ
~
u
In
il!
of
10-11 Structural Evidence from the Electronic Spectrum 449

(A)
600
500
400
300
200
cm-
1
(B)
in assigning structures to comp\exes.(36) Use of magnetic da ta will be described
in the next chapter.
The aboye examples are only a few of the very man cases that indicate the
utility of near infrared visibl e and uItraviolet spectroscopy in providing infor-
mation about the structures of complexes. The number of bands, their frequencies,
and their molar absorpt ivi ties should all be considered. Solution spectra should
be checked against the solid-state spectra (reflectance or mulls) to be sure that
changes in structure are not occurring in solution. These changes could involve
ligand rearrangement, Iigand replacement by sol vent, or expansion of l he
coordination number by sol vation.
Other kinds of st ructural applications of visible spectroscopy have been
reported. The Dq values fo r the nitrite ion are different for the nit ro (-N0
2
)
and nitrito (-ONO) isomers. As a result of the difference in average Dq,
[(Co(NH
3
)s ONOJ 2+ is red, while [Co(NH
J
)sNO
l
J2+ is yellow. Li mitat ions of
this kind of application have been reported(37)
The use of electronic spectra to provide structural information is nicely
illustrated in a study of the elect ronic structure of t he vanad yl ion.( 38) Specl ra
of the vanadyl ion, V O2-+- , are interpreted to indicate that there is considerable
FIGURE 1D-25 The
electronic spectra 01 (A)
Co(HaO)/+ [0.021 M Co(BF
4
h
in H
2
0 l; (B) CoCI.
2
- [0.001 M
CoCI
2
in 10 M HCll . The
dotted line in (A) gi ves the
resolution 01 the two bands
contr ibuti ng to the observed
spectrum.
,
Bonding
Parameters
trom Spectra
oxygen-to-metaln bondi ngin theV-O bond.Thesimila rityin thechargetransfer
spectra of sol ids known by x-ray analysis to contain the V0
2
+ group and of
solutions is presented as vidence that aqueous solutions contain lhe species
VO(H
2
)/ + and nol V(H
2
0)6
4
+ or V(H
2
)4(OH)/+Protonation of VO
H
would have a pron unced effect on the charge transfer spectrum. Tt is proposed
that the oxygen is not protonated because its basicity is weakened by n bonding
with vanadium. A complete molecular or bital scheme for VO(H
2
0)/ + i'
presented,(38) and assignment s are made for the spectrum ofVOS0
4
'5H
2
0 in
aqueou sol ution. Simi lar sludies on other oxy-calions provide evidence for
con id rabIe metal-oxygen n bonding( 39) and ai d in el ucidat ing the c1ectronic
structures of these spe ies.
The electronic pectru m has been particularly valuable in determining the
coordinat ion numberand li gandarrangementin metallo-enzymes. Whenzi nc(I l)
is replaced by cobal t( H) in carbonicanhydrase, th electr ni cspectr um indicate
tl1at the metal ionis in a disl rt ed let rahedral sitC(40) In such applications, one
must be part icularly e rcful lO ascertain thal l he strucl ure ofthe enzyme hasnot
been changed by met al substitution. Ir t he enzyme is sti l! active, one can ha e
sorneconfi dence thatthestruct ure is lhesame. In thls exampl e,subsequent x-ray
structure determinat ion confi rmed the distorted tetrahedr IIi gand arrangement
aroundzinc(IT). Theband po ition in thevi sibl espectr umofa coppcr( TI )protein,
erythrocuprein, was interpreted(40) as indicative ofcoordi nation by at least four
nitrogen donor ligands.
The bl ue copper(lT) protein stell acyani n has been con ert d to a cobalt(Ir)
derivali ve.(41) C pper(lI )and cobalt(JI )wereshown to compelefor the samesile
in the protein. Since cobalt(II) speclra are more rcadi ly interpreted than thosc
ofcopper(IT), (he authors werc able to concl ude lha t lhe cobalt was in ci ther a
distortcd letrahedral ora five-coordinateenvironment. Astrongcha rge tra nsfer
band indicated the existence ofa Co-SR linkagc. All ofthe bands in the nat ive
copper protein were assi gned by anal ogy. The existence ofporphyrin complexes
in an enzyme ystem can be detect ed by lhe characteristic Soret band around
25,000 cm- l. This is a ligand-based n -+ n* charge transfer type of tra nsilion,
discussed in Chapter 5. Two other lower intensily bands are also fo und in lhe
elect ronicspectraofthesecomplexcs.Theexistenceofthese band and thei rshifts
upon placing subst ituents on the ri ngs are understood in terms ofresults from
molecular orbi tal calculations. (42) The posi ti ons of these bands have been
employed lo c1assify a whole host ofcytochromes.
10-12 (J ANO n BONDING PARAMETERS FROM THE
SPECTRA OF TETRAGONAL COMPLEXES
As ment ioned ea rlier. when the symmetry ofa complex is lowered from a local
0
1
, or envi ronment additionalbandsappearin thespectrum. Thi sisill ust rated
inFig.1 25,where(hespectraof Co(NH
J
}63+andCo(NH3) 5CI 2 arecompared.
As indicated by theTanabe and Suganodiagram(Appendix D),fora sl rongflel d
d
6
complexthespi n-all owed lransitionsare 1A 19 -+ 1 T
19
and 1 A Ig - I T
2g
andlhe
bands are assigned a indicated. When one of the ammonia molecules in the
be
(bCl
par
trar
Her
The
Wh
labe
labe
equ
n
he
1(}-12 (J and 71 Bondng Parameters from the Spectra of Tetragonal Complexes 451
complcx is replaced by a different group, which we arbitrari ly locate on d t hat 2,
z
group int racts di!'I' rently wit h cobalt t han does ammonia. Ir this gr up were
chloride, the (J interaction would be weaker a nd the Te intcraction great r. The
relative energies of ( 1, d :, a nd el)'z will b affected diffe rentl y in Co( NH
3
)sCIl+
x
and Co(NH
3
)6 3+; the stronger Te interacti n of Cl - raises the energy of dxz a nd
d
yz
and a weaker (J interaction fr om CI - lower lha of d:,- The degeneracy of
the triplet state is r moved and I TI is spl it into l E and lA states, producing the
spectrum indicated in Fig. 10-26(8).
(A)
FIGURE 10-26 Spectra of (A)
Co(NH
3
)63+ and (B) Co(NH
3
)sCI
2
+.
(B)
Frequency, v
The spli tting of the 1 T
2
band is predicted by theoryl22) lo be too smaJl to
be observed. Wi th the addi ti onal band , t here is need for ad itional parameters
(besides IODq and B) to describe the spectrum. The ca1culali on of values for these
parameter depends very much upon the as ' ignment of the ob erved lectronic
transitions.
Several l wer symmetry arrangements are treated by Gerloch a nd Slade(3)
Here we sha ll bricfly consider t 1. r gonally distorted six-coordi nate complexes.
Th total potential is now considered as
(10-17)
When the mat rix elements are evaluated, we obta in quantit ies Lhat we arlier
labeled Dq, plus two other rad ial quant itie. that ari se fr om v' e' " which we shall
label Ds and Dr. Ds invol ve terms and De involves ter ms, as shown in
equat ions ( 1 18) and (1 (9):
2 2- 2 (1 1)
Ds = - Ze r - - - 3 - --3 (10-18)
7 a(" y) bI t )
2 2-4 ( 1 1)
Dt = - Ze r - --5 ---5 (10-19)
7 a(xy) bIt)
Here a and b refer to the different metal-ligand distances (a refers to xy-ligands
and b r e f e r ~ to z-ligands). Dt, being an r -
4
function, can be related to Dq. (Recall
that Dq is a function of r-
4
) It is a measure of the difference in Dq bet ween the
axial and equatorial siles, as shown in equation (10-20):
DI = 7
4
[Dq(xy) - Dq(z)] (1 0-20)
It is to be emphasized that neither Dq(xy) nor Dq(z) is the same as that for the
Iigand in an oCl ahedral complex(43J
Ass uming t hat t he ymmetry of the complex is such that the melal e
g
orbitals
are only O"-antibonding and that the ,nelal t
2g
orbitals are only n-antibonding,
McClure(22) has reported parameters 60" and Cm, defined as:
12 15
00" = O" - O" = - - Ds - - Dt (10-21)
z Xl' 8 8
3 5
071 = 71 - 71 = - - Ds + - Dc (1 22)
; Xl' 2 2
The (J and 71 parameters reportedly indicate lhe relative (J and 71 antibonding
properties of the Iiga nds, Values ror various ligands have been reported and
interpreted.(43-4S1 T he following order of (J bond inlcraction with the metal ion
results from spect ral studies on these complexes:
The order of 71 repulsion is:
10-13 THE ANGULAR OVERLAP MODEL
An alternative approach (with several advantages) to the parameterizati on of t he
spectra of transition metal complexes is the angular overIap model.(3,461 This
model has its origins in a crude molecular orbital treatment of lhe energies of
the transition metal compounds, A simple case, which we will consider first, is
that of a monocoordinated complex ML:
M-L
Tf the meta l is a lransition metal, we are most interested, from a spectroscopic
point of view, in the energies of the d orbitals in the complex. The five d orbita ls
in the eO',) V symmetry of the complex span the 0", 71, and (j representations; i. e.,
d(Z2) is (J, d(xz) and d(yz) are 71, and d(xy) and d(x
2
- )/) are o, Considering. for
instance, the (J interact ion, we can write the secular equations:
(10-23)
\ he!
rcspl
orbit
and I
El ' I!
HL'1
The v
Using
equati
1 )
ion
(10-23)
10--13 The Angular Overlap Model 453
where H M" and H L" are the energies of the appropriate metal and Iigand orbitals
respectively; H
ML
" describes the exchange int egral bet ween the metal and ligand
orbitals, and SML" is the overlap integral. In general, it is found that HM" H
L
"
and that the diatomic overlap integral SML" is small, so tha t one of the root s, say
El' will be quite close in energy to HM" , and the other, E
2
, will be quite close to
H
L
". Invoking this assumption enables us to write two approximate determinants:
HM"-E
I
H
ML
" - SML"HM"
HM" - H
L
"
(10-24)
I
H
ML
" - SML"H
L
"
The values of the roots can be written explicitly as
(10-25)
(10-26)
Using the Wolfsberg-Helmholz approximation for H
ML
" in the form
(10-27)
equations (10-25) and (10-26) can be rewritten as
(10-28)
E - H " = E = _ (HM" + H L"f (S ,,)2
(10-29)
2 L " H "_ H" ML
M L
E" * is positive, and therefore represents the destabilizing elrect on the metal
orbital energies, whereas E" is negative and represents the stabilizing elrect on
the ligand orbitals. As is shown by equation (10-28), the destabilizing elrect on
a particular metal orbital is proportional to (SML"f. This elrect has to be small,
when HM" - H
L
" is large and SML" is small. E,,* might in principie be calculated
using (10-28), but in practice it is more profitable to express it parametrically.
For this purpose, the overlap integral SML" can be factored into a radi al and an
angular product:
(10-30)
where SML is the integral of the radial functions of the metal and of the Iigand
orbitals, and F/ refers to the angular part. SML depends on the particul a r metal
and ligand orbitals considered and on the metal-ligand distance, whereas F/
depends only on the geometrical disposi tions of the metal and the ligand. Once
the geometry is known, F/ can be easily calculated. We can demonstrate this
factoring with a simple example of a Iigand L overlapping a Pz orbital on a metal,
M, in an M-L fragment. In Fig. 10-27(A), the Iigand is located on the z-axis
I
454 Chapter 10 The Electroni c Structure and Spectra 01 Transition Melal lons
L
pz
lb)
FIGURE 10-27 Orbital
overlap with a pz orbital in
M-L fragments .
and the M- L bond is coincident with thi s axi s. If we define F / (sigma Iigand
overlap with a p orbit al) as one, the overlap is gi ven by the magnitude of SML '
Wh n the M-L bond is the same length but not coincident wi th the z-a ' is, l he
net overlap will be decreased. The radial part SML stays l he same, so t he decrease
is accomplished by decreasi ng F/ , the a ngular part. I n Fig. 10027(B), t he M-L
bond is along the x-axjs the ligand (J orbital is orthogonal to pz (overlap is zero)
and, si nce t he radial part doesn 'l change, this is accomplished by having the
angula r term, F/, become zero.
Subst it ll ting equation (1 0-30) into (10-28), one gets
(10-31)
Now letting
(1 0-32)
equation (l0-31) beco mes
(10-33)
Equat ion (10-33) shows that t he (J-antibondi ng effect On a par ticular d orbital
can be expressed by a parameter, e", and a number (F/), which can be obtained
from sta ndard tables (vide infra).
In the case of n-bonding, the Iiga nd can intcract eit her through ligand low
energy fiIJed orbitals, so that lhe same condit ions hold as for the (J case, or
through ligand high energy empt y orbitals, so that HM
n
~ HL", . nd the correcti on
011 the energics or the met al orbit als is of the bonding type. In bot h ca es, howc er,
en can be defined a in eq uati n (10- 32), the only difference being in the sigo (e.
is positive for antibonding, and nega ti e for n- back bonding into empty li gand
orbit als). The energies of the metal d o rbitals in a monoc ordinated M - L
complex are as follows:
E(d
z
' ) = ea
E(d,,) = E(d
yz
) = en (10-34)
E(d
x
) = E(d
x
' _ .\" ) = e,
A t rans ition m tal ion complex di ffers from this simple M-L example, fOl"
we are concerned wit h overl ap of d orbi tals and we have ma ny ligands. For an
octahedral complex, the co rdinat e sy tem, sh wn in Fig, I 28(A), fi xes t he
localion of lhe real"d orbitals. We can now employ a local coordinate system on
each li gand L, such lhat the metal-ligand bond is call ed t he z' -axis. The x' -axis
is in the plane formed by z and l, This local coordi nate system is shown in ig.
10-28(B) for ligand L
2
. The pola r coordina tcs of the Iigand can be used lo Express
the relation bet ween the coordi na tes in lhc primed coordinate system and those
in lhe unprimed coordi nale sys tem. O ur concern is how to describe a d or bital,
whose posi ti n in lhe unprimed system is known, with th varia bles of the primed
I ~
CO
co
In
d e
COL
exp
TAS
Y'
y.:
.\"z
.\"y
.\"" -
-L
10-13 The Angular Overlap Model 455
~ d
IL
he
lse
ro)
he
31 )
-32)
~ 3 3
bita!
lined
110w
e, or
ction
rever,
~ n (e"
igand
I1-L
z
t
L
L, L,
Y
L4 L3/
L3
L
z'
(Al (SI (el
FIGURE 10-28 (A) A coordinate system lor a six-coordinate complex; (B) a local
coordinate system; (e) delinition 01 oand rp in Table 10-8.
coordinate system. These relationships are worked out and the results summarized
in Table 10-8. The results can be used for a complex of any geometry.
We illustrate the use of Table 10-8 by determjning the relation between the
d orbitals in the primed and unprimed set for L
2
. The ligands in an octahedral
complex, labeled as in Fig. 10-28, have angular polar coordinates tha! can be
expressed as follows :
Ligand 1 2 3 4 5 6
e o 90 90 90 90 180
c.p o o 90 180 270 o
Considering L
2
, we have e= 90 and c.p = o. Substituting these values into row
1 of Table 10-8, we find what combination of d orbitals we must take in the
TABLE 16-8. Relationships of the dOrbitals in the Primed and Unprimed Coordinate Systems of Fig. 10-25
Z'2 X'2 _ y'2
y'z' x'z' x'y'
1
Z2
- (1 + 3 cas 2D) O
--
Ji
Sin 20 O -
Ji
(1- cas 2tJ)
4
2 4
1
Ji . . O
yz
- Sin rp Sin 2 cas rp cos 8 sin rp cos 28 -cas rp sin 8 - - sin rp sin 28
2 2
xz
J3 . 1 .
- cas rp sm 28 - sin rp cos D -cos rp cos 2D sin rp sin (-) - - cos rp Sin 2D
2 2
J2
1 1 .
xy
- Sin 2rp (1 - cos 28) cos 2rp sin 8 2: sin 2rp si n 28 cas 2rp cas D - Sin 2rp (3 + cas 2D)
4 4
Xl _ y2
Ji cas 2rp (1 - cas 2D) -sin 2rp sin D -
1
cos 2rp sin 2D - sin 2rp cos (J -
1
cas 2rp (3 + cos 28)
4 2 4
456 Chapter 10 The Electroni c Structure and Spectra of Transition Metal lons
primed system (listed across the top) to be equivalent to dz" The result is obtained
by substituting these values for 8 a nd <p into the first row:
d
z
' = ~ (1 + 3 cos 28)(Z' 2) + O(y'z') - f sin 28(x'z')
+ O(x'y') + J3 (1 - cos 28)(x'2 _ y'2)
4
(10--35)
The interaction energies of the orbitals z'z and x' z - y'z with the ligand will
be given by ~ and e
' where the subscripts indicate that the ligand-d

z
'2 interaction
is (J and that with d
x
" _ y" is b. The coefficients - I/
Z
and + .)3/2 can be considered
as the overlap of the d
z
' orbital with dz" and d
x
" _ y'" Since the energy is
proporti onal to the overlap squared [equation (10--32)J, we can write the energy
of the li gand-d
z
' interaction as
(10--36)
We now must evaluate the effect of Lz on the energies of all the d orbitals. We
accomplish this by substituting 8 = 90 and <p = 0 into all the expressions in
Table 10-8. We can express the result in the form of a matrix as
.)3
o O O
2 2
O O O - 1 O
O O - 1 O O
O O O O
.)3
O O O
-
2 2
Since the columns are in the primed coordinate system, they correspond to (J, n,
n, b, b interactions. These coefficients in the primed set produce the energies by
squaring, leading to :
E(d ) =
yz
e

E(dxzl = en (10--37)
E(d
xy
) = en
E(dx 2 _ y' ) = 4
3
~ + 4
1
e
Sub
mat
Squa
with
E(dy,J
E(d,J
E(d,)')'
E(d, :
E(d)' ,J
E(d'Zl
E(d,rl
E(d" _
You ca
each Iig
up the (
of the e
rr,
by
10-13
Substituting values ofzero for eand <p ofligand L[ into Table 10--8 yields the
matrix
1 o o o o
o 1 o o o
o o 1 o o
o o o 1 o
o o o o
Squaring the coefficients, we obtain an energy ofinteraction of 1 for ligand L[
with each orbital, i .e. , the result given earlier by equation (10--34).
Repeating this procedure for the other ligands, we obtain:
Ligand 1 Ligand 2 Ligand 3
E(d
z
') 1 3 1 3
e"
- e + - e -e +-e
4" 4 4" 4,j
E(d
yz
)
en e,j
en
E(dyz)
en e,j en
E(d
x
) e,j en en
E(dx' - y' ) e,j 3 1 3 1
- e + - e -e + - e
4" 4 4 " 4 ,j
Ligand 4 Ligand 5 Ligand 6
E(d
z
') 1 3 1 4
;;e,,+;;e,j
- e + - e
4" 3,j
e"
E(d
yz
)
el! en en
E(d
xz
)
en e,j
en
E(d
xy
)
en en e,j
E(d
x
' _ y') 3 1 3 1
- e + - e
;;e" + ;;e
e
4" 4
You can check your result by summing each column and thereby noting that
each ligand contributes one eJ, two n, and two j types ofinteractions. Summing
upthe contributions of the individual ligands, we obtain finally the expressions
ofthe energies ofthe d orbital for octahedral compounds as:
E(dz' )= 3e" + 3e
The Angular Overlap Model 457

37)
E(d
yz
) = 4e
n
+ 2e/)
E(d
xz
) = 4e
n
+ 2e/)
E(d
xy
) = 4e
rr
+ 2e,)
E(dx'_)') = 3e" + 3e
(10--38)
11
458 Chapter 10 The Electranic Structure and Spectra af Transitian Metal lans
Miseellaneous
Topies
Involving
Eleetronie
Transitions
/"
Of course, the three orbitals have the same energy and so do the two e t
2g g
orbitals. If the contribution is neglected, the difference between the e
g
and t
2g
orbitals is 3e
a
- 4e", which corresponds to the of the crystal field theory. In a
'f, complex, the e orbitals have energies of %e" + whereas the t
2
orbitals
have energies of 4/ 3ea +8/ ge" + Note that with these parameters, =
In complexes with lower symmetry, the vaJues of al! of the ligands are
added and the d-orbital energies are calcul ated. Numerical values for the ea, e",
and parameters are obtained from octahedral complexes. The ea values
employed in the different complexes are scaled according to the overlap integral.
The value of the model is that one set of parameters results for a particular Iigand
and metal, which can be scaled for geometry and overlap to account fo r the
spectra of many transition metal ion complexes. The relationships of Dq, Ds, Dt,
15(J, and I5n with ea and e" have been presented(47)
In closing this section, it should be emphasized that for these studies, and
other applications dependent upon band assignments, the assignments should be
verified by polarized single crystal results (see Chapter 5).
10-14 ELECTRONIC SPECTRA OF OXO-BRIDGED
DINUCLEAR IRON CENTERS
Theelectronic spectra of high spin octahedral and t t rahedral iron(IlJ) compounds
are as expected from the Tanabe and Sugano diagrams. Three transitions are
found: 6 A
Ig
---> 4T
2
, 6 A
Ig
---> 4T
1
, and 6 A 19 ---> 4A 19 [four transitions are found when
4E(D) is low enough in energyJ; and since Dqis larger for octahedral complexes
than for tetrahedral ones, the 4T
1
and 4T
2
(G) transi tions occur at higher energy
in the former complexes. Al! of the d-d transitions are mult iplicity forbidden and
are weak. However, when the electronic spectrum of the six-coordinate oxo-
bridged dimer (HEDTA Fe)20 (where HEDTA is hydroxyethyl ethylenediaminet-
riacetate) is examined, (48.49) the surprising result shown in Fig. 10-29 is obtained.
The bands labeled a through dare in the correct place to be assigned to t he
four d ---> d transitions, 6 Al ---> 4T
1
, 6 Al ---> 4T
2
(G), 6 Al---> A1
4
El' and 6 Al---> 4E(D),
of an octahedral complexo These bands are two orders of magnitude more intense
than those of a typical iron( llI) complexo This intensity enhancement of spin
fo rbidden bands is common to spin-coupled systems because the coupling partially
relaxes the spin selection rule.
The four intense (e-h) U.V. bands are too in tense for a d-d transition on a
single metal ion. The bands have been attributed(48) to simultaneous d-d
transitions on the two iton(IIl) centers. They are coupled so that the pair excitation
is spin allowed.(49) The band labeled e at 29.2 x 10
3
cm- 1 is assigned to the
si multaneous tran ilion of a on one center and b on the o ther (va +Vb =
29.4 X 10
3
cm - 1) ; band f al 32. 5 x 10
3
cm - [ to a +e (32.2 x 10
3
cm -1); band
g at 36.8 x 10
3
cm - 1 to b +b; and band h at 42.6 x 10
3
cm - 1 to b and d. There
is consid rabIe nterest in this spect ral feature because of the presence of the
Fe-O-Fe group in a wide vanety of ron proteins including hemerythrin and
methane monooxygenase. Resonance Raman(SO) and other studies(SJ) of a series
of hemerythrin derivatives and model compounds has led to the conclusion that
3 12
e

-e
ro
Q)
u
e
-e 8
o
.o
<{
4
the inti
compol
Si milar
thorouf
intensitJ
mechan
Metallo1
bridging
T hese "r
in tense e
deep col,
attribute,
phenorne
10-15
29
e,
h
a
16
lis
lre
e.,
'"
les -
e
12
al.
::J
-

t"
nd
lhe -e
ro
QJ-
Dt,
u
e
ro
.o 8
Ind
O

be <{
4
e
a+b
50 40 30 20 10
mds
are
FIGURE 10-29 Absorption spectrum 010,20 F aqueous solution 01 [(HEDTA
,hen Fe)20l '6H
2
0 at296 K,Calculatedpositions01 SPEexcitationsareindicatedbyarrows,
exes
ergy
and
oxo-
lhe intense near-u,v, features common to all oxo-bridged dinuc!ear iron(IIf)
inet-
compounds should be designated as oxo to iron(IlI)cha rge transfer transitions.
ined.
Similar effects have been observed on other systems(S2 .S3) and have been
) lhe
thoroughly studied(5 3) for (NH3)sCrOCr(NH3)5
4
+ 1 t is concluded that the
E(D),
intensity enhancement arises from a vibronic, exchange- induced, electric dipole
mechanism.
tense
8pin
10-15 INTERVALENCE ELECTRON TRANSFER SANOS
Metallomers, moJecules wi t h two or more metals, can be prepared in which the
bridginggroup permits l he metals to exist in two differentoxidation states, e,g.,
These "mixed valence" compounds have long been of interest because of the
intense colors they possess. For example, KFe[Fe(CN)6J, P russian bl ue, has a
deep color that is absent in K
3
Fe(CN)6 and K
4
Fe(CN)6' This color has been
altributed to an intervalence transfer transit ion. In order to understand this
phenomenon, let us consider as an example the ruthenium pyrazi ne dimer(54):
V
460 Chapter 10 The Electroni c St ructure and Spectra 01 Tr ansit ion Metal lons

N-Ru(1I)(NH
3
)55+
In order to clarify several points to be made about this system, we shall
simplify our discussion by ignoring any ligands in the coordination sphere of
Ru(ll)and Ru(IIJ) except the bridging pyrazine. Furthermore, we shall label the
two ruthenium atoms as RUalll-NON-RUbll. We shall draw a potential
energy curve(55) for the molecule as a whole as we vary the RUalll_N distance,
X, in the molecule in uch a way that the RU -Nplus Rllb-N distance is
a
constant. Curve a of Fig. 10-30 results when a harmonic potential function is
assumed, i.e., V = e/2)kX
2
.
Nextwe shaH constructa simil arcurvefor theRunll-N distancefor thestate
RU/-O-Ru
b
lH
The equilibrium Ruall-Ndistance is longer than the
equilibrium RUblll_N distance.The curve for the Rllall-N state is indicated by
curve b. We can view the two curves as defining our tot al system in which we
now have provision for the electron jumping from one center to the other. E'h
is the activation energy for the jump, and it corresponds in this system to the
molecule arriving at a place where the Rlla-N and Rub-Nbond lengths are
identical. The thermal energy required for the electron to surpass the barrier
between metals, E'h' is given(55) by
1(1 )2 1(1 2) 1
E'h =2k 2Xo ="4 2kXo ="4 EIT
(10-39)
By the Franck-Condon principie, electronic absorption occurs without
changein nuclearcoordinates, so the energy ofthe intervalence transfer band in
the absorption spectrum (i.e., a charge transfer transition from one Ru atom to
the other) is represented by the vertical line, EIT.
Theactualsituationis morecomplex,sincethecoordinateX is acomplicated
coordinate involving aH the ligands and electrons in the complex. Depending
upon the proximity ofthe two metal centers and the overlap ofvarious orbitals,
the two orbitals(one on each ruthehium) that can contain the oddelectron may
mix to form a bonding and antibonding combination. This would produce the
situations depicted in Figs. 10-30(B) or (C). The quantity labeled 2H,esin Fig.
10-30(B)is twotimes theresonanceintegral,i.e.,theoff-diagonaleIernentbetween
the two d-orbitals which can hold the odd electron (one on each rut heoium) in
the secular determinant. (56) In Fig. 10-30(B), we have shown E
th
<e/4)E
IT
.In
Fig. 10-30(C), the odd e1ectron is completely delocalized on all time scales,and
the electron absorption cannot properly be termed an intervalence transfer.
Robinand Day(57) havepointed outthatin Fig. 10-30(B),oneoftheenergy
minimacorresponds to an electronic wave function in which the odd electron is
mainly on one metal but, to a smaIl extent, is delocalized onto the other metal.
They have proposed that mixed valence compounds be classified as Class 1, n.
orIrI, dependingon whethernone,sorne, orhalfofthe unpairedelectrondensity
is delocalized from one metal center onto the other at any one instant.
t
i
V
t
v
The
at 1570 r
JabeJedEl
of 3 x 10
(10- 39). T
The t
has been 1
morethan
can be sur
extent of(
en, m]. A
formaton
__
curve (a) curve (b)
I
v
t---xo FIGURE 10-30 Potential
x_
energy curves lor var ious
classes 01 mixed valence
1
compounds. The systems
vary Irom completely
localized systems (A) to
intermediate (B) to
(A)
completely delocalized
V
(e). x is a coordinate
expressing the RUa"I_N
distance as the sum 01
RU
a
-N and RU
b
- N is
held constan!.
x __
(B)
39)
t
V
The ruthenium pyrazine dimer(54) shows an intense band in the near infrared
at 1570 mJ1, assigned to the eleetronie transition shown in Fig. 10-30(A) and
labeled E
IT
. From the energy of this transition, a thermaJ rate of eleetron exehange
of 3 x 10
9
see - 1 has been ea1culated employing a erude model and equation
(10-39). The eleetronie transition is deseribed as a [2, 3] -> [3, 2] transition.
The existenee of high intensity bands in the d-d region in other eomplexes
has been used as evidenee in support of mixed valenee in moleeules eontaining
more than one metal ion. The assignment of the band to a mixed valenee speeies
can be supported by foll owing the intensity of the transition as a funetion of the
extent of oxidation or reduetion of the en, n] oxidation state compJex to form
en, m]. A maximum is observed when en, m] is formed, and it disappears on
formation of [m, m].
x
(e)
I
i
462 Chapter 10
REFERENCES
CITED
The ElectronicStructure and Spectra of Transition Metal lons
10-16 PHOTOREACTIONS
The principIes discussed is this chapter and Chapter 5 are of importance to
chemists for applications other than structure determination. Fluorescence,
phosphorescence,and photochemistry all have to do with electronic transitions.
In photochemical reactions,the reactant is a molecule in a reactive excited state.
Understanding ofthe photochemical reaction requires an understanding of the
structure and reactivity of the excited state. In some cases, molecules that are
singlets in the groundstate become reactive radicals by beingexcited to a triplet
state containing unpaired electrons. Often, two molecules that do not form a
complex in theground stateform a complex (called an exciplex) when One ofthe
molecules is in an excited state. The principies ofelectronic transitions studied
here and in Chapter 5 are thus importantin many areas.
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1962.
2. B. N. Figgi s, " Introduction to Li gand Fields," Interscience, New York, 1966.
3. M. Gerloch and R. C. Slade,"Ligand Field Paramelers," CambridgeUniversit y Press,
New York, 1973.
4. a. C. K . J0rgensen, "Absorption Spectra and Chemical Bonding in Complexes,"
Pergamon Press, New York, 1962.
b. C. K. J0rgensen, "Modern Aspects of Ligand Field .heory," North Holland
PublishingCo., Amsterdam, 1971.
5. H. L. Schliifer and G. Gliemann, "Basic Principies of Ligand Field Theory,"
Interscience, New York, 1969.
6. C. E. Moore, " Atomic Energy Levels Ci rcular 467," Vol. 2, National Bureau of
Standards, 1952. Volumes 1and 3 contain simil a r data for other gaseous ions.
7. E.U.Condonand G. H. Short1ey, " TheoryofAtomicSpectra,"Cambridge Universily
8. 1. S. Griffith, " The Theory ofTransition Metal Ions," Cambridge Universi ty Press,
New York, 1961.
9. D. S. McC1ure, "Electronic Spectra of Mo1ecu1es and lons or Crystals," Academic
10. A. B. P. Lever, "Inorganic Electronic Spectroscopy," 2nd Ed. E1sevier, New York,
1984.
11. "SpectroscopicPropertiesofInotganicand OrganometallicCompounds," Vols. I-IV,
The Chemica1 Sociely, London, 1968-1971.
12. T. M. Dunn, "Modern Coordination Chemistry," eds. J. Lewis and R. G. Wi lkins,
Interscience, New York, 1960.
13. Y. Tanabe and S. Sugano,1. Phys. Soco Japan, 9, 753, 766 (1954).
14. R. S. Drago, D.W,Meek,M.D.Joesten,and L. LaRoche,Inorg. Chem.,2,124(1963).
15. F. A. Cotton and M. Goodgame, J . Amer. Chem. Soc., 83, 1777 (1961).
16. D. W. Barnum, 1. norg. NucJ. Chem. , 21,221 (1961).
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18. A. D. Liehr and C. 1. Ballhausen, Phys. Rev., l06, 1161 (1957).
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20. R. W. Kiser and T. W. Lapp, Inorg. Chem., l, 401 (1962).
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22. D. S. McClure, "Advances in the Chcmist ry of Coordination Compounds," ed. S.
Kirshner, p.498, Macmillan, New York, 196 1and references therein.
23.
24.
25.
26.
27.
28. I
29. I
30. J
31. r
32. (
(
33. L
R
34. d
35. a.
b.
36. B.
R.
37. M
38. C.
39. H.
H.
40. A.
cd.
41. D.
42. w.
43. D.
44. a. A
b. F
45. C.
46. a. S
b..
47. 1. Be
48. H.1.
26 (1
49. L. lA
SO. 1. Sal
51. R. C.
52. A. E.
53. H. U.
54.C. CrI
55. N. S.
56. B. Ma
57. M. B.
J. Refcr t
andal
these t
)
.
"
s.
e.
le
re
et
a
he
ed
'ork,
'ress,
!xes,"
)\land
eory,"
:au of
versity
Press,
(1963).
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73,5079 (1951); K. Nakamoto, J. Fujita, M. Kobayashi, and R. Tsuchida, J. Chem.
Phys. , 27, 439 (1957); and references therein.
24. R. C. Fay and T. S. Piper, 1. Amer. Chem. Soc., 84, 2303 (1962).
25. C. Furelani and G. Sartori,1. Inorg. Nucl. Chem., 8, 126 (1958).
26. W. Manch and W. Feroelius, 1. Chem. Educ., 38,192(1961).
27. G. Mak, J. Chem. Phys. , 29, 162 (1958); ibid., 29,1129 (1958).
28. F. A. Cotton and E. Bannister, J. Chem. Soc., 1960, 1873.
29. N. S. Gill and R. S. Nyholm, J. Chem. Soc., 1959, 3997.
30. J. T. Donoghue and R. S. Drago, Inorg. Chem. , 1, 866 (1962).
31. D. K. Straub, R. S. Drago. and 1. T. Donoghue, lnorg. Chem., 1, 848 (1962).
32. C. K. J0rgensen, "Energy Leyels of Complexes and Gaseous Jons," Gjellerups,
Copenhagen, 1957.
33. L. Sacconi, Pure AppL Chem., 17,95 (1968); Transition Metal Chem. , 4, 199 (1968);
R. Morassi, J. Bertini, and 4 Sacconi, Coord. Chem. Rey., 11, 343 (J973).
34. C. Furlani, Coord. Chem. Rey. , 3, 141 (I968).
35. a. M. Ciampolini, Struct. Bonding, 6, 52 (I969).
b. B. 1. Hathaway and D. E. Billing, Coord. Chem. Rey., 5, 143 (I970).
36. B. N. Figgis and J. Lewis, "Modero Coordination Chemistry," eds. J. Lewis and
R. G. Wilkins, Jnterscience, New York, 1960.
37. M. Linhard, H. Siebert, and M. Weigel , Z. Anorg. Allgem. Chem. , 278, 287 (1955).
38. C. 1. Ballhausen and H. B. Gray, Jnorg. Chem., 1, 11 I (1962).
39. H. B. Gray and C. R. Hare, Inorg. Chem. , 1, 363 (1962); C. R. Hare, J. Bernal , and
H. B.Gray, Inorg. Chem. , 1, 831 (1962).
40. A. S. Brill, B. R. Martn, and R. J. P. Williams,"ElectronicAspects ofBiochemistry,"
ed. B. Pullman, Academic Press, New York, 1964.
41. D. R. McMillin,R. A. Holwerda,andH. B. Gray,Proc.Nat.Acad.Sci., 71, 1339(1 974).
42. W. S. Caughey el al., 1. Mol. Spect. , 16,451 (1965) and references therein.
43. D. A. Rowley and R. S. Drago, Inorg. Chem., 7, 795 (1968); bid. , 6,1092 (1967).
44. a. A. B. P. Leyer, Coord. Chem. Rey., 3, 119 (1968).
b. R. L. Chiang and R. S. Drago, Jnorg. Chem., 10, 453 (1971).
45. C. D. Burbridge,D. M.L. Goodgame,and 1. Goodgame,J. Chem. Soco (A),1967,349.
46. a. C. E.Schiiffer and C. K. J0fgensen, Mol. Phys., 9, 401 (1965).
b. E. Larsen and G. N. LaMar,J. Chem. Educ. , 51, 633 (1974).
47. J. Bertini, D. Gatteschi, and A. Scozzafara, Inorg. Chem., 15, 203 (1976).
48. H. J. Schugar, G. R. Rossman, J. Thibeault, and H. B. Gray, Chem. Phys. Letters, 6,
26 (1970).
49. L. Lohr, Coord. Chem. Rey. ,8,241 (1972).
SO. J. Sandere-Loehr el al. J. Am. Chem. Soc., 111,8084(1989).
51. R. C. Deem el al. J. Am. Chem. Soc., 111, 4688 (1989).
52. A. E. Hansen and C. J. Ballhausen, Trans. Faraday Soc., 61,631 (1965).
53. H. U. G del and L. Dubicki, Chem. Phys., 6, 272 (1974) and re[erences therein.
54. C. Creutz and H. Taube,J. Amer. Chem. Soc., 91,3988 (1969).
55. N. S. Hush, Prog. Jnorg. Chem., 8,391 (1967) and references therein.
56. B. Mayoh and P. Day, 1. Chem. Soc., Dalton, 1974, 846.
57. M. B. Robin and P. Day, Ady. Jnorg. Chem. Radiochem. , 10, 248 (I967).
Exercises 463
1. Refer to the Tanabe and Sugano diagrams n Appendix D. For octahedral Cr(llI) EXERCISES
and a ligand with Dqj B of 1, how many bands should occur in the spectrum? Label
these transitions and list them in order ofincreasing wayelength.
20
15
f
10
5
Cr
3
(d
3
)
5,000 10,000 20,000
cm-
I
(B)
30,000 35,000
Cr'+(d')
0.10 M in 0.75 M H
2
SO,
20,000 30,000
cm-
I
(C)
35,000 10,000
2
2. Incomplexeswithweakfieldligands(Dqj B = 0.7),octahedraleo + exhibitsaspectrum
with three wcll-separated bands. Make a tentative assignment using the Tanabeand
Sugano diagrams and li st the assignments in order ordecreasing rrequency. Would
the spectrum ofa strongfield complex be any different? Describe the spectrum you
would expect ror a slrong field complexo
3. A nickel complex NiR
4
Cl
2
has an absorptionspectrum with peaks that have evalues
oraround 150. R and e l occupy similar positions in the spectrochemical series. Are
the chlorines coordinated?
4. Two differentisomersor o(NH
3
)4(Se )2+ wereseparated.Howcould youdetermine
whether the SeN groups in both were bonded through the sulrur ? Ir both isomers
were coordinated through suJrur, how would you determine which is ci s and whi ch
is lrans? (Hint:- SeNisnear 1- in thespectrochemicalseries,while- es- creates
a stronger field : eo(NH3)4Cl 2' is easily prepared.)
5. UsingtheTanabeandSuganodiagrams,assign thefollowingspectraofsix-coordinate
aquos pecies [except ror (A)].

cof
w K3 S
__ _________ __
5,000 10,000 15,000 20,000 25,000
(A)
0.00145 M Cr(Bf ')3

Exercises 465
Fe'+ (d
6
)
0.077 M Fe(CI0
4
),
,':k
--/ ,
5,000 10,000 20,000 30,000 35,000
-
1
cm
(O)
Mn'+(,p)
0.36 M Mn(CI0
4
) 2
<
0.05
O
5,000 10,000 20,000 30,000 35,000
cm-
1
(E)
(d')
0.143 M TiCI
3
,1
Ti
3

,6,
,,
,
[ I
,,I , ,,
( !
5,000 10.000 20,000 30,000 35,000
cm-
1
(F)
(G)
5
Ni
2
+ (d
8
)
0.0025 M Ni(CI0
4
),
30,000 35,000
cm-
1
(H)
Cu2+ (d
9
)
0.0030 M Cu(CIO.),
20,000 30,000 35,000
cm-
I
(1)
l
,
l
466 Chapter 10 The Electroni c Structure and Spectra 01 Transition Metal Ions
6. Using the spect rum in problem 5( H), calcul a te the value or 10Dq and B ror H20 .
7. Given l he rollowing information ror d
3
[see, e.g., A.B.P.Lever,J. Chem. Ed. ,45, 711
(1968) ]: 4A zg ---> 4T
29
= 10Dq and "A2g--->4 T
Jg
(F)=7.5B'+15Dq- J/
2
(225B'Z +
100Dqz - 180B' Dq)J /2; calculate the va lueof10Dq and f3 (B' / B where B = 1030cm- J)
ror:
a. HzO, using the spectrum in problem 5(B).
b. CzO/ -,USIng the roll owing spectrum:
150
100
E
50
10,000 15,000 20,000 25,000 30,000 35,000
cm-
1
c. The value or 10Dq ror H
2
0 toward Ni2+ is 8500 cm- t, and f3 = 0.88. Compare
your results in part (a) with these values and offer an explanation. Al so compare
yo ur results towa rd Cr(lJl) for water with those ror oxalate.
d, Given lhat "A 2g ---> 4T
Jg
(P) is given by 7.5B' + 15 Dq + J1z(225 B'z + 100Dq2 -
180B' Dq)J /z, ca\clllate the rreqllency o rlhis band in Cr(C
2
0
4
b
3
-
8. The ion [Ni(pyridineUH
2
0)zJ 2+ has d-d absorption bands at 27,000, 16,500, and
10,I SO cm- 1 No low symmetry splitting is observed. Treating it as an octahedra l
compl ex, determi ne 10Dq. Compare this vallle with the average (rule or ave rage
environment) orlhe vallles predicted rrom the two six-coordinatecomplexes. The Dq
va lues for the six-coordinate complexes can be predict ed rrom Tabl e 10-6.
9. Why are octahedral Mn2+ complexes (weak fie ld) mllch less intensely colored than
those orCr
3
+ ?
10. The electro nic spectrllm or trisoxalatochromium(rII) doped into a host Jattice of
Na MgAI(C
z
0
4
h . 9H
z
O has been reported. The ground sta te is 4 Azg if octa hedral
symmel r yisassumed. The lowest exciled states(not m.o.'s) rorocta hedra lsymmetries
are then 2E , 2T , 2T
29
, and 4T
2g
. Theo bserved bandsand extincli oncoefficientsare:
g 19
17,500 cm-
J
e = 40
23,700 cm-
1
e = 67
14,500 cm-
I
e= 2.6
15,300cm- J E = 2.0
20,700 cm- 1 e= 0.3
a. 1
s
b. i
Ir the
axis,
pola
polal
are u
theC
band
one t
11. In R
orbit
Is il
12. The I
a. e
ah
b.
d
C', SI
a
13. a. O
0 1
b. N
w
01
Exerci ses 467
a. The aboye transitions have been shown lo be electronically aJlowed. Why is lhis
speclrum inconsislenl wilh oclahedral symmelry? (Multiplicily-forbidden lransi
tions have low intensilies ;generally, eis Jess lhan 5.)
b. Actually, lhe speclrum is consislent with lhe lrue symmetry of lhe molecule, DJ '
Lowering lhe symmetry causes the foll owing:
01, DJ
A
2g
A
2
Tg A
2
+ E
T
2g
A + E
Eg E
Ir the spectrum is lakenwith light polari zed perpendicularand paralleJ to the lrigonal
axis, all the abso rplions except lhe one at 17,500 cm- occur with perpendicularly
pol ari zed lighl ,butonly the bandsat 17,500 and 15,300cm-1 are presentwith parallel
polari zed light. Given that splittings of thedoublet octahedral states in DJsymmetry
are unresolved and thal 2E g is lower in energy lhan 2'[g, assign lhe transitions using
the DJexcited states. You muSl explain your choices.(Remember thal some doublet
bands represent unreso lved mullipletsand will consequentlycorrespond to more lhan
one transilion.)
11. In Re
2
CI
s
2 - (see problem 6, Chapler 3) the transilion of an electron from the b
2y
orbital lOthe b ,u orbital is a dd transilion in a molecule wilh a center of inversion.
Isil allowed? Explain.
12. Thefollowing is thesplittingof the stateenergies ofa high spin 3d
2
ion in an01, n.eld:
(*)
a. Calculate the free ion ground term symbol (*). ( ote the T and A Slales wrilten
aboye will have the same spin mullipli city as the free ion. )
b. Whalwould thisdiagram lookIike ifwe considered spin-orbital(I,L' S) effects?( o
only lhe T 9 state.) Show thesplitting and label each level with its J value and its
degeneracy.
c. Show the splitting pattern for a d
2
case for all J states aboye and label with
appropriale M J values. Show theeffect ofa magnetic field on the levels.
13. a. Of the states arising from an ion wilh a configuration oftwo 2p electrons, only
one is a spin triplet. What is the term symbolof thi s lriplet ? Show all work.
b. Nowconsiderspin-orbitcoupling.WhatJ slateswill this triplet give riseto?Whi ch
will have the lowest energy?
468 Chapter 10 The Electroni c Structure and Spectra of Transition Metal lons
14. a. Determine the irreducible representations for the terms ari sing fr om the splitti ng
ofa gaseous ioo 4F state by ao octahedral ligand field.
b. Usiog the method of descent in symmetry, determine the spio multiplicity ofthe
states in part a.
15. Determine the irreducible representations of the states ioto which the 2T
29
level of
Fe(CN)6J- is split by spin-orbit coupling.
16. a. List lhe operations of the double group DJ ' that are obtained by combioing the
operatioos ofDJ with the operation R. Make sure your lis t has the propert ies of
a group.
b. Howmany c1asses areio DJ'? Whataretheoperationsio eachc1ass? You may wish
toutilizethefactthatequivalentsymmetryoperationsaremembersofthesa meclass.
17. Iodicate the Squantumnumbers and ca lculate the energies ofthe states arising from
the magnetic coupling ofS1 =2 and 52 =5/ 2 metal centers.
-
In thi
an ur
Magr
magn
chapt
that &
systen
arran!
measu
field. '
FIGURE
values)
the line
define a
ofsubsl
HereHd
ofmagn,
' w
though IVI
thedivi si l
11- 1
Magnetism
he
of
11-1 INTRODUCTION
In this chapter we will consider certain aspects of magnetism that are critica! to
an understanding of the nmr and esr spectra of transition metal ion complexes.
Magnetic effects a rise mainly from the electrons in a molecule beca use the
magnetic moment of an electron is about 10
3
times that of the proton. In the
chapters on nmr, we ha ve discussed the electron circuJations of paired electrons
that give rise to diamagnetic effects. When there are unpaired electrons in the
system, we observe magnetic behavior that is rel ated to the number and orbital
arrangement of the unpaired electrons. The magnetic behavior is determined by
measuring (vide infra) the magnetic polarization of a sl.l bstance by a magnetic
field. Various types of behavior are ill ust rated in Fig. 11-1. Tt is convcnient to
N N s
(A) (B) (e)
FIGURE 11- 1 (A) Magnetic lield lines 01 Ilux (i.e., contour lines 01 constant lield
va,lues) in vacuum; (6) the lines 01 Ilux lar a paramagnetic substance in a lield; (e)
the lines 01 Ilux lar a diamagnetic substance in a lield.
define a quantity called magnetic indl.lction, B, in order to describe the behavior
of su bstances in a field.
B = Ha + 4n M (11-1)
Here Ha is the appli ed field st rength and M is the magnetization, i.e., the intensity
ofmagneti zation per unit volume. When we divide* by Ha, equation (11- 2) results:
We assume in an isotropic system that the directi ons or Ho and Mare coincidenl. Thus,
though we cannot divide a vect or by a vector, we can factor out the direclional pr oper ty and perrorm
he divi sion, leaving an equat ion in whi ch only he magnitudes a ppea r.
469
l
x
470 Chapter 11 Magnetism
B M'
-- = 1 +4n - = 1 +4nx (11-2)
Ho Ho u
Here M'/Ho is given the symbol Xl' and is referred to as the magnetic susceptibility
per unit volume. The volume susceptibility is thus related to the magnetization by
M' . .
Xv = H (dlmenslOnless)
o
B/Ho is the permea bility of the medium and is the magnetic counterpart of the
dielectric constant. Di viding Xv by the density of the substance, d, produces the
gram susceptibility, X
g
:
(11-3)
Multiplying X
g
by the molecular weight produces a molar susceptibility, x:
X x MW = X (emo/ mole) (11-4)
g
The value of X is negative for a diamagnetic substance and positive for a
paramagnetic one. In an ordered crystal, the susceptibility may be anisotropic,
i.e., represented by a tensor with several components. We shall discuss five types
of magnetic behavior: diamagnetism, paramagnetism, superparamagnetism, fer-
romagnetism, and antiferromagnetism. The behaviors eorresponding to various
classifications are described in Table 11-1 and superparamagnetism will be
discussed in a later seetion. The latter two types of behavior can be eheeked by
studying the field dependence of X. The behavior of the susceptibility as a function
of temperature is also quite characteristie for these different substances. This is
illustrated in Fig. 11-2.
TABLE 11-1. Various Types 01 Magnetic Behavior
Field Dependence
Type Sign Magnitude 01 X Origin
Diamagnetism 1O-
6
emu units Independent Field induced, paired electro n
circulations
Paramagnetism
+
Oto 10-
4
lndependent Angular momentum ofthe electron
emu units
Ferromagnetism
+
10-
4
to 10-
2
Dependent Spin ali gnment from dipole-dipo!e
emu units interaction of moments on adjacent
atoms,11
Antiferromagnetism
+
Olo 10-
4
Dependent Spin pairing, 1 from dipole-dipoJe
emu units interactions
t
nete
the bl
comp
temp
liq ud
Diam
As me
of pai
molee
ti bililj
the sq
Large
smalle
moleel
the di8
in fune
11-2
11-2 Types 01 Magnetic Behavior 471
3)
- 4)
1
x
Ferromagnetic
Paramagnetic
Antiferromagnetic
T he temperature at which the maximum occurs in t he plot of antiferromag-
netic behavior is rcferred to as the Nel temperature. The temperature at which
the break occurs in the ferromagnetic plot is called the C ~ r i e temperature. M any
compounds which, in the solid state, exhibit paramagnetic behavior around room
temperature exhibit slight ferromagnetic or antiferromagnetic behavior below
liquid helium (4.2 K) temperature.
11-2 TYPES OF MAGNETIC BEHAVIOR
Diamagnetism
As mentioned earlier, diamagnetism arises from field-induced electron circulations
of paired eJectrons, which generate a field opposed to the applied field. Thus, all
molccules have contributions from diamagnetic effects. ':he diamagnc tic suscep-
tibility of an atom is proportional to the number of elcctrons, 11, and lhe sum of
the squared values of the average orbital radius of the ith electron ;:.:
Ne 2 n 11
X = - -- L;:.2 = -283 x 10
10
L;:. 2 (11-5)
~ A 61nc
2
i 1 i
Larger atoms with more electrons have greater diamagnetic susceptibilities than
smaller atoms with fewer electrons. T he molar diamagnetic susceptibility of a
l110lecule or complex ion, X, can be obtained to a good approximation by summing
the diamagnec contributions from a11 of the atoms, XA' and from a11 of the bonds
in functional groups, X8'
x= I XA + L XB
(J 1- 6)
. j . )
, J
FIGURE 11-2 Temperature
dependence of
ferromagnetic, paramagnetic,
and antiferromagnetic
behavior .
,
TABLE 11- 2. Pascal 's Constants

Atoms, X ... Bonds, Xa
ca
XA ( x 10-
6
x... ( x 10-
6
Atom cm" mol e - ') Atom cm' mole-
I
) Bond
H
e
-2.93
-6.00
F
el
-63
-20.1
c=c
e-e
+5.5
+0.8
e (aromatic)
N
(aromatic)
N (monamide)
(diamide, imide)
o
O
2
(carboxylate)
S
p
-6.24
-5.57
-4.61
-1.54
-2.11
-4.61
- 7.95
-15.0
-26.3
Br
I
Mg2+
Zn2+
Pb2+
Ca
2
+
Fe
2
+
Cu
2
+
Co
2
+
- 30.6
-44.6
-5
-15
-32.0
-lOA
-12. 8
- 12.8
-12.8
C=N
e-
N=N
N=O
C=O
+82
+0.8
+1.8
+17
+6.3
Ni
2
+ -12.8
TI
rnl
us:
(2)
tht
di
Pa
Th,
ort
con
Thevalues ofXA and XB are referred to as Pascal's constants, and sorne common con
onesare listed in Ta ble 11-2. Thecalculation ofX is illustrated here for pyridine syst
and acetone.
he 6
CM
3
SUM OF C ONTRIBUTIONS TO X. (x 10 - MOLE-
1
)
disc
in e
5 x C (ring) = -31.2
5 x H = -14.6
field
1 x N (ring) = -4.6
This
(see
The functional groups areaccounted for by using the ring values for carbonand
nitrogen,'so L XR equals zero.
j
J
with
3 1
SUM OF ATOM CONTRIBUTlONS (x 10-
6
CM MOLE - )
3 x C = -18.0
6 x H = -17.6
1 x 0 = - 4.6
1
SUM OF B OND C ONTRIBUTlONS (x 10-
6
CM
3
MOLE- )
1 x /C= O/= +6.3
" "
3 1
L XA + L X.R = -33.9 X 10-
6
cm mole-
11-2 Types af Magnetic Behaviar 473
1)
lOn
line
1 and
For a transition metal complex, one can measure only the net magnetism,
XMEAS' which is the sum of the paramagnetic, XPARA' and diamagnetic, XOIA'
contri bu tions.
(11-7)
XPARA = XMEAS - XOIA
Thus, to obtain the paramagnetic susceptibility, the diamagnetic susceptibility
must be subtracted from the net susceptibiJity. This can be accomplished by: (1)
using the values fo!" Pascal ' s constants reported in Table 11-2 to estimate XDlA ;
(2) by measuring the diamagnetic susceptibility of the ligand and adding that of
the metal from Table 11-2 to obtain XOIA; or (3) by making an analogous
diamagnetic metalcomplex and using its value as an estimate of XOIA'
Paramagnetism in Simple System where S = 1/
2
The paramagnetic contribution to the susceptibility arises from the spin and
orbital angular momenta ofthe electrons interacting with the field. First, we sha ll
consider a system that is spherical , contains only one electron, and has no orbital
contribution to the moment. T he magnetic moment, 11', associated with such a
system is a vector quantity given by equation (11-8):
J = -g[3S ( 11-8)
where S is the spin angular momentum operator, 9 is the electron g-factor
discussed in Chapter 9, and [3 is the Bohr magneton onhe electron, also discussed
in Chapter 9 ([3 = 0.93 x 10 - 20 erg gauss - ').
T ~ ~ e Hamiltonian describing the interaction of this moment with the applied
field, H, is given by
(11-9)
This Hamiltonian, operating on the spin wave functions, has two eigenvalues
(see Fig. 9-1) with energies given by
E = msg[3H with m
s
= +1
- 2
(11-10)
with an energy difference
f..E = g[3H (ll-ll)
When H is about 25 kilogauss, f..E for a free electron with 9 = 2.0023 is about
2.3 cm - " which is-small enough compared to kT (205 cm -, a t room temperature)
that both states- are populated at room temperature, with a slight excess in the
ground state.
The magnitude of the projection along the field direction of the magnetic
moment, J.l.n, of an electron in a q uantum state n is given by the part ial derivative
of the energy of that state, En' with respect to the field, H, as shown in equation
(11- 12):
u = _ ~ E n - mg[3
(11-12)
, " oH s
In order to determine the bulk magneti c moment of a sample of any material,
we must cake a sum of the individual moments of the sU/tes weight ed by their
Boltzmann populations.
The Boltzmann factor for calculating the probability, P
II
, for populating
discrete states having energy leveis EII at thermal equilibrium is given by equation
(11-13):
N
II

P = -= (11-13)
n N
(
-E )
exp _ "
11 kT
Here N
n
ref rs to the populati on of the state n, whilc N refers to the total
populaton of all existing states. We have a wave function for each state, and \Ve
use the term ' level' to indicate all of the states that have the same energ y. The
population-weighted sum of magnetic moments over the individual states, which is
the macroscopic magnet ic moment, M, then, is given for a mole of mat erial by
equation ( 11-14):
M = N IlIlPII (11 - 14)
where _ is Avogadro 's number. Substit ut ing equation (1 1- 13) fo r P
n
in equation
(11 - 14) produces ( 11 - 15) for an S = 1/
2
sy temo
N Jl
n

/vI = IIJ. 1, _
( 11- 15)
+f 2 exp( - E
n
)
11 1, =- 1/2 k T
Substitut ing equation (11-12) for Ln and equation (11-10) for E,,, and summing
over m, = 1/
2
, produces:
9{3H) ( - 9{3H)
M _ fY. g/3 exp ( ID - exp 2kT'
(11 16)
- - 2-
[
(q{J H) (- Y/JH )
exp -- + exp --
2kT 2kT
When (g{3H/ kT) 1 (g{3 H cquals 1 cm - 1 for 9 = 2.0 and common fields of
5000 to 10,000 gauss, and k T is 205 cm -1 at room temperat ure), we can introduce
the following approxima:ion :
+g/3
H
) ( Y/3
H
)
(11-17)
exp ( 2 k T 1 2kT
Substituting equation (11- l7) into (1 1- 16) a nd simplifyi ng leads to
(11-1 8)
we
not
but
SCCs
wu h
Thls
13)
by
14)
ion
- 15)
ng
1- 16)
1- 17)
1- 18)
11-2 Types of Magnetic Behavior 475
Since the mol a r susceptibility is rel a ted to the moment by
M
X
=- (11-19)
, H
we can write
(11 - 20)
Equation (11-20) is the so-called Curie law, and it predi cts a straight -l ine
rel ation between the susceptibility and the reciprocal of tempera ture, giving a
zero intercept ; .e., X-> O as T approaches infinity. Thi s type of behavior is usually
not observed experimentally. Straight -Ii ne plots are obtained for many systems,
but the intercept is non-zero:
C
(11-21)
X = T- e
Equa tion (11 - 21), where C = [lg2/32/4k and ecorrects lhe temperature for the
non-zero intercept, describes lhe so-called Curie- W eiss behavior. Tt is common
to have a non-zero intercept in systems that are not magnetical ly dilute (i. e. , pure
solid paramagnetic ma teri al). In these systems, interionic or intermolecular
interactions<l ) cause neighboring magnetic moments to bec me aligned a nd
contribute to the value of lhe intercept.
For the case of molecules with no orbital angul ar momentum, one commonly
sees equation (11-20) written as
(11 22)
with units of Bohr magneton, BM.
This reduces to equation (11-20) for S = 1/
2
and yields the so-called spin-only
magnetic susceptibilities of complexes contai ning different numbers of unpaired
electrons.
Ho th X a nd M are macroscopic properties. In describing the magnet ic
properties of trans it ion meta l complexes, it is common to employ a microscopic
quantity called the effective magneti c moment Ileff' lt is defi ned as follows:
11
e
ff = ~ ; 2 1/2 (xT)1 /2 = 2.828(XT)1 /2 (BM) (11- 23)
The susceptibility employed in this equation i XrARA described above. Equa tion
(11-23) can be obtai ned by replaci ng g2 SeS + 1) in equation (11 - 22) by 11c1/ a nd
solving for 11eff' T hus, any efrects thar tend to make S not a good quantu.m number
beco me incorporated into the g-value (Recall lhe vari a bilit y of the g-value in epr,
TABLE 11-3. Spin-Only Magnetic Moments for Various
Numbers of Unpaired Electrons
Number01 Unpalred
Electrons S 11 (spln-only)(BM)
1/ 2 1.73
2 1 2.83
3 3/2 3.87
4 2 4.90
5 5/ 2 5.92
6 3 6.93
7
7/ 2 7.94
Chapter 9.) Equation (1 1-24) can be used to calculate the spin-only magnetic
moments for various values of S:
l1eff (spin-only) = g[S(S + 1)]1/2 (BM) (11-24)
where 9 equals 2.0 for an e1ectron with no orbital angular momentum.
The spin-only results in Table 11-3 are obtained for va rious numbers of
unpaired electrons. Tn many transition metal ion complexes, values close to those
predicted by the spin-only formula are observed( 1- 9) However, in many other
complexes, the moments and temperature dependence of the susceptibility are at
variance with these predictions. Ot her effects are operative, and a more com plete
anaJysis is in order.
11-3 VAN VLECK'S EQUATION
General Basis of the Derivation
In this analysis, we will introduce orbital contributions and also anisotropy in
the magnetic susceptibility for low symmetry molecules. Defi ning the principal
molecular axis as the z-axis, we can write the necessary part of the Hamiltonian
including these additional effects as:
(11-25)
where L and S are operators with x, y, and z components. In this chapter, g"
will be used when referring to the free electro n g-val ue. The first term on the
right of the equality sign describes the spin-orbit coupling (A i the spin-orbit
coupli ng constant) and is seen to be field independent. The other term sums the
spin and orbital contribut ions lo the electron momenl. [Note its resemblance to
equation (11- 9).J In using t his Ha miltonian, we have to worry about what basis
set to employ. In a free ion, ror a dI case with L' Scoupling ignored, the complex
functi ons I + 2), I + 1), et c. , are a good choice for they are already eigenfunctions
of H. Hence, when the full mat rix with elements <<fJ,, 1 Lo + geSz I <fJm ) f3H is
evaluated, there wil1 be no off-diagonal elements.
In
The
term
11-3 Van Vleck' s Equation 477
In a dI complex, with the liga nds defining the x, y, and z axes, the orbitals
are a convenient basis set. Now we have, for example:
(11- 25)
and
In this basis set, the off-diagonal elements will be non-zero; for example,
1
<dXl' ILz Idx' - )',) = 2i [< d + Z I Lz Id +2 ) + <el + Z I Lz Iel - z) - <d - z ILz Id +2 )
- <d-
z
I41 d_z ) J
= 2i
1
[2 + O+ O - ( - 2)] = - 2i
The 5 contribution to this matrix element will be zero, since
z
+ ('\ + (1)
<el,y I.) zld
x
: _ ' )=<el,yldx' _y, )< +ISzl+ ) =(O) 2: =0
The non-zero off-diagonal elements account for a distortion of the ground state
wave function by the applied field [we worked out the a boye mat rix elements
for Lz and 5z> but the full Hamiltoni an is f3( l + ge5) . ii]. This distortion is
accompli shed by mi xing in appropriate excited states. The diagonal elements are
called the first-order Zeeman terms, and the off-diagonal elements give rise to
second-order Zeeman terms. Ir there were no off-diagonal terms, a ll ofthe diagonal
ma trix elements would be to the first power in I-I and the resulting energies would
be first order in I-I .
Off-d iagonal elemen ts connecting sta tes of very differen t energies are
generally small compared to the energy difference, so l his problem is generally
treated with perturbation theory. We saw in the di scussion of the Ramsey equation
( hapter 8) tha t this approach gave [se to terms of the general fonn
A
where Op is an abbreviation for an unspecified operator. Th.e field-induced mixing
of excited states was used as an interpretation of the paramagnetic contribution
to the chemical shift. In the present case, we obtain from per lu rba tion theory a
term that looks similar:
[<1/1; I Z::z + ge Sz I1/I ) f3 HJ2
(11- 26)
Ni E i - Ej
478 Chapler 11 Magnetism
When the ion configuration becomes other Ihan dI , the advantage of lhe
perturbation treatment is seen, for the full matrix would be large.
Fora weakcomplex,the basis set for a full matrixevaluation would involve
using Ihe wave functions that resulted after a weak field approximalion in the
cryslalfield analysisoftheelectron-electronrepulsions.Forastrongfield complex,
the real d orbilals provide a good basis set for the complex. Thus, we see that
the relative magnitudes of the factors influencing the d orbital energies are
important in determining the best basis set. We can list sorne common, rough
orders ofmagnitude as follows, using C.F. to abbreviate the crystal field:
(A) Weak fie ld, first row transition metal ion:
C.F. > low-symmetry C.F. perturbation >
10
4
cm- 1 10
1
to 10
3
cm- 1
(B) Strong field, first row:
C.F. > e
2
/l'ij '> C.F. perturbation > }.I':'S
5 x l0
4
cm -
1
3 x 10
3
cm-
l
10
3
cm-
l
102
cm
- l
(e) Third row:
C.F. >
}, L 'S

el /rij
10
4
cm-
l
10
3
cm -
l
10
3
cm -
l
(D) Lanthanides:
J.LS

el/r
IJ
> C.F.
5
x 10
3
cm-
l
5 x 10
3
cm-
I
10
3
cm-
I
The magnetic field effect is about 1cm- l.
In our analysis so fa r, we have not taken spin-orbit coupling (the },LS
term) into account. F?rl!rst row transition metal ions, this is accomplished by
adding Ihe effecls of L' S to the energies as a perturbalion on thcir magnilude.
This is a good approximation only when ALSis small c mpa red to electron-
electron repulsions and cryst al field effects. The diagonal t S' matrix elements
art:evaluatedin t he real orbital basissetandadded to theenergiesascorrections.
When spin-orbitcouplingi large, this perturbationapproachis notappropriate.
For example, d
l
- a nd dI+ (signs r fer to the electron msvalue) have the same
m) value (%) and are mixed by r: .S.
Derivallon 01 the Van Vleck Equation
This very general discussion of how lO proceed in a crystal field evaluation of
the effects of the Hamiltonian in equation (11- 25) on the molecule or ion of
interest is sufficient for ourpurposes. We shalI now return to a di cussionofthe
inft uenceofthcscfactorsonth magneticmoment.Whenweli t thecontributions
to l he energy ofa given state, n,from t he factors discussed in the earliersection
forS = 1/
2
syst ms,in termsofthefi cld dependenceoftheeffect ,eq uution(ll- 27)
results:
En = En
IO
) +
HE"ll) + H
2
E
n
(
2
) (11- 27)
first -order Zceman second-order Zeeman
JcL' S
(diagonal terms)
(off-diagonal terms)
M
Ex
En
( 11
lhe
lhe
olve
the
lex,
that
are
lIgb
of
01'
11-3
Recalling tbat tbe projection of tbe magnetic moment in tbe field direction is
given by - oE,/oH [equation (11- 12)], we see tbat the first ter m, E,,( O) , makes
no contribution to the moment of a given state; the second term makes a
contribution that is independent of the field strength; and the third term makes
a field-dependent contribution. Thc E,,(I) term in equation (11- 27) is the same
term that we had in the Curie law derivation, except that the orbital moroentum
is now included. The magnitude of the second-order contribution wilI depend
upon E - Ej' It can be very large when the electronic excited state is close in
energy to the ground state and has correct symmetry.
In order to determine the influenee of these effects on the susceptibility, we
retllrn to the earlier Curie law derivation and rewrite eqllation (11-15) by replacing
exp( - Ej kD with
- E (O) _ HE (1) _ H
2
E (2) +".) ( HE (1)) ( - E (O))
" " --"- --'-'- exp n 1 -
(
kT - kT
Also, we let
- BE
11 = --" = - E (1 ) _ 2HE (2 )
""" n fJ 11 aH
M aking these substitlltions into equation (11-15) leads t o:
I (- E (1) - 2fTE (2)) 1 _ -
HE
'-"-
(l))
exp
n" n
(
kT
1'v1 =
Limiting this derivation
- L (0))( HE (1!)
I exp --'-' - 1 _ _ _n _
(
n kT kT
exp
kT
(11- 28)
(11- 29)
( E (O))

kT
(1 1- 30)
to paramagnetic substances, this eqllation must yield
M = oat / I = oand, in order for this to happen, the following must be true :
E (O) )
- En(l) exp -k; = O (11-31)
(
Expanding the numerator, and neglecting terms higher than E,,(2) as well as the
E
n
(2) En(l) product in equation (1 1- 30), and recalling tbat X = MIH [equation
(11-19)], we obtain from equations (11-30) and (11- 31):
(En(l)f ? ] (-En(O ))
I - - - 2E (-) exp
[
X N " kT ( _ E ''' ) kT
(11- 32)
I exp ---,j-
where E,, (O) has conlribll tions from AL ' S. etc. The En() term is a lway ' zero for
the ground levcl ; for a higher energy state the quantity giving rise to this energy
term in the absence of a fi eld is substi tu ted fo r EI/(O) T he term EI/(I ) contains lhe
m
s
g{3H and oth r first.-order cont ribulions, and EY ) he::; the conlributions fr m
the second-order Zeeman termo
Van Vleck ' s Equation 479
Thus, the susceptibility is determined by taking a population-weighted
averageofthesusceptibilityoftheleve!. Anr-folddegeneratelevelhasrcomponent
states, each ofwhich must be inc/uded in the summations ofequation (! 1-32). Its
use will become more clear by working out sorne
Applcation 01 'he Van Vleck Equatlon
We shall demonstrate the use of the Van Vleck equation [equation (11- 32)J by
applying it to the ground state of a free metal ion with quantum number J
(Russell-Saunders coupling applies). In all of the examples worked out in this
section, it is important to appreciate that all we are doing is taki ng a
population-weighted averageoft he individual momentsofthe level .The 2J + 1
degeneracyi removedbyamagneticfi el d,andtherelativeenergiesoftheresulting
levels are given by mJg[3H. We are considering only the ground level En( ) and
E
n
(2j , which are taken as zero. (l n doing a Boltzmann population analysis,c ;le
zero ofenergy is arbi trary; we set the energy ofthe ground level in the absence
ofH[i.e., En()J at zero for convenience.) Equation ( 11- 32) becomes
+J In 2g2[32
Y. =t:!. kT(2J + 1)
mJ - -}
n=O
= Ng
2
[32 (J
2
+ (J - 1) 2+ ... + (-J+ 1)2 + (-J)2)
kT 2J + 1
2 2
_ Ng fJ2 (J(J+ 1)(2J + 1))_ Ng fJ2 1
(11-33)
- kT 3(2J + 1) - 3k T J(J + )
Written in terms offlerr, we obtain for the free ion
fl eff = g[J(J + l)J1/ 2 (BM) (11-34)
Fora free ion,following the Russell-Saunderscoupling seheme, we give without
derivation(2) the expression for the g-value as:
S(S + 1) - L(L + 1) + J(J + 1)
(11-35)
g=l+ 2J(J+1)
We see from this equation that, in the free ion, eont r ibutions to L
eff
arise from
both thespin and the orbital angular momenta. Furt hermore, when L =O, then
J =S. Then9 = 2.00 andequation(11-34) reducestothespin-onlyformulagiven
in equation (11- 24).
The next example selected to illustrate the use of equation (11-32) is a
Ti 3+(d
1
) complexD)The spli tti ng ofthe gaseous ion terms by the crystal field,
spin-orbit coupling, and the magnetic field is ill ustrated in Fig. 11- 3. The
expl'essions fol' the enel'gies given in the figure are obtainee! from the wave
functions resulting from a weak erystalfield analysis by operatingon them with
the),1.. Sane! [3(1. + g.5) . Hopcratorsof equation(11- 25). Since10Dq is generally
large in an octahedral complex, we can ignore the 2 E state in evaluating the
susceptibility with equation ( LJ - 32). We shall discuss this entil'e problem by
starting with the ground 21'2 level and numbering the states 1 to 4 in order of
G

l led
l1ellt
. lts
1] by
er J
Ihis
a
1+ 1
llting
I and
. Ihe
senee
l l - 33)
11-3 Van Vleck's Equation 481
/ --:r&-- ---r
8
/ (4)
/
/
/
/
/
/
/
/
/
I
I
I FIGURE 11-3 The splitting
/
/
100q
01 the gaseous ion 20 state
/
20 /

(10) ",
" ,
" ,
,
"
,
,
Gaseous Oh Fleld
ion
inereasing energy. The En() terms for states 1 to 4 are - }, j2, - ;,/2, }" and l,
respectively (see Cha pter 10). The (1) terms are O, O, - {J I-/ , and + (J H,
respectively, while the E
n
(2) terms are _4/
3
((J 2I-/ 2j},), 0, +4iJ([J2 H
2
/),), and
+4M[J2H
2
jl), respectively. Substituting these values into equation (11- 32) and
multiplying each term by the degeneracy of the corresponding level produces:
N= {{ + exp + - (2)(0) exp
+ - exp + - exp
7 {ex
p
(2:T)+ exp + exp
Recalling that X = (N[J2/ 3kT)Jlef/' we obtain:
[
3), ] (-3}')
8 + - - 8 exp --
kT 2kT
Jlorf
2
= }. [ ( _ 3),)] [J
2
- 2+exp - -
kT 2kT
where [J is the Bohr magneton. Note that our analysis predicts that the Curie
law will not hold. As T approaches infi nity, Jler/ approaches zero, As '{ becomes
small, Jlef[2 becomes small; and as T approaches zero, the equations no longer
apply because g[JH kT. As }. approaches zero, Jlef/ approaches 3. Finally, as
T approaches zero, we have the very interesting result that a system with one
unpaired electron has zero susccptibi li ty. The result ari ses because t he spin and
orbi tal contributions cancel. These predictions are confirmed by experiment.
(6)
AL S H
Energl es
by an Oh field, by },L' S and
by a magnetic lield. The
degeneracies of the levels
are indicated in parentheses,
and the energies are listed
on the right.
/ ~ %
(4) // I
~ I
' , , ~ -+- -1
-2
FIGURE 11-4 The splitting
01 the 4A
2
state by a
tetragonal field D. (O is the
tetragonal splitting or
zero-field splitting
parameter .)
In Ol\[ analysis of this problem, we have ignored any contributions from the
2 Eg excited leve!. However, the aboye approximation is valid for many magnetic
applications. In the more sensitive epr technique, one can detect the contribution
from the excited state to lhe g-value (se e Chapter 12). With spin-orbit coupling,
the ground level (r8) and the r 8 excited level from 2Eg (f3 X f 6 = r 8) can mix,(4)
changing the g-value from 4fJH/ 3}, to 4},/11 + 4fJH/3 Jc, where 11 is 10Dq. The
second-order Zceman term mixes the ground level with the excited level, and the
exten t of mixing depends upon 11.
The next system (9) that we shall consider is chromium(rTI) (ce). An octahedral
field gives rise to a 4 A2 ground state and 4T2 and 4T) excited level s, as shown
for the quartet states in the Tanabe and Sugano diagrams. Since 4T, is about
J8,000 cm - ) higher in energy than 4A
2
, its contribution to the susceptibility can
be ignored. Since the ground state is orbitally singlet (A), there is no orbital
contribution to the magnetic susceptibility (vide ;nfra). The magnetism is predicted
with the spin-only formula and S = 3/
2
, Next , we shall consider the effect of a
tetragonal distortion on chromium( lIl). This removes the degeneracy of the
In, = 1/
2
and the Ins = 3/
2
states as shown in Fig. 11-4. The splitting by the
tetragonal component is described by the parameter D. Si nce this splitting exists
in the absence of a field, it is one of the many effects that are referred to as a
zero-field splitting. F or the case of an axial zero-field splitt illg, one can represent
this with the Hamiltonian, DSz2 The suscept ibility for this system when the
applied field is parallel to the principal molecular axis is obtained by inserting
values for E,,(Il, which equals e /2 )gJJ and e /l )gzfJ, re, pect ively, for the two levels
shown in Fig. 11-4. Wi th E}OI given a value of zero for the lower energy level
and a value of D for the higher one, we have :
Thus we see that when (D/ kn ~ J, which is true for a very small distortion or
at a very high temperature, the expression for Xz reduces to e/4) g/fJ2/kT,
while the spin-only formu la fo r S = 1/
2
rcsults as T approaches zero or D becomes
very large* To calcula te the powder average susceptibility, Xx and X
y
must be
evaluated using the x and y components of L and Sin equation (11-25) with the
DSz2 term added. The anisotropy in X can be ca1culated this way.
As a final example, we shall consider a nickel(lI) complex with a small
tetragonal distortion. The splitting is shown in Fig. 11-5.
Experimentally, D is approximately 0.1 cm - I for pseudooctahedral er
3
+ fr om a spin-orbital
mixing in of exciled sta les.
Ga
Ion
Whe
For C
cm "
is 42:
3359
1
del oc;
the m
below
for th
than (
it will
11-4
Spin-
When
agreen
sorne t
level
with the
a small
pin-orbital
11-4 Applications 01 Susceptibility Measurements 483
Energes
+{3Hz + O
FIGURE 11- 5 Splitting 01 a
-(3H, + O nickel(ll) ion in a tetragonal
lield.
o
Gaseous
Oh
Tetragonal H
ion field fleld
XII = (O) exp (-O) + (_::/)2 exp (if) + exp (if)
!:{ 1 + 2exp
exp (if)
XII = kT ( - D)
1 + 2 exp kT
When D <:g kT, the following ex prcssion results:
2.2( D)
, _ 2/i gz 1 - kT (1
Xn- ( 2D) 3kT kT
kT 1 + 2 - -
kT
For (NH4)2 Ni(S04)2 ' 6H
2
, t he experimental value(4) of gz is 2.25 and D i -2.24
cm-
l
, giving a value of XII of 4260 x 10 -
6
cm
3
mole-
1
The experimental value
is 4230 x 10-
6
cm
3
mole -
l
, whereas the spin-only formula predicts a value of
3359 x 10 -
6
cm
3
mole -
1
There is one additional point to be made in this section. If electrons are
del ocalized onto the ligands as a rcsult of covalency in the metal ligand bond ,
the matrix elements corresponding to orbital angular momcntum are reduced
below the value calculated by using the metalcentered operator L. To compensate
for this, one can use kL (where k, the orbitalreductionJactor , is a constant less
than one) to correct for d::.:locali zation of electron density onto the Iigand where
it will have redu ced orbital angular momentum.
11-4 APPlICATIONS OF SUSCEPTIBllITY MEASUREMENTS
Spin-Orbil Coupling
When equation (11- 34) is applied to compl exes of the rare earth ions, excellent
agreement between calculated and observed susceptibilities resulls, a shown for
sorne trivalent ions in Table 11-4.
i
TABLE 11-4. Calculated and Experimental Magnetic Moments for Some
rr
Trivalent Rare Earth lons
o,
H
Element Conll g. Term !leH(calc) !le. (exp)
Ce3+
Pr
3
+
Nd3+
Pm
3
+
Sm3+
Eu3+
Gd3+
Tb3+
Dy3+
Ho3+
Er
3
+
Tm3+
Yb
3
+
41'
2
41
3
41
4r
5
41
6
41
7
41
41S
9
41
10
41
41'1
4fl2
13
41
2F
3H
4
4/
9/ 2
5/
4
6 H
5
/2
7F
O
SS7 /2

6 H 15/ 2
5/
S
4/, 5/ 2
3H
6
2F / 2
2.54
3.58
162
2.68
0.84
O
7.94
9.72
10.63
10.60
9.59
7.57
4.54
2.4
3.5
3.5
1.5
3.4
8.0
9.5
10.4
9.5
7.3
4.5
n
ax
ele
TABLE 11 - 5. Calculated and Observed Magnetic Moments for Complexes
CO
of the 3d lons
(Calculated results a(e presented using equation (11-34) and the spin-only
fro
formula.)
of
sec
Ion Contlg. Term g[J(J + 1)]'/2 2[5(S + 1 )]'/2 11 (exp)

Ti3 +, y4+
y3+
Cr3+, y2+
Mn
3
+, Cr
2
+
Fe
3
+, Mn
2
+
Fe
2
+
Co
2
+
Ni2+
Cu
2
+
3d
l
3d
2
3d
3
3d
4
3d
5
3d
6
3d
7
3d
s
3d
9
2D 3/2
3F
2
4F3/2
5D
o
6S
5/2
5D
4
4F9/2
3F
4
2D l.
1.55
1.63
0.77
O
5.92
6.70
6.63
5.59
3.55
1.73
2.83
3.87
4.90
5.92
4.90
187
2.83
1.73
1.7-1.8
2.6-2.8

5.1- 5.5
4.1 - 5.2
2.8-4.0
1.7- 2.2
Th
ind
Sptr
ml x
an (
This excelJent agreement is obtained because the crystal field from the liganos
does not effectively quench the orbital angular momentum of the electrons in the
inner 4f orbitals. A very much different result is obtained with the 3d transition
series where, as can be seen in Table 11-5, the spin-only formula comes much
closer to predicting the observed results.
Thus, in many of the complexes, the orbital contribution is largely quenched
by the crystal fie\d. There is a very simple model that enables one to predict
when the orbital moment will not be completely quenched. If an electro n can
occupy degenerate orbitals that permit ci rculation of the electro n about an axis,
orbital angular momenl um can result. * There must not be an electro n of the
same pin in the orbital into which the electron must move.
In an octahedra:I dI complex, for example, the electron can occupy d
x z
and
d to circulate about the z-axis, and the compl x possesses orbital angular
yz
momentum. In an octahed ral , d
3
complex, there are elcctrons with the same spin
quantum number in both dxz and d
yz
, so this ion does not have orbital angular
T hi s rule is often expressed by reguiring that a rotation axis exists that enables one to rotate
one of the degenerate orbitals containing the electron into another vacant one.
met:
and
kind
here
J A
2
(
mea:
valUi
valul
cour
esser
As a
cont
arou
es
n/y
exp)
- 1.8
- 2.8
- 3.8
4.9
-5.9
.1 - 5.5
.1-5.2
.8-4.0
.7 2.2
gands
in the
Isttion
much
:nched
~ r e d i t
:)11 can
In aXIS,
of the
d .; and
angular
me spin
angular
: to rolate
11-4 Applications of Susceptibllily Measurements 485
momentum. Using this crude model, we would predict that the following
octahedral complexes would have effectively al! of the orbital contribution to the
moment quenched:
High-Spin:
Low-Spin:
The one electro n in e could only occupy d
z
' and d
x
' - .1" so circulaton about an
g
axis cannot result. If an E state in an appropriate ligand tield consisted of an
electron in d
xy
and d
x
' _ y' orbitals, an orbital contribution would be expected.
For tetrahedral complexes, for which high spin complexes result , the orbital
2 3
contribution is quenched in el, e , e
2
t
2
, e
3
t/, and e
4
t/.
Many molecules with A
2g
and Eg ground states have moments that differ
from the spin-only value. This variation results from two sources: (1) mixing in
of excited states that have sorne contributions from spin-orbit coupling, and (2)
second-order Zeeman effects (temp rature-independent paramagnetism). For
example:
(11- 36)
The . last term is the temperature independent paramagnetism which is tield
induced. The 4},/ lODq term arises from the mixing in of an excited state via
spin-orbit coupling. In lower symmetry complexes, the states are split 'l.rd more
mixing becomes possible. For an Eg ground state, the moment from mixing in
an excited state is given by:
(11- 37)
As we can see from the aboye discussion, the magnetic moments of transition
metal ion complexes are often quite characteristic of the electronic ground stale
and structure of the complexo There have been many reported examples of this
kind of application. A few nickel( H) and cobalt(IT) complexes will be discussed
here to illustrate tbis application.
In an octahedral tield, nickel(J1) has an orbitally nondegenerate ground state,
3 A
2
(t 2g 6 e/ ), and no contribution from spin-orbit coupling is expected. T be
measured moments are in the range from 2.8 to 3.3 BM, very close to the spin-only
value of 2.83 BM. Values for octahedral complexes slightly aboye the spin-only
value arise from slight mixing with a multiplet excited state in which spin-orbit
cou pling is appreciable. Tetrahedral nickel(Tl) has a 3 TI ground state that is
essentially (e
g
4
t2
/), and a large orbi tal contribution to the moment is expected.
As a result, even though both octahedral and tetrahedral nickel(fl ) complexes
contain two unpaired electrons, tetrahedral complexes have magnetic moments
around 4 BM compared to 3.3 BM or less for octahedral complexes. Experimen-
tally, it is found (8.10) that NiCV- , Ni(HMPA)42+ (lOa) (HMPA = hexamethyl-
phosphoramide). and(IOb) NiX Z . 2(C6H ShAsO (X = halogen) have moments in
excess of 4 BM. An inverse rel ationship exists between the magnitude of the
moment and the distortion of nickel(TI) complexes from tetrahedral symmetry.
The complex Ni X . 2(C
6
H
5
hP, which is known(ll) to be seriously distorted, has
a moment ofabout 3 BM. The structures of NiX
z
' 2 AMPA and CoXz' 2AMPA
(where X = CI - , Br - , 1- , N0
3
-) were deduced from combined magnetic and
spectroscopic studies'< IZ) This work provides a good illustration of the use of
these techniques.
In octahedral cobalt( If) complexes, the ground state is 4T
I 9
and a large
orbital contribution to the moment is expected. Mixing in of an excited state
lowers the moment somewhat but a value in excess of 5 BM is usually found
[,u(spin-only) = 3.87 BM]. The ground state for tetrahedral cobalt(TI) complexes
is 4A 2 and a Jow moment approaching the spin-only value might be expected.
However, an excited magnetic state is comparatively low in energy in the
tetrahedral complcxes and can be mixed with the ground state. M oments in the
range from 4 to 5 BM have been predicted(13) and are found experimentally. An
inverse relationship exists for tetrahedral cobalt(IT)( l3J complexes between the
magnitude of the morr.ent of a complex and the value of Dq as predicted by
equation (11-36).
11-5 INTRAMOLECULAR EFFECTS
In our treatment so far, we have assumed that there is no interaction between
the electron spins on the individual metal ions in the solido Next we wi sh to
consider molecules containing more than one melal ion with unpaired :; pins.
Consider the planar ML
4
X sys tem:
The influence of one met al, i, on the other, j, can be treated as arising from
pairwise interactions of metal d orbitals on centers i and j leading dimeric m.o. 's,
I/l and I/l j' When two d orbitals, each containing one electron, are orthogonal,
the two m.o. 's are degenerate, a t riplet state arises, and the coupling is said to
be ferromagnetic. When the lwo a.o.'s undergo a bonding interact ion, I/l and I/lj
differ in energy. lf the energy difference is greater than the pairing energy, a si nglet
state arises and the metals ar said to be antiferromagnet ically coupled. The
Hamiltonian for t h interaction between a pair of spins on atoms i and j is given
in equation (11- 38)
(11 - 38)
In the literature, one finds equation (11-38) writlen with - J, 2J, or -2J
instead of 1. Wit h the conventi on in equation (11 - 38), J is positive for an
antiferromagnetic interaction and negative fol' a ferromagnetic systcm.
R
Si
Fr
and
whi
.e.,
law,
where
l app

cernin;
the e
analy
To a
sta tes I
11-5 Intramolecular Effects 487
ween
to
spins.
is given
(11 - 38)
or - 2}
for an
Substituting the energies for Sl = S2 = 1/
2
from Fig. 10--8 into equation
(11-32) produces
2(gf3)2 ex (-J)
kT P 4kT
N
X
(
-J)
+ exp
(+
--
3J)
3 exp --
4kT 4kT
Rearranging, we find
2/1g 2 f3 2 1
X=
3kT ex p (J/ kT)
1 + 3
Since /1f32/3k is about l/S we obtain when 9 = 2
1 1
X - (11-39)
T exp(J/kT)
1 + 3
From this exp ression we find that Xapproaches zero as T approaches infinity
and becomes small as T becomes smal!. As a result Xmust have a maximum,
which is given by setting oIn X/o T equal to zero. From this we find
(11-40)
.e., Xhas a maximum value at
5 J
=-- T
N
2k
When J kT or when T T
N
, the susceptibility follows the Curie-Weiss
law, .e.,
3 1
(11-41)
X=4T+e
where e = J/4k. We al so see that as the quantity J approaches positive infinity,
X approaches zero.
Magnetic susceptibility measurements have provided information(J4) con-
cerning the influence of electronl c and structural change on the magnitude of J,
the energy separation of the triplet and singlet states.' A molecular orbital
analysis<l"S) provides a model to these infl.uences on the magnitude of 1.
To a first approximation, the energy separation of the singlet Es and triplet }:;r
states is given by
(11-42)
FIGURE Orbital
overlap and molecular
orbitals leading to (A) an
antilerromagnetic interaction
and (B) a lerromagnetic
interaction. M represents the
same metal with one
electron in its d orbital and B
the bridging group. In (A) B
has a pair 01 electrons in an
s orbital and in (B) pairs 01
electrons in two or thogonal p
orbitals.
whereH refers to a two-electron Coulomb integral, K an exchange integral,and
El and e2 the m.o. (f;1 and f; 2) energies. When the two m.o.'s are degenerate,
El = e2' J = - 2Kab anda ferromagnetic system results. When theenergiesdiffer,
the second term domina tes and the splitting leads to a si nglet ground sta te.The
value ofJ, which corresponds to the energy difference of the singlet and triplet
states, has contributions from a direct overlap ofthe metal orbitals and from an
indirect mechanism (referred to as superexchange) in which the orbitals interact
through the intermediacy of lone pairs or n-electrons ofa bridging ligand.
(14
)
Orbital interactions involving orbitals on the bridging atom that can lead to
antiferromagnetic or ferromagnetic interactions are shown in Fig. 11-6(A) and
(B), respectively,(I6)
-- IjfIlI
+ +
-1-t-ljf ll
\,
M' M

-1+-Ijf I
-1+-
d - orbital d- orbital
B(ep2)
(ep,)
O MO OMO (ep 3)
Lone pair
Molecular
s-orbital
orbital s 01 the
bridged syst ern
(A)
+ +-:>-+t- -+t-
M' M '-+t- + B lone pai r
d- orbital d- orbital Molecular p-orbitals
orbitals 01 the
(B)
bridged system
In complexes in which the M- B- M angle is 90, the situat on is close to
thatin Fig. 11- 6(A)with lhe lowenergy 2s orbitalofchlorinemakingonly smaIl
contributions to the bonding. As the angle changes to 180", more s character is
employed in thechlorinehybrids used to bridge the twoatomsand the situation
described in Fig. 11-6(A) results. !-;xperimentaIly,larger values ofJ are found as
the bridge angle increases to 180
0
The J values of a large number of di-
J.1-o xo-bridged copper( lI) complexes whose structures are known from x-ray
crystaIlographyhave been compiled_
CI7
) Forsquareplanarandsquare pyramidal
geometries the unpaired electron resides in d
x
' _)" orbitals.The J values for the
dihydroxo-bridgedcompl xes varylinearlywith lhe bridg angle beingferromag-
neticaIly coupled when the angle is less than 96". At angl es of 105 the J value
is greater t han 500 cm- l. A general trend ofincreasing J with increasing angle
is also observed in this system for bridging alkoxo, phenoxo, kl, to, and N-oxo
groups. Additionalstudies involvinga binucJearSchiffbaseIigand system shows
that J decreases from 660 cm- 1 for the Cu-Cu pair to 1SO cm- 1 for a Cu-Ni
*The combination - S,(S, + 1)- S2(S2+ 1) is constant for each level oC the di mer and is
Crequently dropped ; .e., the zero oC energy is redefined.
Q
S
1
Ir
c'l
fr j
10
10
10
of

dis

wh
R=
RJ
R==
stat!
com
(H)
solll
In
The
lOS
mole
strllc
nng
10 ce
com!
o
d
, pair
itals
:lse to
small
cter is
uation
und as
of di-
1 x-ray
'amidal
for the
romag-
.1 value
Ig angle
IN-oxo
n sho\Vs
Cu-Ni
rner and is
High Spin-Low Spin Equilibria 489
pair. Ferromagneticsystems a rise for Cu-V(IV)O a nd Cu-Cr(I1I), which ha ve
electrons in orthogonal d
x
' _ y' and d
xy
orbitals. In higher symmetry complexes,
\Vith triply degenerate T ground states, the problem becomes more complicated
\Vith the spin Hamiltonian formalism breaki ng down and more than one
parameter being needed to describe the exchange interaction.
A bimetallic doubly bridged oxo system formed by coordina ting
bis(hexafluoroacetylacetonato)copper( lT) totheoxygensof aSchiffbasecopper(lT)
complex \Vas found(l8) to have a J of only 20 cm- 1 The ligand distortions in
the adduct, were determined by x-ray diffracti o n 'allo\Ving an assignment ofthe
locationofthed
x
' _ )" orbitalcontainingthe un pairedelectrononthe t\Vo centers.
Ofthe two bridging oxo groups only one is common to the t\Vo d,' )' orbitals.
As a result,thi scomplexdoes notobeythea boyecorrelationsfor doubl y bfidged
oxo dimers. The reader is referred to extensive literature(19- 21)for additionai
studies ofthe influence ofgeometry and orbit al energies on the values ofJ .
11-6 HIGH SPIN-LOW SPIN EQUILIBRIA
If oneexaminestheTanabeandSuganodi agramsfor d
4
, d
5
, d
6
, andd
7
octahedral
complexes,it can beseenthatfor cert ai n valuesofDq/8 thegroundstatechanges
from a high spin to a low spin complexo For d
4
the SEg and 3T
I9
states a re
involved, whereas d
5
involves 6A and 2T
zg
, d
6
involves 5T and 1A I g, and d
7
I 9 29
involves 4T
I9
and 2 Eg. When the ligand fi Id is such that the twostates a re c10se
inenergy,theexcited statecan be thermaUypopulated andthesystem wi ll consist
of an equilibrium mi xture of the two forms. There have been ma ny reported
studi es of this type of behavior(22a) A typical system, which is selected for
di scussion because it has been studied(2 2b) in the sol id st ate and in sol uti on,
involves iron(II) complexes of ligands that are Schiff base type condensation
products oftren [N(CH
2
CH
2
NH
2
)3J and 2-pyridinecarboxaldehydc.The resull-
ing complex is shown in Fig. 11- 7, where only one ofthe pyri di ne aldimines has
been drawn in for c1arity of presentat ion. T he whole series of compounds in
which R,R', and R" are - 1-1 or- CH
3
were prepared.
The symbol (1 ) will be used to abbreviate the complex [Fe( PY)3trenJ2+
where R= R' = R" = H; (U) symbolizes [Fe(6 MePy)(PylztrenJ 2+ where
R= R' = H and R" = eH
3
; (lIJ) symboli zes [ Fe(6 MePylz(Py)trenr + where
R= H and R' = R" = CH); and (IV) symbolizes [Fe(6MePyhtrenJ 2+ where
R=R' = R"= CH
3
.
An equilibrium invol vingthe low spin IAI9(t2g6) a nd high spin ST
29
(t
2
/e/)
states was found both in the solid state and in solution for several of these
complexcs. Complex (1) is fuUy low spin at and below room temperature, while
(II )and (111)undergo spin equil ibrium both in the solid st ate and in solut ion. [n
solution, complex (IV) is essentially high spin at all temperatures aboye 180K.
In the solid state, a spin equ ili bri um exists that is very anion dependent.
Thermodynamicdatafor theint erconversioncanbe from thechange
in suscepti bi lity wit h temperal ure, and are reported to be +4.6 and +2.8 kcal
mole-1, respectively, for complexes (11) and (III) in soluti on. An x-ray crystal
structure determination indi cated that the methyl substituents on the pyridine
ringinteractwith the adj accnt pyridine moiety.T hus, theligandfield is weakened
in compound (IV) to the extent tha t a high spin compound results, while
compound(l)islow pino In thecaseofcompoul1d(TV), theaveragemetalnitrogen
(:2) ,.
' N
I 'N
4 # 6 R 1 R"
5 R'
FIGURE 11-7 Structural
formula of
tris{4-[(6-R)-2-pyridyI1-3-aza-
3-butenyl} amine iron(ll)
complex.
.
distance is found to decrease by about 0.12 Ain going from the high spin to the
low spin complex.
11-7 MEASUREMENT OF MAGNETIC SUSCEPTIBILlTIES
In this section, the measurement of bulk magnetic susceptibility will be briefly
covered(23) in the course ofpresenting the pertinent references for a more complete
discussion. The Gouy method(23b) employs a long, uniform glass tube packed
with the solid material or solution, which is suspended in a homogeneous magnetic
field. The sample is weighed in and out of the field, and the weight difference is
related to the susceptibility and field strength. If a standard ofknown susceptibility
is used, the field strength need not be known. Evans(23c) has reported a very
clever and inexpensive device for routine measurement of the magnetic suscep-
tibility by the G ouy method.
The Faraday method(23.) uses a small amount of sample that is sus pended
in an inhomogeneous field such that H(3 Hj3X) is a constant over the entire
volume of the sample. The method is very sensitive, so small sample. can be used
and studies can be made on soJutions.
Susceptibilities can al so be determined conveniently over a wide temperature
range, down to liquid helium temperatures, with a vibrat ing sample mag-
netometer.(23d) The change in the inductance of a coil upon insertion of a sample
can be related to the sample susceptibility. A mutual inductance bridge has been
described and used for susceptibility determination.(23
e
.n An ultrasensitive,
superconducting quantum magnetometer with a Josephson juncti on element has
also been described.(24)
When one studies the susceptibility of single crystals, the anisotropy in the
susceptibility can be determined(25-28) This information has several important
applications, as we shall see in our study of the nrnr and epr of transition metal
ions. The Krishnan critical torque method has been commonly used(29.30)
An nmr method has been reported( 31) for the measurement of the magnetic
susceptibility of materi a ls in solution. In this method, a solution of the paramag-
netic compJex containing an internal standard is added to the inner of two
concentric tubes. A solution of the same inert standard, dissolved in the same
solvent containing the dissolved complex, is placed in the outer of the two
concentric tubes. Two separa te nmr lines corresponding to the standard will be
observed, with the line from the paramagnetic soluti on Iying at higher frequency.
The contribution to the absolute chemical shift of a nucleus from t he bulk
magnetic susceptibility of the sample is given by(32):
(11-43)
where is the shift in Hz, V
o
the spectrometer frequency, m the mass of solute
per unit volume, a a demagnetization factor (vide infra), X and Xo the mass
susceptibility of the sol:.e and solvent, respectivel y, and Po and Ps the densities
of the solvent and solution respectively. X has contributions from a paramagnetic
x
P
and diamagnetic term XD as follows:
(11-44)
s
t
[
d
(
e
T
to
En
the
ofl
11-
Sup
thei
disr
are
cent
susc
fem
"gal
IS en
IS ar
ClrCI
abbr
tseU
(Oe)
42 in
Series
and tI
11--8 Superparamagnetism 49-1
For a spherical sample ex = 1/3 and the contribution to the shift from bulk
susceptibility vanishes. For a cylindrical sample whose cylinder axis is perpen-
dicular to the magnetic field direction, ex = 1/
2
, 1 n most superconducting magnets
the magnetic field direction is parallel to the cylinders axis, and ex = O. Thus,
[e/
3
) - ex] equals - 1/6 in the former case and 1/3 in the latter.
The shift of the standard in the paramagnetic solution is measured as just
described. The measurement is repeated for a n analogous diamagnetic complex
(e.g., the zinc complex). If the concentration of paramagnetic and diamagnetic
complex used is the same, the difference in the two shifts ~ ~ v / v o ) is related to
the mass susceptibility X: by:
(11-45)
The paramagnetic contribution to the molar susceptibility X
P
, whieh is related
to Ilerr (equation (11-23)), is given by :
(11-46)
Errors can arise if the reference material undergoes a ehemieal interaction with
the paramagnetic center. It is best to repeat the experiment with different types
of references.
11- 8 SUPERPARAMAGNETISM*
Superparamagnetism is observed in very small particles of transition metals and
their compounds, particularly their oxides. It can be used to characterize fine
dispersions of metal(s), alloy(s), and their oxides and has applications in several
areas including catalysis .
. It should be noted that parameters sueh as the magnetizat ion per eu bic
centimeter (M) or magnetization per gram (O") are better parameters than the
suseeptibility (X) for deseribing superparamagnetism and magneti cally ordered
ferro- and ferrimagnetic materials. Magnetization (M) is expressed in units of
"gauss "; this unit in reality stands for "gauss per cm]" Quite often "emu/cm
3
"
bulk
is employed. Dividing gauss by the density (g/ cm
3
) gives " gauss cm
3
per g," which
is an awkwa rd unit for the magneti zation per gram (0") . This situation is often
circumvented by naming it " emu/ g." It should be stressed that " emu" is an
1-43)
abbreviation for electromagnetic system of units in the cgs system and "emu"
itself is not really a unit. The applied magnetic field (H ) is expressed in oersteds
(Oe). Furthermore, the magnetie moment in ferro- , ferri-, and superpa ramagneti sm
*This contribution provided by L. . Mulay is an abbrevia ted, modified form of hi s Cha pter
42 in "Cata lys t Characterization Science," Ed. 1. L Deviney and J. L. Gl and, A. e. S. Symposium
Series No. 288, Washington, D.e. (1985). This malerial is reproduced by permission of lhe aulhor
and lhe American Chemical Sociely.
l
l
/11
Oe
G H
./ I
diagram al a hysteresis
curve lara typical
ferramagnet shawing
magnetizatian (a) as a
functian af the applied
magneti c field (H). Saturatian
magnetizatian is indicated by
/12
FIGURE 11- 9 Schematic
representation of a
multidamain lerromagnetic
parti cle in the unmagnetized
state. Each al the thr ee
damains with net moments
/11' /12' lkJ remain randamized
in this state. Circles 01
varying sizes represent the
subdamain
superparamagnetic clusters.
refers to the sat uration moment (11 or I1J and not l he effective moment (l1eff)
which is important in paramagnetism;133,34)
l1
e
ff = Jn(n +2)
where n is the numberofunpaired spins associated with discrete species such as
ions and free radicals.Thesaturation moment is given by
Ils = n
(11-47)
This situation arises because n, the number ofspins in a cluster, is very large-
of the order of 10] A of various systems of units, wit h factors for
conversion to ::; units is given by Mulay and Boudreaux(33) and by Mulay and
MUl ay(34), who discuss many applications to catalysis.
Superpa ramagnet ism is bes! understood by compaJing it wilh paramagnetism
and ferromagnetism. Ferromagnetic metals, such as Fe, Co, Ni , and insulators
such as y- Fe
2
0
3
and Fe
3
0
4
, show the well-known hysteresis curve (Fig. 1\- 8),
which stems from their domaio structure. In lheir unmagnetized state, the
unpaired electrons associated wit h each atom (or structural unit) have a net
(spontaneous) magnet ic momen! (11, ) or magneti zalion (0-,) which is the vector
sumofalJ unpairedelectronsinthatdomain ;theseareshownby thelargearrows
in Fg. 11-9. Saturaton s shown by (fs, lhe remanence, lhe rema ning magnetic
induction by (fr' and the reverse field TI cessary to brng (fr 10 Os given by H e'
the coercive force. Between the domai ns, a "Bloch wall" is formed, wit b spins
curled up in a helical fashion.The magnetizati on presentwithin a ferromagnetic
domain at zero degrees Kelvin and with zero appli ed fi eld is called l he
spontaneous. intrinsic, or lechnical magnetization (lsp)' The subdomain cl usters
with varying sizes represenl superparamagnetic c1usl rs (Fig. 11 - 9), with no
inLract ion between neighbors.T hesec1ustersare thermallyunstabl ,Lhatis,thei r
magnetic momenls (repres nted by moment vectors) experience thermal fluctu-
ations with great ease, as is the case with paramagneli c species due to the lack
oflong-range ordering.
Itis weJl known that when ferromagnetic and ferrimagnetic materials are
heated aboyea critica1Curie temperature(Te)' theychangeoverto paramagnetic
behavior; thus the hysteresis disappears. In cont rast ideal superparamagnetic
systems, when sufficiently cooled below a cri tical blockingtemperat ure (T u) will
experience a very slow relaxat ion time. Their net magnetic moment will align
parallel to lbeapplied fi eld (H) and appeartobehave as ifthey had an apparent
"bulk-like" ferromagnetic behavior. This aspect will result in hysteresis of
"apparent"ferrornagneticbehavior.Conversely,abovethe T
B
, the hysteresiswiU
disappearandlhec! ustersw.illshowauniquecurvewithnohystere is(Fig. 11-10).
Each fcrromagnetic dornain consists of rnyriads ofspins. e ne can imagine
smaJl c1usters wit hi neach dornai n havingdi fferentvolumes(VI' V
2
, ..., V). These
subdomain particles,whiehconsistof severalthousandspinsarethesuperparamag-
netic c1usters. They wi ll have large magnetic moments ofseveral tbousand BM
(Bohr magnetons : recaJl one BM = eh/4nmc). When such supcrparamagnetic
c1ustersarewell-dispersedon(or"wi thin")asubstrate(e.g. , Si0
2
, carbon,zeolites,
etc.), there is no magnetic interaction between their moments. Hence, the
I
I
I
I
o.
0 6
o.
J
O
superp
param
Peff are
thesup
magnet
wil h de
constan
magnet
runctior
is no ca
in conl
behavi o
and fem
anical st
Sine
Ism, one
interacti
Flere,Il e
1I for sin!
02
as
for
md
ism
.ors
- 8),
the
net
etor
ows
letic
He'
,pins
netic
the
Isters
It no
their
uctu-
: lack
ls are
1.0
" : fJ.> 10
6
(el Ferromagnetism
I ,
: : per domain
b
ti
0.8
(81 Superparamagnetism ill
0.6
OA
80 100 120 140
HIT (oersted degreel

per cluster
superpararnagnetic clusters bebave in the sarne manner as magnet ically dilute
pararnagnetic ions. For pararnagnet ic ions, the susceptibil ity (X = ajH) and the
J.i eff are good pararneters for the interpretation of rnagnetic results. However, for
the superpararnagnetic clusters with a giant BM nurnber of 10
4
, the per gram
rnagnetization (a) is a good parameter. The a increases with increasing H and
with decreasing tempera ture (Y) . Thcrefore, it is custornary to measure a at
constant field strength and varying ternperature, and vice versa. When the relative
magnetization ajas (where as is the saturation rnagnetization) is plotted as a
function of HI T, one obtains an excellent superposition of data points, and there
is no coercive force (He = O). Therefore, hysteresis is not observed in Fig. J1- 8
in contrast to the bulk fe rrornagnetic rna terial. Hence, superparamagnetic
behavior may be regarded as a phenomenon interrnediate betwcen pararnagnetisrn
and ferrornagnetisrn. Note that for pure fer romagnetic rnateri als, without rnech-
anical strain, the He ca n be as small as 0.5 oersteds.
Si ncc " superparamagnetism," as t be name implies, is similar to paramagnet-
ism, one can apply the c1assical Langevin function, first derived for the non-
interact ing paramagnetic spins, to the non-interacting, ideal S.O. c1usters. Thus,
(11--48)
Here, J.ie stands for lhe (giant) magnetic moment of the cluster which repJaces the
J.i for single, isolated paramagnetic spins; k is l he BoJtzmann constant.
11--8 Superaramagnetism 493
FIGURE 11- 10 Plot of the
relati ve magnetization (JI (Js'
as a function of HI T. (A) A
paramagnetic system is
characterized by an eHective
moment with a maximum
80hr Magneton number 01
10 per ion and by the
absence 01 hysteres is. The
very small slope 01 the
straight line is exaggerated
lar clarity. Paramagnetic
saturation occurs al a very
high rati o HIT = 10
4
Oe/K.
(8) Langevin curve lar
superpar amagneli c clusters.
Large cl uslers wi th r el at ivel y
high moment s are shown to
reach saturati on easi Iy at
lower values of HIT.
Simil arly small clusters with
a net smal l moment are
shown to reach satur atl on
wi th difficulty, at hl gh values
of HI T. (e) Top part 01 a
hysteresis curve observed in
a ferromagnetic curve.
'
I
494 Chapter11 Magnetsm
In the aboyeequation, all quantities except /-le can be measured. The/-l ecan
bederived for (ideal)superparamagneticc1usters by a curve-fitting procedure(el
Ref. 3). The gist of obtaining the average volume (v) of a superparamagnetic
cluster hes in the basic definition of(Js, which for a superparamagnetic system
can be written as (Js= /-l clv.Itshould be noted thatat the atomiclevel, the molar
saturation magnetiza tion (XM) is given by
emu per mole
here N is the Avogadro's number ofspecies,each carryinga moment/-l s= n(the
number of unpaired electrons per species), and fJ is the Bohr magneton. (A
convenient number, NfJ = 5585).
From the low-field (LF) and high-field (HF) approximations(35.36) of the
Langevinfunctionstatedbelow,onecancalculatetheV
LF
for largec1usters(which
magnetically saturate easily at low values of HI T) and for small c1usters V
HF
(which saturatewith difficulty at high values ofHI T) From thev
L
F and v
Hr
,the
averagevolumevof c1usterscanbeestimatedbytakingthearithmeticmeanO5.36)
- 3 18k
d
LF
= - ((JI(Js)/(HIT) (11-49)
nI.,
- 6k
d
H
/ = - (1 - (JI(J,)-I/{ HIT) (11- 50)
nIs
Here Is is the spontaneous magnetization for the bulk material. F'or elemental
Fe,Is is 1707gauss(or oersted) at room temperature. Cluster diameters as small
as 2 nm and ranging up to 20 nm have been deduced from magnetic results for
variouscatalysts such as Fe, Fe-Co,Fe-Ru, and Ni, supported on high surface
areaalumina, silica and carbonP4-36)
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n
f
ie
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u
he
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ieh
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the
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Jin "PhysicalMethodsofChemistry,"Vol. lJfB,ed.B. W.Rossiterand1. F. Hamilton,
Wiley Interscience Publishers, New York, 1989.
35. H.Yamamura and L ..Mulay, 1. Appl. Phys. , 1979,50,7795 (1979).
36. P. W. Selwood, "Chemisorption and Magnetizalion," Academic Press, Ne w York,
1975.
EXERCISES
lo Consider the following system of energy levels, which could arise from zero-field
splitting of an S = 1state:
2 g2FH
2
E(IO) = - 3D- W-
1 g202H
2
E(I - 1) =3D - gflH +----w
Here D is the zero- nel d splitting parameter and all other symbols have their usual
meanings. Determine the molar paramagnetic susceptibility of this sys tem.
2. ThepI conngurationofa free ion hasa 2P groundstate. Considertheion in a magnetic
field directed along the z-axis.
a. What is the degeneracy ofthis state?
b. Write the wave functi ons for this state in Dirac notation, .e., 1M!.> M
s
)'
c. The major perturbation o n thi s state is spin-orbit coupling:
Consider the major contribution in a strongz field leading to:
Does this give diagonal elements, off-diagonal elements, or both, in the basis set
ofpart b? Evaluate the energies ofthese wave func tions using H.
d. The Zeeman Hamiltonian is f =fl H' (L +28)=flH ,(L, +25,). Evaluate the
energies ofwa ve functions ofpart b using thls Hamilt onian.
e. Use the energies obtained in parts e and d, and the Van Vleck equation,
to calculate X.
3. The following represents the approach taken to the magnetic susceptibility dataofa
complex ofthe form shown as follows.
Consideroctahedral Fe(TI). In many systems, the low spin lA19 state is less than
1000cm- 1 below the high spin sT
2g
state, so that both are appreciably populated at
room temperature. The 1A state is non-degenerate and the 5T is IS-fold degenera te
(why?). Mathematically, a T state in an octahedral field is equiva lent to a P state in
a free ion; .e., it may be considered to have L = 1 and ML =- 1, O, -1- 1. Consider
the 1A state to be unshifted by all perturbations.
a. Write the 15 basis functions for the sT state in Dirac not ation, using T-P
equivalence. Hin!: The wave function having M
L
= 1 and Ms = -2is denoted
11, -2). In this formulation, M
L
and Ms are often referred to as "good quantum
numbers."
H 3 4
eH eH _N):--o5
2 2
R'
N,CH, >-Q + Fe(H) --CH-
R"
b. ow, let the complex undergo a trigonal distortion, .e., one for which the
octahedron 's thredold axis is retained. The effect of this distortion is described
phenomenologically by the Hamiltonian
- (2 2)
J-J = :3 - L,
where is the trigonal distortion or zero-field splitting parameter and L: is the
z-component of the equivalent orbital angul ar momentum. As is often the case,
chemical factors influencing the magnitude of 11 are poorly understood, and values
oblained in experiments such as t his may help elucid ate the factors invol ved. The
Zeeman Hamitonian for a magnelic field oriented along z is:
Fl = f3H)L, + geS,)
] [ere we are considering only the z-direction (parallel to the threefold axis) , so OUT
final expressio n will be for XII'
The following illustrate the use of the Hamiltonian and wave functions:
G-1,2} 1, - 2) = G-M/} 1, - 2) = G-l} 1, - 2) = - / 1, - 2)
5,11 , -2) = Msll, -2) = -2 11, - 2)
Apply the two lerms of Ihe Hamiltonian discussed aboye lO the sT wave
funclions derived in parl a. Show t hat all' off-diagonal elemenls of Ihe 15 x 15
matrix must be zero. (This means tha l al! E(2) terms of Ihe Van Vl eek equation
will be zero.) Hence, determine the energi es of the 15 wave functions. Confi rm that ,
as the total Hamiltonian has been constructed', (he cenler of gravity is maintained;
Exercises 497
i.e., that f = bL,z, though giving the correctsplitting pa llern would not maintain
10. \
a center ofgravity.
ll. I
c. Let the difference between the 1A and sT states be parametri zed by E. The
energy level diagram should look like this: .
5A
_: ~ g
5T
.
. f
t
,
-
--
sE
*
o
c::::::'::' _
E -:::::::
lA lA
1
mag
Oh D3
Use the Van Vleck equation to determine XII as a function ofE, (j , and T
In the actual experiment, spin-orbit coupling was included, introducing
off-diagonal elements that complicated the analysis. The experimental X uso T
re lation was computer fitted to the theoretical expression to yield best values for
A, E, and (j. It is interesting to note that a poor fit was obtained unless E was
a llowed to vary with temperature.
4. The 300 K molar magneticsusceptibility for a solid sample of
H3H3 H W<
Cu(hfaclz-O- N H
H
3
C H
H
3
C H
was determined to be X = - 186 X 10-
6
cm
3
mole- l. Calculate the mojar paramag-
netic susceptibility by correcting for the diamagnet ism ofthe complex. What is /Cff ?
How can you explain this /crr?
a. I
t
b. I
h
d
5. a. Co(N2H4)2C12 has a magnetic moment of3.9 BM. ]s hydrazi ne bidentate?Propose
a structure.
b. Howcould electronicspectroscopy be employed lO support the conclusion in part
a?
6. In which ofthefollowing tetrahedral complexeswouJd you expect contributionsfrom
spin-orbitcoupling? y 3+, Cr
3
+, Cu
2
+ , Co2+, Fe
2
+, Mn
2
+
7. In which ofthe following Jow spin square planarcomplexes would you expect orbital
d
6
contributions?d
2
, d
3
, d
4
, d
5
,
8. Why is Fe
2
(CO)9 (with three bridging and six terminal carbonyJs) diamagnetic?
9. ExpJain whymixingofa D
4h
componentin with a T
d
groundstatelowersthemagnetic
moment in nickel(Il)complexes.
Exercises 499
10. What is the expect ed magnetic moment for Er
3
+?
11. In the figure below, effective magnetic moment us. temperature curves are showr, for
two simil ar tri s-bidentate Fe(III) compounds:
s R)' Fe , e-N/
.yY "-
S R 3
~
A: R = n-propyl
B: R = isopropyl
T.
3.0
-:
2
en
;;
2.0
:1.
3.0
(B)

Temperature
in part
3.
b.
Pro vide an explanation in ,crms of the electronic structure of an Fe( l lI) complex
that accounts for lhe changes in !lerr over the given temperature range for each of
the lwo complexes. In other words, why are the lwo curves so different whil e the
two co mplexes appear to be so si mil ar?
In the above plOlS the poinls represenllhe experimental dala and lhe lin es rep resent
least-squares fits to theoretical equations. With lhe use of an cnergy level diagram,
describe what parametcrs might be used in such a theoretical trealmen!.
from
orbital
ic
12-2
We sh
Nuclear Magnetic
compo
Resonance of
Paramagnetic Substances
in Solution
IVANO BERTINI AND CLAUDIO LUCHINAT
12-1 INTRODUCTION
In the early days of nmr, there was a widespread belief that one could not detect
the nmr spectrum of a paramagnetic complex because the electron spin moment
was so large that it would cause rapid nuclear relaxation leading to a short
nuclear TI and a broad nmr line. This is the case for complexes of certain metal
ions [e.g., those of Mn(II)J , but it is not the case for many others. For instance,
in Fig. 12-1, t he proton nmr spectrum(J) of the paramagnctic complex
Ni(CH
3
NH
2
) 62+ is presented (B) and compared to t hat of CH
J
NH
2
(A).
Hinc. - B o i n c ~
CH TMS TMS
CH
3 NH
2
~ -A ~ ~
3.081 .92 O 79.9 - 98.3
v. ppm v. ppm
(A)
lB}
FI GURE 12- 1 Proton nmr spectra (simulated) 01 solu!ions 01 (A) CH
3
NH
2
and (B)
Ni(CH
3
NH
2
)6
2
+ Note tha! the relative scales in (A) and (B) differ.
These spectra raise several questions:
1. Why do we see a spectrum for the paramagnetic complex?
2. Why are the observed shifts from tms in the complex so la rge relative
to those of the uncoordinated li gand? The normal range of proton shifts for most
organic compounds is about 10 to 15 ppm and the shifts in the complex are well
outside this range.
3. Why does the NH proton resonance shift upfield, whereas t bat for the
CH3 protons shifts downfi elcl?
We shall answer all of these questions in the course of logically developing
500 this topic and in the process introduce a powerful t ructural tool.
nucleus an!
S = 1/
2
, the
in F ig. 12-1
In this
the fJ spin sial
~
-
dctect
loment
l short
1 metal
stance,
omplex
relative
for most
are well
12-2 Properties of Paramagnetic Compounds 501
12-2 PROPERTIES OF PARAMAGNETlC COMPOUNDS
We shall briefly review and expand upon those properties ofparamagnetic
compounds important to understanding their nmr. Unpaired electrons have
magnetic moments whose intensity is given by:
(12- 1)
where ge is the free electron g factor, S is the total spin quantum number that is
equal to one-half times the number of unpaired electrons, and /-lB is the Bohr
magneton*, equal to eh/2m. (9.274096 x 10- 24 J. T-). Unpaired electrons reside
in molecular orbitals and are delocalized over the entire molecule. The unpaired
electron in one molecular orbital can also spin polarize an electron pair in a
doubly occupied molecular orbital as discussed in accounting for the proton
hyperfine in the epr of the methyl radical. At every point in the molecular frame
there are contributions from the direct (except at a node) and spin polarization
mechanisms. Thus, a nucleus in a molecule, containing one or more unpaired
electrons, may eX;1erience spin density at its point in space and/or feel spin density
that is nearby. Referring to atomic orbitals as composing molecular orbitals, net
spin density exists at the nucleus of the atom under investigation only through
its atomic s orbitals since only the wave functions for s orbitals have a fin ite
value at the nucleus. A node cxists al the nucleus in all other type orbitals. I n
addition, there are fractional un paired electrons in orbitals other than s on the
atom of interest and on neighboring atoms. Finally, a large fraction of the unpaired
electrons in the molecule is always located in the aramagnetic metal orbitals.
Magnetic nuclei in a paramagnetic molecule interact with t he unpaired
electrons just as a magnetic dipole interacts with another magnetic dipole. The
interaction is formally divided in two parts, one with the spi n density at the
resonating nucleus and another with the spin density cloud in the rest of the
molecule. The former is called Fermi contact coupling, wbereas the latler is
through-space dipolar coupling.(2) The Fermi contact coupli ng can arise from
either the direct delocalization mechanism or spin polarization. The calaculation
of the dipolar interaction req uires evaluation of an integral over all space, along
with a detailed knowledge of the spin density distribution. Jt is customary to
further divide the dipolar interaction into a so-called metal-centered term and a
ligand-centered termo The former considers the unpaired electrons localized on
the metal center and the interaction is eval uated using a point dipole approxi-
mation. The latter considers unpaired eiectron density delocalized on the ligand
and is often restricted to one or a few atomic orbitals of the atom in the Jigand
whose nucleus is being studied. l ndeed, spin density near the resonating nucleus
is always relatively small providing a significant contribution only at small
distances.
In the absence of an external magnetic field, the cou pling between a magnetic
nucleus and an electron gives rise to new energy levels. In (he cas of = 1/
2
and
S = 1/
2
, the coupling partially removes the degeneracy ofthe fom functions shown
in Fig. 12-2(A) leading to Fig. 12- 2(B).
In this chapter we shall use /lB instead of (3 for the Bohr magneton to avoid confusion with
the f3 spin sta te. SI units are used throughout except sec is used for seconds.
502 Chapter 12 Nuclear Magnet ic Resonance of Paramagnetic Substances in Solution
FIGURE 12-2 Energies 01
the spin wave lunctions lor
an S = '/
2
, 1= '/
2
system in
the absence (A) and in the
presence (8) 01 hyperfine
coupling between the
electron and nuclear spins.
The lower-Ievel and one 01
the upper-Ievel lunctions are
linear combinations 01 the
non-interacting IM
s
, MI >
lunctions. II the coupling, A,
is negative, the splitting
would be reversed, with the
single degenerate level
higher in energy.
FIGURE 12-3 Ellect 01 the
appl ication 01 a magnetic
lield Bo 01 increasing
strength on the spin energy
levels 01 an S = ' /
2
, 1='/
2
system. The labeling 01 the
spin lunctions in the high
lield limit is shown. The
ligure is drawn lor a positive
value 01 A. The electron
transitions are indicated by
arrows.
E
A
(lt3eaN) - laet3N )
(A) (B)
The application of an external magnetic field* splits the levels according to
the orientation of the electronic or nuclear dipoles with respect to the orientation
of the magnetic field (Fig. 12-3; also see Fig. 9-2). When we consider the
nucleus- electron coupling from the point of view of the nucleus, we should keep
in mind that the orientation of the magnetic dipole of the electron changes very
fast compared to that of the nucleus. Nuclei relax with lifetimes of the order of
seconds whereas electron relaxation leads to lifetimes of 10 - 5 to 10 - 6 sec for
radical s and 10-
7
to 10 - 13 sec for metal ions. (2) Therefore, the nucleus sees an
oscillating magnetic dipole corresponding to the electro n exchanging between
the positions depicted in Fig. 12-3. To a first approximation the average coupling
E
*In thi s chapter the magnetic induction, Bo, wiJl be used instead or the magnetic field, H. Thc
SI unt for B s the tesIa (T) and al! eq uat ions are presented in tbis unir. In the discussion, magnetic
induclion will be called lhe magnelic fieId .
12-3
80
12-3 Considerations Concerning Electron Spin 503
JI. The
magnetic
energy IS zero because the two electronic orientations provide equal moments
with different signs. However, in a magnetic field, the different populations of the
two ms levels lead to a time average different from zero, as shown in Fig. 12-4.
The nuclear coupling with an average electronic spin gives rise to a chemical
shift contribution in the nmr spectrum whose magnitude is proportional to t ~
nature and extent of the coupling. The magnitude of the shift may be anisotropic
depending on the orientation of the molecule with respect to the external magnetic
field. In solution, rapid molecular rotation produces an average value of the shift
anisotropy. Consequently, this shift is called the isotropic shift or isotropic
hyperfine shift and can be determined experimentally by measuring the difference
in shift of a given atom in a paramagnetic compound and that of the same atom
in an analogous diamagnetic compound. In the next section on the isotropic
shift, we will address the questions concerning the large shifts seen in paramagnetic
proton nmr as well as why sorne shifts are upfield and others downfield.
Electron relaxation provides mechanisms for nuclear relaxation beca use the
nucleus senses a ftuctuating magnetic field. In sorne cases, the effect is moderate
and reasonably sharp nmr resonances result. 80th the shifts and nuclear relaxation
times can be analyzed to produce valuable structural and dynamic information.
In other cases, the efficient nuclear relaxation mechanisms lead to broad nmr
lines, often to the point where the spectral line escapes detection. However, even
very broad lines can be exploited. For example, when the protons of water
coordinated to a paramagnetic metal ion are too broad to be detected, the
spectrum can be studied in water as a solven!. When the exchange of the
coordinated water molecules with solvent water is fast compared to the difference
in chemical shift between the bound and free water, a single li ne results whose
tine width is a linear function of the mole fraction of the bound and solvent
water. The smaller the T
2
of the bound water proton, the greater the possibility
of detecting line broadening of the average ti ne in dilute aqueous solution. Thus,
information about the structure and dynamics of the systems can be obtained
by understanding the effect of hyperfine coupting on nuclear relaxation.
When the discussion of relaxation is completed, we will understand why the
nmr of sorne paramagnetic complexes can be detected while others are too broad
to be seen. Finally, examples of the analysis of shift and relaxation data to
chemical problems wi ll be prcsented along with the use of nmr to investigate the
electronic properties of paramagnetic polymetallic clusters. We will see that
answering the simple questions raised at the start of this chapter provides us
with a powerful tool for studying the struct ure and dynamics of paramagnetic
compounds.
12- 3 CONSIDERATIONS CONCERNING ELECTRON SPIN
So far the discussion has involved pure electro n spins. In contrast to the nuclear
spin, the electron moves around the nucleus giving rise to an orbital angular
momentum that is small but different from zero.( 3) We discussed the coupting of
the spin and angular momentum in ig. 9-17. The orbital contribution should
m s = + ~ + Shortert mes E
~ (a)
N m,= - '2 Longer time
'+ .
(13)
FIGURE 12-4 The nucleus,
N, senses a weighted time
average 01 the magneticlield
produced by the unpaired
electron in the two energy
states.The time average 01
the electron magneticlield is
non-zero and along the
direction 01 8
0
because the
electron spin spends slightly
more time in the lower leve!.
l
i
504 Chapter 12 Nuclear Magnetic Resonance of Paramagnetic Substances in Solution
FIGU RE 12-5 In the
presence of spin orbit
coupling, the electron spin
transition energy differs from
gell-BBo and depends on the
orientation of the molecule in
the magnetic field, Bo. The
diflerence can be expressed
in terms of changes in the
value of the g-factor. In this
example, both the extreme
values g1. and gil are taken to
be larger than ge
(gil > g1. > gel
be kept in mind when, for the sake of simplicity, we refer to electro n spin. The
electro n in a magnetic field has two different orientations whose energies are
-C/2)ge/1B Bo and (1/2)ge/18BO' If, however, the total magnetic moment is larger
or smaller than that of the free electron beca use of spin orbit effects, the Zeeman
energies will be changed accordingly as modeled in ligand field theory. We account
for these changes by using a q-value that differs from the free electro n value, Fig.
12-5. Therefore, we will refer to ge = 2.0023 for the free electron and to 9 i= 2.0023
when spin orbit coupling is taken into consideration. Information about the
actual value of 9 can be obtained directly or indirectly with epr spectroscopy
(Chapter 13).
E
.1.
4

'4

8
0
The Expectation Value 015z, (5
z
)
When a bulk sample of a paramagneticmolecule containing one unpaired electron
is placed in a magnetic field, the two ms spin states are not equally populated.
The rate of electron exchange between the two levels is described by the quantity
- l. The pieture is equivalent to that of a single moleeule (S = l/2) in a magnetie T
2
field spending more time in one leve! than the other. The population fraetion of
the two spin levels is described by Na (the fraetion of spins with m, = - 1/
2
or a)
and N
p
(the fraetion of spins with ms = + J/
2
or f3). One may speak of the
probability, p. and P
p
, that a single spin has an ms vaJue of _1/2 or +%. The
average value of the spin aJong the field direetion, z, is referred to as the expectation
value of Sz, ( Sz) This numerieal value is proportional to the moduJus of the
vector eomponent along the z-direction of either a single spin or of an assembly
of spins normalized to one spin. A single nuclear spin feels this component of
the el
the ev.
The H
field
r or an
Solvin
Since e
and equ
where N
by solvil
The nuo
n = 2 a
(l + xt

The
direction
down sp
unpaired
12- 3 Considerations Concerning Electron Spin 505
911)1a B o
a magnetic
fraction of
- 1/2 or a)
k of the
+1/
2
, The
the electron spin and appropriatel y the rema inder of this section will deal with
the evaluation of an expression for <Sz) . Recall that
(12- 2)
The Hamiltonian for the interaction of the electron magnetic moment with the
field was given by
(12-3)
For an S = 1/
2
system, applying Boltzmann statistics, we obtain
N.
- = exp (-I1E/kT) = exp (-gJ1
B
B
o
/ kT) (12-4)
N
B
Solving for the total number of electron spins in the f3 state, we get
N = N exp (9J1
B
B
o
)
(12-5)
p. kT
(12-6)
and equation (12-5) becomes
(12-7)
where N = N. + Np (i.e., the total number of spins). Rearranging thi s expression
by solving fo r N
p
, we obtain
N =N 1 + (gJ1n
B
o/ kT) =!!.- 1 + (gJ1B Bol kT)
(12-8)
p 2 + (gJ1
B
B
o
/ kT) 2 1 + (gJ1nBo / 2kT)
The numerator in parentheses in equation (12- 8) is of the form 1+ nx where
n = 2 and x = gJ1
B
B
o
/2 kT. When x 1, we may use the approximation
(1 + x)" 1 + nx to o btain
(12-9)
Similarly, we can show that
(12-10)
The difference between N
p
and N. gives the excess spin along the field
direction a nd is rela ted to the modulus of the resultant vector of the up and
down spin vect ors. It represents the net magnetic effect induced in the system's
unpaired electrons by the external field. The magnitude of the expectation value
ID
506 Chapler 12 Nuclear Magnetic Resonance 01 Paramagnetic Substances in Solution
of Sz is the quantity of interest to us in the nmr experiment. This is given by a
population-weighted average of the +1/
2
and - 1/
2
states:
( S> = (+ 1/2)Na + (_1/2)Np = -gJ.1nBo
(12-11)
z N ~
where 1/
2
and - 1/
2
are the ms-components along Bo of a and f3 spins, respectively.
There is a direct relationship between ( Sz > and the bulk magnetic moment
M discussed in Chapter 11. We have seen that the number of excess spins in the
lowest level is twice the expectation value of Sz times the total number of electrons
N. This number of excess spins must be multiplied by the component along the
field direction of the magnetic moment of one spin in the lowest sta te, C/2)g/ln ,
in order to find the average magnetic moment, that is,
(12-12)
This is the Curie law expression, described in Chapter 11 and arrived at by
population weighting of the various le veis.
For the general case of more than one spin, ( Sz> is given by
s
S exp (- EAf ,lkT)
( Sz > = M,,- =s- --- _ . - """"-s--- (12-13)
exp (- EMj kT)
M
s
= - s
J-Iere EMs is the energy of the state with quantum number M s and according to
equation (12- 1) is equal to g/lnMs Bo Thus, equation (12- 13) is consistent with
the equation for one electron spin (S = 1/
2
), I n equation (12-13), a state with a
particular value of the spin magnetic quantum number S is weighted according
to its equilibrium population. T he weighted values are summed over all the energy
levels and divided by the total number of levels to give the expectation value of
Sz' 1f f..E ~ kT, then exp (- E/ kT) = 1 - E/kT, and after some algebraic manip-
ulations, equation (12-14) results:
(
S >= -g).lnBoS(S + 1)
(12- 14)
z 3kT
For a free lectron, the energy separation between two M s levels is g/lnBo
with 9 = 2.0023. The contribution from the orbital magnetic moment (in the spin
Hamiltonian formalism) is accommodated by using values for 9 that are different
from 2.0023 and different for different orientations of the molecule with respect
to the molecular frame. For a molecule or ion rotating rapidly in solution lhe
g value of Equation (12-14) is substituted by an average value of 9
(
S >= _ gav/1n BoS(S + 1)
(12-15)
z 3kT
Now that we have an exprcssion for ( Sz)' we shaIl proceed to evaluate the
quantitative expression for the nmr contact shift assuming equation (12- 15). T his
electron
12--4 The Contact Shift 507
a
1\)
e1y.
Icnt
lhe
'ons
the
OJlB '

lt by
_- 13)
li ng lo
Il wilh
wilh 3
ording
cnergy
allle of
manip-
(12- 14)
. UIla Bo
lhe spin
differen t
1 respect
Ilion, the
(12- 15)
alllale lhe
- 15). This
holds everytime a single S multiplet is populated. However, when two or three
S multiplets are degenerate (as in the cases of E and T ground states) or c10se
in energy with respect to kT, the energy separation between Ms states is different
from 9avllBBo, and equation (12- 15) becomes a rough approximation. More
thorough calculations are needed for these cases.(4)
12-4 THE CONTACT SHIFT
The contact shift arises from the presence ofunpaired spin density at the resonating
nucleus. It is proportional to the amount of spin density. It is al so called the
Fermi contact shift. Fermi provided the first theoretical justification for electron
density at the nucleus in accounting for sorne details in the electronic spectrum
of the hydrogen atom. (S) The contact shift is also referred to as the scalar shift
beca use it is independent of molecular rotation.
The spin density at the nucleus of an atom in a Iigand is a small fraction of
an electron which, in the presence of an external magnetic field, gives rise to a
permanent, time-averaged, additional magnetic field that adds to the applied
magnetic field. Therefore, the nucleus experiences a further shift in resonance
freguency. In other words, the nuclear energy levds are affected by the presence
of spin density at the nucleus as shown in Fi g. 12-2(8). If we had a fuI! unpaired
electron at the nucleus, this nucleus would sen se a magnetic moment egual to
9I1B<S2) aligned with the external magnetic field, with given by eguation
(12-15). We do not have a fuI! electron at the nucleus whose nmr is studied, but ,
in general , only a small fraction of an electron, resulting from direct delocalization
and spin polarization. :-or simplicity let liS consider the case of a single electron
in a molecular orbital \}J that is directly delocalized on the resonating nucleus
without any spin polariza tion. The spin density at the nucleus is \}J(O) 2 where O
means at Odistance from thc nucleus. The shift from paramagnetism comes from
the magnetic field B' arising from the electron density at the nucleus:
(12-16)
For more than one unpaired electron, a normalization term C/z)S must also be
included. The expression for the shift is:
2
(12-17)
v Bo 2S 9 Iln 3kT
where \}J(Of is summed over all molecular orbitals containing unpaired electrons.
In guantum mechanical terms, the contact hyperfine tenn is
(12- ]8)
where Ac is the con tact hyperfine coupling constant and is the same as a di scussed
in Chapter 13. Capital A indicates that there may be more than one unpaired
e\ectron in the molecule or ion. Ac is defined as:
(12-19)
i
l
FIGURE 12-6 The dipolar
illteraction energy between
the electron and nuclear
magnetic dipoles in an
isotropic situation is a
lunction 01 the angle y
between the electron-nucleus
vector, r, and the external
magnetic lield, 8
0
.
If J.1.B' J.1.N (the nuclear Bohr magneton), k, T, '1', and J.1. o are expressed in SI units,
Ac is given in J(A - 2J
3
T-
2
m
2
). However, it is customary to report the Ac value
in terms of Ac/(Ii/rad sec-
1
) or AJh (sec-
1
or H). If we substitute the eguation
for Ac into eguation (12-17), we obtain the following expression for the contact
shift:
(12-20)
We can now see that a very small Ac value can give rise to a huge isotropic
shift. For example, an Ac value of Ir 27 J gives a contact shift of 40 ppm. The
reader is encouraged to convert the isotropic frequency shifts in Fig. 12- 1
(at room temperature) to the equivalent field shifts in tesla. The equality
- /':l B/ B
o
= /':lv/ v, where v is the fixed probe frequency, follows di rectly from the
fact that hu = gN J.1.NbO for nuclear spins.
If one measures the temperature dependence of /':lv , a plot of /':lv vs. l / T
should prod uce a straight line with a slope proportionaJ to Ac for systems
exhbting Curie law behavior. For syslems with an orbitally non-degenerate
ground state, such as octahedral nickeJ(lJ) and tetrahedral cobal t(JI) complexes,
the application of equation (12-20) is valid; otherwise, equation (12- 20) represents
ao approximation. Equation (12-20) holds iodependently of the orientation of
the molecular frameas loog as 9 = ge. It is also valid in solution when an average
value of 9 is considered.
12-5 THE PSEUDOCONTACT SHIFT
Magnetic moments aligned along the external magnetic field from spin density
at every point all over the molecule (except that at the resonati ng nucleus) can
also couple wth the nuclear magnetic moment. The coupling is dipolar in origino
The relevant Hamiltonian for the general case of coupled magnetic moment
vectors = gNJ.1.
N
I aod = gJ.1.
B
S was giveo in equation (9-23).
(12-21)
When both J and S are aligoed along the external magoetic field (as is the
case when 9 is isotropic) the energy of interaction is:
J.1.1J.1.2( 2 1)
Edip = -3- 3 cos y - (12-22)
r
where J.1.1 is the nuclear magoetic moment, J.1.2 is the electron magoetic moment,
and r is t he distance between the origios of the two vectors. The meaning of the
angle y is illustrated io Fig. 12- 6.
The electron magnetic moment arises from the excess populatioo of the
Zeeman levels times the spio density at a given point and r is the distance between
the nucleus and the giveo poiot. lo order to evaluate the interaction energy over
all S)
hyp
epr
ener o
for c
to o
cond
the o
field.
(12- 2
coupl'
givin
emisor
by it
9- 17).
Thus,

averag
contrib
litera tu
pseudo
discuss
for difTe
pseud e
lhl
the spin
not avai
metal iO
tact con
Here, N,
compone!
x, y, and.
tensor.
Forc
be approx
terms of g
Note I
its,
lue
ion
tact
-20)
opic
The
\2- 1
lality
1 the
'. l i T
stems
~ e r t e
,lexes,
esents
.ion of
verage
density
:us) can
lorigin.
t
(12- 21)
is the
(12- 22)
moment,
of the
over
12-5 The Pseudocontact Shift 509
aH space, integration is needed. This dipolar contribution to the electron- nucleus
hyperfine coupling can be measured in the solid state or a frozen solution, with
epr and ENDOR. In solution, where random and isotropic rotation occurs, t he
energy described aboye averages to zero for an isotropic 9 because the integral
for cos y ranging from 1 to -1 of equation (12-22) is zero. For this averaging
to occur, the rotation rate in radians/ sec - 1, has to be faster t han Edip/ h. This
condition is easily satisfied in solu tion even for macromolecules.
Now, let us suppose that iJ.2 is not isotropic but changes its magnitude as
the orientation of the molecule changes with respect to the external magnetic
field. Under these circumstances, iJ.2 is anisotropic and the integration of equation
(12-22) over cos y is not zero. Thus, an added contribution to the hyperfine
coupling results, that is, an additional magnetic field is sensed by the nucleus
giving rise to a contribution to the chemical shift. T he value of iJ.2 wiU be
anisotropic when there is an orbital contribution to the magnetic moment which,
by its nature, changes in different directions of the molecular frame (see Fig.
9- 17). In this case, 9 aJso becomes anisotropic and therefore orientation dependent.
Thus, the same effects that give rise to anisotropy in 9 also give rise to a shift
contribution. This shift contribution is isotropic beca use the dipolar effect is
averaged by rotation in solution. Because it is isotropic, Iike the contact
contribution, it is caJIed a pseudocontact shift and is also referred to in t he
literature as an isotropic dipolar shift. The through space nat ure of the
pseudocontact effect is comparable to the neighbor anisotropic contribution
discussed in Chapter 8, which was seen to be dependent upon di fferences in XOIA
for different orientations. In a similar fashion, anisotropy for Xpara leads to the
pseudocontact shift.
T he complete evaluation of the pseudocontact shift requires knowledge of
the spin density distribution over the entire molecule. This information i ' usually
not available. If the unpaired electrons are assumed to be localized only on the
metal ion, a point dipole model leads to equations for evaluating the pseudocon-
tact contribution to the isotropic shift. The general equation in SI units* iS(7,8):
(12-23)
z
Here, N A is Avogadro's constant, Xxx , Xyy ' and Xzz are the susceptibiJity
components, and the angles eand cP are defined in Fig. 12-7. The coordinates
x, y, and z are defined by the principal directions of the magnetic susceptibility
tensor.
For cases where the magnetic susceptibiJity along a given coordinate k can
be approximated by equation (12-24), equation (12-23) can then be rewritten in
terms of 9 values.
(12-24)
FIGURE 12-7 Delinition 01
the quantities in equation
(12-23).
Note that X{SI) = 4n x 10-
6
X (cgs emulo
510 Chapter 12 Nuclear Magnetic Resonance 01 Paramagnetic Substances in Solution
The anisotropy in the g tensor is more easily obtained than that in X, especiaUy
for S = 1/
2
systems.
Rewriting equation (12-23) in terms of f't..g for an axiaUy symmetric system,
we obtain the following equation for the pseudocontact contribution:
f't..V(pc) _ 110 I1B2S(S + 1) 3 cos
2
e - 1 (2 2)
(12- 25)
V - 4n 9kT r3 gil - g.l
I
An example of how these terms are defined for a typical molecule with local axial
symmetry is given in Fig. 12-8.
r
FIGURE 12-8 Delinition 01 terms in
equation (12-25). The parallel and
perpendicular axes are shown. The
radius vector Irom the metal center to
the nucleus being investigated is labeled
j , and the angle that it makes w ith the
highest-Iold rotation axis is (J . For a
proton shift, r would be drawn to the
hydrogen 01 the phenyl ringo
In view of the simplicity of equation (12-25), many studies have been
performed on S = 1/
2
systems. Equation (12-25) is valid when the nucleus studied
feels the unpaired electro n as a point dipole (i.e., when delocalization can be
neglected and the nucleus is relatively far from the metal).(9) The significant
delocalization of unpaired electrons, at least within the coordination cage, may
prevent the quantitative use of equations (12-23) and (12-25) '0r donor atom
nuclei or for nuclei c10se to the donor atoms.(lO)
The foregoing discussion should be made more specific by considering
different types of nuclei. Protons and deuterons only have spin de'lsity in an
s orbital and since this spin density is isotropic, a pseudocontact shift does not
result. If the protons are attached to a carbon or nitrogen atom, for example,
bearing spin density in a P
n
orbital, a pseudocontact shift can arise at the proton
that is then called ligand centered. In this case, ligand-centered effects cannot be
neglected. Combined information on the carbon or nitrogen and an attached
hydrogen ato m is needed for a complete treatment. It is also sometimes useful
to obtain independent information from the relaxation parameters (vide injra).
The pseudocontact shift equations are particularly useful for nuclei in metallo-
proteins which are within 10 of the metal but are removed from the metal
by many sigma bonds. In this case, the spin density and the contact shift is zero
as is spin density on neighboring atoms.
12-0 LANTHANIDES
Lanthanides are cha racterized by large spin-orbit effects so that both the spin
and orbital angular mornenta are sizable and strongly coupled. This means that
for each elect ron, the various projections of the orbital angular momentum mi
will interact differently wi th t he various projections of the spi n a ngular momen-
tum, m., giving a total angular momentum component equal to mI + ms = mj'
The m
j
values identify a j multi plet, just as mI and M s were related to the 1and
been
is zero
12-6 Lanthanides 511
TABLE 12-1. Some Electronic Properties of Lanthanide lons
p
Ion Conliguration 2S+ 1Lj 01 GroundState(multiplicity)
g/ <5,)/ <5,>/ (ppm)d (AVr
Ce
3
+ 4[1
2F5/2(6)
%
107 0.98 + 1.6
Pr
3
+ 4[2 3H
4
(9) 4/5 3.20 2.97 +2.7
Nd
3
+ 4[3
41
9
/
2
(10) S/11 4.91 4.4Y + 1.05
Pm
3
+ 4j'4
51
4
(9)
%
4.80 4.01 -0.6
Sm
3
+ 4[5
6H
5
/
2
(6) 2/3 1.79 0.06 +0. 17'
Eu
3
+ (Sm
2
+) 4[6 7F
o
(l )
-10.68 - 1.0'
Gd
3
+ (Eu
2
+)
4F BS
7
/
2
(8) 2 - 31.5 - 31.50 O
Tb
3
+ 4js
7F6(13) 3/
2
- 31.5 - 31.82 + 20.7
D
y
3+
4j9 6H15/2(16) 4/3 - 28.30 -28.54 + 23.8
Ho
3
+ 4f10
51
s
( 17) 5/
4
-22.50 -22.63 +9.4
Er
3
+ 4f1l
4J15 /2(16)
%
-15.30 - 15.37 -7.7
Tm
3
+
4f12
3H
6
(13) 7/
6
-8.17 -8.21 -12.7
Yb
3
+
4f13
2F7/A8)
%
-2.57 -2.59 - 5.2
"CaJcul ated from equa lion (12-27) : lhe formul a does not hold forj 6 ions.
b CaJcula led according lo equation (J2- 26).
'CaJculated by inclusion ofthe excited sta tes(l2)
d Dipolar shift predicted from Equatioll (12- 28) for r =300 pm, 3 cos
2
e- 1= 1, T = 300 K, axial symmetry, and D. values for each
lantha nide estimated fr om reference 11. .
' lncluding contributi ons from excited J manifolds.( ")Forj 6 ions, the contributi o n ofthe g.round state manifold is zero.
s manifolds. When electrons are allowed to interact, then J terms are obtained.
Thegroundstatesfor lanthanidesin theoxidationstate +3are reported in TabJe
12_l.(11,12) They arecharacterized by S, L, and J. Forexample, cerium(III) has
one electron in an f-orbital;S = 1/
2
combines with L = 3 to give both J = 3 +
t2 = 7/
2
and 3- 1/
2
= %.Thelatterterm is the ground state. Although it is not
completely correct, we will consider only the ground state in our analysis. This
is an even poorer approximation for actinides, which have larger spi n orbit
coupling and excited states ofdilferent J multiplicity closer in energy than the
lanthanidcs.
The f orbitals are often assumed not to be involved in covalent bonding
with the donor atoms. Little electron delocalization on the li gand molecules is
assumed to result and the contact contribution is often neglected. The validity
ofthisassumptiondependson thenumberand type ofbonds between themetal
ion and the resonati ng nucleus. It is notjustified for nuclei directly coordinated
to the metal ion. We should next consider the spin density at the resonating
nucleus and <Sz>' which is now labeled <Sz >J ' It is generally assumed that
crystalline field elfects are much less tban kT and completely neglected in the
evaluation of<Sz> /12):
(12-26)
wbere
_ 1+J(J +1) - L(L +1) +S(S +1)
gJ - 2J(J +1)
(12-27)
512 Chapter 12 Nuclear Magnetic Resonance 01 ParamagneticSubstances in Solution
FIGURE 12-9 Calculated
patterns 01 (.) pseudocontact
sh ilts(1 1)and (.) - <5 >
z
values(12) lor lanthanide ions.
The shilts are lor a nucleus
3 from the metal with 3
cos
2
e- 1equalto 1at300K.
The numerical values are reported in Table 12-l.
The values of <5
z
) are shown in Fig. 12_9(11 , 12) Note that whereas <52)
valuesfor unpairedelectronsin dorbitalsarenegative,theycan beeithernegative
or positive in lanthanides. A positive value results when the orbital contribution
to the energy level is !argerthan and differentin sign from thespincontribution.
------------------------------.40 40,-
30
20
E
o.
.9.-
o. 10
i5

O
-10
-20
,. --11"
I ...
I '
30 , .....
,
j ,
,
:
, ,
, ,
20
"
,
, ,
,
\
j ,
, ...
10 ul
V
: ...,
I , I
I ,
. 0
-10
-20
La Ce Pr Nd PmSm Eu Gd Tb Dy Er HoTm Vb Lu
D ue to the small contact terms, the poi nt dipole approximation for the
pseudocontact cont ribution is a better approximation for lanthanides Lhat for
first row transition metal ions. The ligand field splitting causes the magnetic
anisotropy. The Dz, D
x
' and Dy parameters take the Iigand field spli tt ing jnto
account. As long as D is larger than the Zeeman energy and smaller than kT,
the expression for the pseudocontact term iS: (II)
= _ J.l. og/J.l.8
2
J(J +1)(21 - 1)(21 +3)
v 4n 60(kTf
D
2
(3 cos
2
8 - 1) +(D
x
- Dy) sin
2
8cos2U
x . (12-28)
r 3
The shifts at 300 K for a nucJeus i at 3 with 3 cos
2
8 - 1= 1 and Q = Oare
reported in Fig. 12-9.
12-7 FACTORING THE CONTACT ANO PSEUOOCONTACT
SHIFTS
In principie, the observed isotropic hyperfine shifts contain contact and
pseudocontact contributions. The latter can be further divided into a metal
centered and Ji gand-centered contributions. In lanthanides, the metal-centered
pseudocontact term prevails at least for nucJei a few angstroms away from the
metaLFurthermore,sinceequationsareavailableforbothcontactandpseudocon-
tact terms, attempts have been made to factor out the two contributions
U2
,1 3)
Ifwe consider a series ofcomplexes differing in the metal ion, with the same
nucJeus and same contact hyperfine constant, the factorization is possible(13,14)
furt
dep
avai
equ
comp
anisOI
and
suscep
contril
Sllscep
in sol u
provid
(12- 25
12-7 Factoring the Contact and Pseudocontact Shifts 513
TABLE 12- 2. Contributions to the Hyperline Sh ift 01 Carbon Atoms in a
Porphyrin Ring 01 a Low Spin Iron (ll l) Complex(1 7)
Conlribullon eL Pyrrole I J co Pyrrole u C
a
Meso I }C Pyrrole 13CH3
A
V;
V
I
o
12-28)
oare
(v/ vo);SO 101.5 36.0 73.2 46.8
3 1 11 22 5.0
36 78 -10
(v/ vo)eon 34 -53 61 47
The values ror el and fJ carbons rerer to TPP; those ror meso and pyr roJe e H} ca rbons rerer lo
etioporphyrin.
Let us consider two different metal complexes, i and j, of similar geometry. The
measured shifts [or a given proton are given [or axial symmetry by
= A( Sz) + Dz;.G
= A( Sz\ + Dzj G
Here, the unknowns are A and G for each nuc1eus, whereas ( Sz> and /.:Z
depend only on the lanthanide, and reasonable estimates of their values are
available0
1
.
12
,15) By using these estimates for ( Sz) and we are left with two
equations and two unknowns. If more than two metal complexes are studied,
further equations can be used without introducing more unknowns. More
complicated methods that do not involve the assumption ofaxial symmetry have
been proposed( 16)
For first row transi tion metal ions factoring is more complexo Liga nd-
centered effects complicate the interpretation of nuclei other t han protons and
deuterons. In Table 12-2, the rel ative contributions to the hyperfine shifts o[
carbon atoms in a porphyrin ring containing low spin iron ITI) are shown. The
contact and the two pseudocontact contributions a re similar in magnitude. For
protons and deuterons, the metal-centered pseudocontact contribution can be of
the same magnitude as the contact termo
For orbitally non-degenerate systems with excited states far removed in
energy, the orbital contribution is small and so is the magnetic anisotropy.
Accordingly, the pseudocontact shifts are smal!. Examples inelude octahedral
nickel(II) and tetrahedral cobalt(n ). Some anisotropy in the magnetic suscepti-
bility arises from zero field splitting as in the case of hi gh spin iron(III)
complexes.(18) Orbitall y quasi-degenerate ground states provide large magnetic
anisotropies and large pseudocontact contributions (e.g., octahedral cobalt(IJ)(19)
and pseudotetrahedral nickel(II)(20) sys tems). The knowledge o[ the magnetic
susceptibility tensor provides a direct tool for the evaluation of p eudocont act
contributions. Some examples are reported in Table 12-3 where the magnetic
susceptibility information obtained on single crystals is transferred to the molecule
in solution.
When equation (12-24) is valid (e.g., S = 1/
2
systems), single-crystal epr studies
provide 9 values and a n estimate of the pseudocontact shifts through equation
(12-25).(27)
l
TABLE 12-3. Isotropic Shifts and Pseudocontact Con-
tributions from Known Magnetic Susceptibility Tensors
(A) lH and 13C Isotropic Shifts (ppm) of the Pyridine
Signals in the bis-Pyridine Adduct of Cobalt(ll) bis-
Acetylacetonate Using Single Crystal Magnetic Sus-
ceptibility Data(21.22)
Alom
e:f
P
c;-H +32.9 -39.5
f3-H +50 - 18.1
y-H -9.4 -15.6
c;-C -199 -92.5
f3-C +229 -35.7
y-C -73.8 -28.3

01'
ca
du
de
wh
nOI
on
den
eva
elee (B) The Aromatic Protons in Nickel(ll) Bis-
dele
ceptibility Data(2o.23.24)
Salicyladiminate Using Single Crystal Magnetic Sus-
IS TI!
wer
eou)
grol
Prolon Structure
and
prot,
3 -23.7 +1.4 beca
dom
+ 19.0 -2.3 4
orbit
-23.7 -4.5 5
pair.
octal
+3.7 -8.4
6
pol ar
onto
(e) Phenyl Protons in Dichlorobis(triphenylphos- oppo
ph ine)Cobalt(ll) and Nickel(II)(25.26) In the
the u
Metal/ Proton

oeeu:
e
g
ort
{Ortho
Co meta
-10.35
+8.08
-2.13
-0.54
atomi
deloc
para -11.51 -0.53 thein
{ ortho
Ni meta
-6.38
+8.03
+0.56
+0.14
examr
beeaw
para -11.16 +0.14
at the
12-8 THE CONTACT SHIFT ANO SPIN DENSITY
As mentioned, if the contact contribution i ' dominating the isotropie shifts or if
we have fact ored out t he pseudocontaet shift, a measure of the contact hyperfine
coupling constant is available. The contact contribution is then related to the
actual spin density on the resonati ng nucleus through equation (12-19). Spin
compl
TABLE
n-Ethy
14.4
12--8 The Contact Shiftand Spin Density 515
density arises from a direct delocalizationmechanismand from spin polarization
ofan orbital occupied by two electrons. In principIe, both contributions can be
calculated through a molecular orbital treatment. IfK is the hyperfine coupling
due to a full electron on an atom (listed inside the back cover), then the direct
delocalizatic:in contribution is obtained from equation (12-29)
(12-29)
whereAd is thecontributionfromdirectdelocalizationandp/2S is thespindensity
normalized to one electron.(28)
In the 1970s Drago et al. pioneered the calculations ofdirect delocalization
on hydrogen nuclei through extended Hckel calculations(29) Unpaired spin
density delocalizes through the highest occupied orbital and spin density is
evaluated by calculating jJfo) at the hydrogen nucleus. The orientation of the
electron in the magnetic field is such that the ms ground state is - %. Direct
delocalizationfrom themetal implies thatthesamesignis maintained;then <S)
is negative and from equation(12-20) the shift in Hz is positive ordownfield. If
we maintainthesignof<Sz) negative,we havetochangethesignofthehyperfine
coupling constant when spin po!arization leads to spin density with an ms = 1/
2
ground state. The aliphatic protons ofoctahedral amino complexes ofnickel(JT)
and cobalt(lI) experience direct delocalization and shift downfield. The amino
protons, on the contrary, experience an upfield (negative figures in Hz) shift
because the large spin density on the nitrogen atom makes spi n polarization
dominantatthe proton. In thesecases, the unpaired electrons arein thee
g
metal
orbitals, which have the correct symmetryto form a (] bond to the nitrogenlone
pair. When the unpaired electrons are present only in metal or bit als in
octahedralcomplexes, theycannotcontributeto thedirect (] delocalization.Spin
polarizationofthe(] mo'l ecularorbitalsis needed toconveyunpai redspindensity
,
onto the ligando This is the reason that early transition metal
t
2g
ions give rise to e
Q
;
/'
,
'+'0'*
\
\
+
,, '
opposite shift patterns compared to those on the right hand side of the series.
,
,
,
Inthemetal-ligandmolecularorbalscheme,theantibondingorbitalcontaining
,, ' ,
,, ' ,
the unpaired electroD (Fig. 12-10) is partly constituted of the ligand highest
occupied molecular orbital (HOMO)when the metal un paired electron is in an
, ,
, , L
\ \*0
e
g
orbital. (Usually the HOMO contains the lone pair.) The coefficients of the
a\-4t-/
atomicorbitalin thatmolecularorbitaldeterminethespindensityat nuclei. Spin
delocalizationthroughthehighestoccupiedmolecularorbitaldecaysrapidlywith
FIGURE 12-10 Unpaired
theincreasingnumberof(] bondsfr omthemetalto the resonatingnucleus.Sorne
spin density transferred onto
examples are reported in Table 12-4. The treatment for carbon nuclei differs the ligand bysigma bonding
becausedirectspindelocalizat iononap orbitalinducesspindensitycontributions between the e
g
metal orbital
at the carbon nucleus [rom 15 and 25 orbitals through spin polarization. This
containing one electron and
complicates the problem(30)
theliganddonorlonepairO'L'
TABlE 12-4. Estimated AJh Values (MHz) lor lH, l3C, and 14N Nuclei 01
n-EthylAmine Coordinated to bis-Acetylacetonate Nickel(II)(30)
hifts or if
hyperfine
C'H,
ted to the
14.4 -2.64 - 0.70 1.02 1.80 0.22
- 19). Spin
Spin polarization effects are, in general, hard to handle with theoretical tools.
Sorne results have been obtained in the case of aromatic moieties since independent
tests come from the investigation of radicals through epr. Assume sorne spin
2
density is present in a P
n
orbital of a carbon atom that is hybridized sp . To first
order, it does not contribute to contact contributions on either the carbon or
the attached hydrogen nuclei. However, spin polarization (Fig. 12-11) induces +
spin density at the carbon nucleus through the 15 and 25 orbitals as well as to
the nuclei of attached atoms through the (J covalent bond. An attached proton
therefore experiences spin density at the nucleus. The larger the spin density on
the P
n
orbital, the larger the spin density at the hydrogen a tom. The propor-
tionality constant for this relationship is constant for various systems as long as
the nature of the orbitals involved is the same.
fror
1111
lo (
(12-30)
H e
Ihe
FIGURE 12-11 Positive Prr 1
2
where Ap is the hyperfine constant due to spin polarization, Pc
n
is the n spin
spin density on an sp
density on the carbon atom, and Q is the proportionality constanl, which is about
carbon induces unbalancing
-70 MHz.(31) The negative sign is due to the ract that spin polari zation induces
01 the spin density on the
spin density on the hydrogen atom of different sign than the spin density in the
doubly occupied C-H
bonding (J orbital. The sign 01
Pn orbital. If the carbon bearing the spin density in the Pn orbital is attached to
the induced spin density is a CH
3
moiety, the 15 orbital of the CH} protons can directly overlap with the
positive in the outer region Pn orbital and then directly transfer spin density with the same sign onto the
and negative in the inner
hydrogen nuclei. The proportionality constant Q(C-CH
3
) is now posi tive and
region 01 the (J orbital.
is predicted to be around 75 MHz when rotation around the C-C axis is fast
enough to provide a space-averaged hyperfine coupling constant. (32) Experimen-
tally, the value of Q is found to vary considerably from one system to another.
Furthermore, delocaJization through the n molecular orbitalleads to large values
of contact shifts for nuclei at a large distance from the paramagnetic center.
In the case of nuclei of the second row of the periodic table, there are several
unpa
contributions to spin density at the nucleus. As previously mentioned, the unpaired
spin on a Pn orbital induces spin density through 15 and 25 orbitals of the same
atom. Furthermore, the P spin density of the nearby atom contri butes, via spin
n
polarization of the (J-bond electrons, to the spin density at the resonating nucleus.
For an sp
2
carbon atom, the contributions to spin density through the 25 orbital
are given by(33):
Ap
} 3
h
L + L Q;iCPXin
(12-31)
h
=l j= 1
where Xi are the three atoms bound to the carbon under consideration, Qx . is
a constant describing the polarization effect of the spin density in the Pn carb'on
on the two electrons of the C-Xi bond, and Qx .c is the constant relative to the
polarization effect of the spin density in the P
n
of Xi on the same C-Xi
bond. Sorne of these Q values are reported(33-3S) in Table 12-5. To this value
of A
p
, a contribution from the polarization of the 15 orbital should be added.
A
--....!!. = const p n (12-32)
h e
where the const is -35.5 MHz(33)
12-8 The Contact Shift and Spin Density 517
TABl E 12-5. Q Values (MHz) lor Fragments Involved in n Electron Spin
Delocalization Systems(33- 3S)
01'
a ~ H a ~ H a'c a ~ c
0"
a ~
CCH) FC
:s
o
n
In
r-
as
30)
,in
)ut
es
the
i to
the
the
and
fast
nen-
ther.
alues
:r.
:vera\
,aired
same
aSpll1
Ieleus.
12- 31)
(12- 32)
+54.6 -65.8 +40.3 -39.0
-75.6 +53.2
+14-:-+115
-410 +237
Spin density on Pn orbitals are present when there is n spin delocalization
from the metal.(361 Forexample,vanadium(IlI)is d
2
with two unpaired electrons
in t
2g
orbitalsin octahedralcomplexes. These orbitalshave thecorrectsymmetry
to overlap with n ligand molecular orbitals. It should be noted, however, that
the n ligand molecular orbitals C(ln be either empty (Fig. 12- 12(A)) or full (Fig.
12- 12(B)). In the lattercase,thedescription is similar totha t ofthe(J bonds.The
,--In'
, '
, '
:
I
, "
,
:--n,
:
,
,
:
I
I
I I
I I
+
I I
(2 9 " /
\
\+:
I
\ I
'n
(A) (B)
unpaired electron resides in an orbital that is partly constituted of the ligand
highest occupied molecular orbital. This mechanism is called ligand-to-metal
chargetransfer. Electrondelocalization from t
2g
directly into the ligand n system
occurswhen then orbitalis unoccupied. n delocalizationis improbablein ligands
having only (J bonds. The lowest unoccupied molecular orbital ofthe ligand is
far removed in energy and we should also consider whether the d electron has
thecorrectsymmetry to interact with the ligand orbital ornot. In the lattercase,
spin density on the ligand occurs through spin polarization.
Al! the ligands ofthe type
e H- eH
up H/ Q\---x
~ /
eH-eH
Iown ~
where the X donor group can be - NR
2
, -N= HR, or 0 - ,1 37- 39) experience
unpairedspin density in the n syst em thatarises from non-orthogonality between
the coordination bond and the n system. The ortho signals are shifted upfield
(i.e., the spin density is negative (excess ofspin = 1/
2
)on the hydrogen a tom and
FIGURE 12- 12 Unpaired
spin density can be
transferred onto the ligand
by n-bonding between a 1
2g
metal orbital containing one
unpaired electron and an
empty (A) or full (B) ligand n
orbital.
,
1
TABLE 12-6. I H nmr Contact Shift Patterns (ppm) on Some Aromatic Ligands
L 2 3 4 5 6 Rel. No.
A
CHJ ' / H a -4.8 1.7 -5.2 37
fi
th
"" ,1
b -12.8 10.7 -17.1 40,41
'CI
O
I
",,'
c -8.2 8.6 -11.0 25,42
wl
un
(6),
fre
d -6.9 7. 9 - 11.3

tYI
e -1.5 14 -1.6 51 ofl
anc
"",. ,1
the
O
724 23.1 6.2 21,43,52

g 87.7 26.6 8.0
(J
\
CH,
h 55.0 12.0(CH
3
) 52.0 71.0 47
and
OC=N.
,R
desl

the -25.1 21.3 -19.2 12.1 20, 24,39
a In Ni(2,4 pent anedionate),L,.
b In NiL!+
' In CoL,CI,.
d In NiL CJ, .
2
' In NiL +.
6
fin Co(2,4 pentanedionate),L,.
"In Ni(2,4 pentanedionate),L,.
"In
In NiL, (R = i-propyl).
positive on the Prr orbital of the carbon atom). The para proton experiences a
similarshift bothin magnitudeandsign. Themeta protonsexperiencedownfield
shifts. This alternalion of spin density on six-membered aromatic rings is
characteristic of n spin delocalization and a(ses from a node in the n system
leading to spin polarization ofthe meta carbono
Thesamepatternis observedfor pyridine-N-oxide(29.40,41) andfor triphenyI-
phosphines(25.42) Pyridine(43-46)and imidazole(47.48) experience (J spin density
delocalizat ion, although spin polarization introduces some spin density on the
n system. When thearomatic ring is three bonds from the metal as in the case
of triphenylphosphineoxide,(49) or benzaldiminates,(50) or benzamides,(40) the
shifts stiU alternate but are about one order ofmagnitude smaller than in the
caseofphenylaminetypeofligands.] nthecaseof salicylaldiminates,twopathways
sum up: one typical ofthe phenate moiety and one typicaI ofbenzaldiminates.
ThelattergivesriselO asmaller ,hiftandleadtoasystemthat is notalternating(39)
(Table 12-6). The porphyrins are another interesting ligand system that wiII be
treated later.
disc
mag
mec
whic
mag
ligan
of th
lons.
chan.
orien
are e
nuele
a rot
4.39
12-9 Factors Affecting Nuclear Relaxation in Paramagnetic Systems 519
12-9 FACTORS AFFECTlNG NUCLEAR RELAXATION IN
PARAMAGNETIC SYSTEMS
As seen in Chapter 7, nuclear relaxation is determined by fluctuating magnetic
fields, and the larga the coupling between the nuclear magnetic moment and
the fluctuating magnetic fields, the faster the relaxation. In general, we can write
(12-33)
where E
2
/1
2
is the square of the aforementioned coupling energy in frequency
12
units and f(T e> w) is a function of the correlation time, Te> and of the Larmor
frequency, w. The correlation time, discussed in Chapter 7, is a time constant
typical of the system under investigation. lts reciprocal , Te -1 , is the average rate
of change of the reciprocal position or orien tation between the resonating nucleus
and any other particle whose movement relative to the resonating nucleus causes
the fluctuating magnetic field. The correlation function is of the form
1,52
.
r
(Te> W) = .
Te
2 2 (12-34)
l+WT
and provides the density of frequencies present in the system from the motion
described by the correlation time, Te- T he frequency W is that needed to induce
the nuclear transition.
The difference in a paramagnetic system compared to those in the previous
discussion of nuclear relaxation arises from the contributions from the fluctuating
magnetic fields caused by the unpaired electrons.
The unpaired electrons cause fluctuating magnetic fields by three main
(1) the electron reJaxation itself, (2) the rotation of the frame
which contains the electron and the nuclear spins both aligned along the external
magnetic field (Fig. 12-13), and (3) chemical exchange involving bound and free
ligands (Fig. 12-14).
IceS a
The first mechanism is self-explanatory. EJe"ctron relaxation occurs with T. 2
of the order of 10-
5
to 10-
7
sec for radicals and 10-
7
to 10-
13
sec for metal
ions. From time to time, in an absolutely random manner, the electron spin
changes its orientation. In a large ensemble of electrons, the process of changing
orientation is a first-order process having a time constant T
I
2
where TI and T
2
are electro n relaxation times. Here Tu represents the correlation time for the
nucleus as far as this mechanism is concerned. The second mechanism leads to
a rotation of the electron magnetic moment directly around the resonating
FIGURE 12-13 Rotation 01 the
molecular Irame holding the electron
and the nucleus together causes nuclear
relaxation. 'r is the rotational correlation
time.
J
FIGURE 12- 14 Binding and detachment
01 the molecular frame, holding the
nucleus to the molecular frame, holding
the electron, causes relaxation . 'CM is the
chemical exchange time.
nucleus. This causes a ftuctuation of the magnetic field at the nucleus ; the
correlation time is the rot ational correlation time. The third mechanism is typically
produced by chemical exchange. A given molecule containing the resonating
nucleus binds to a molecule containing the unpaired electron and then dissociates
from it. The correlation time for this mechanism is the residence time in the
bound sta te.
As discussed in Section 12-2, we have spin density both on the resonating
nucJeus and outside it that fluctuates with a time constant I. due to spin
reorientation. This is a fraction of an unpaired electron, equaJly distributed
between the Zeeman levels, which relaxes between the Zeeman levels just like a
fu I! electron. Consideration of the exis tence of an ex ces s population between the
Zeeman levels does not appreciably change the picture under these conditions
owing to the sma!! exLent of such an excess. (Thi s is at variance with the isotropic
shift that arises only beca use of the excess Zeeman population.) When there also
is che mi cal exchange, spin density appears and disappears at the nucleus with a
time constant ''''' Thus, spin density causes ftuctuating magnetic fields due to lhe
electron relaxation and in certain cases, to chemical exchange. The energy of the
coupling is the contact hyperfine coupling constant, AJ I, in frequency units.
Spin density outside the resonating nucleus, including the large spin density
at the metal ion where a large fraction of the uopaired electrons reside, is a source
of nuclear relaxation through dipolar coupling. The coupling energy now resulls
from an integral over al! space of terms of the form of equation (12-22) summed
over the spin density distribution(2,S3.54) Upon rotation the integral averages to
zero; however, its square [see equation (12-33)] <loes not average to zero upon
rotation beca use (3 cos
2
y - 1)2 averages to 4j5' As with the isotropic shift a
metal-centered contribution and a ligand-centered contribution (plus a cross
term) is considered.(2.55) The presence of spin density in a p" or bital of a carbon
atom affects the relaxati n of a proton attached to the carbon.(56,57) The ,. - 6
dependence of the a verage squared energy enhances the effect of the small fraction
of unpaired electrons 0 0 the nucleus when it is close to the resonating nucleus.
The ligand-centered contribution is often treated as a parameter.
48
The relevant
nuclear relaxation mechanisms, a rising from lhe dipolar coupling with spin
densities and unpaired electrons, are the electronic relaxation, the rotation of lhe
molecular frame, and chemical exchange.
When more than one effect is operative, the fas test one is dominant. Recall
the fastest process corresponds lO the small est correlation time. If l he reorientation
due to rotation occurs for example with a time constant, (lj,), of 10-
7
sec and
13
that due to intri nsic electron relaxation occurs with a time constant of 10 - sec,
the electro n spin reorientation occurs on average one million times for a si ngle
rotational reorientation and electron spin relaxation dominates.
w
t ",
0 11
rel
F I
an
do
its
re/a,
cond
ofch
popu
diffen
discw
givin1!
smalI
time e
the eft
dipola
(or a fl
perma
time ce
(12- 151
fields \\
latter 1
mechan
:he
IBy
ing
ltes
the
ing
Ipm
lted
e a
lhe
ions
opic
also
ith a
othe
,f the
ts.
:nsity
ource
esults
nmed
ges to
upon
ruft, a
croSS
:arbon
he ,. - 6
:action
ucleus.
elevant
:h spin
1 of the
. Recall
:ntation
sec and
- 13 sec,
a single
l
We can define a correlation time, ' c- as
-1 -1 - 1 - 1
' e = TI' + ' s + 'm
(12-35)
where 'r is the rotational correlation time, ' s the electronic correlation time, and
'm the residence time. In a more precise way, we should define 'si and 's2 dl.;lending
on whether the correlation time is the longitudinal or transverse electron
relaxation time, but this distinction can be overlooked without serious errors. (2.53)
For different situations, each of the lhree mechanisms can dominate the dipolar
l 1
relaxation. In the case of certain copper( II) proteins 's- l > 'r- , 'r-
l
10
7
sec-
and 's-1 dominates 'e-l. In smaller molecules ,; 1 approaches 10
11
sec - 1 and
dominates 'e-l. The time-average coupling energy is zero in every case, whereas
its squared value is different from zero.
In the case of contact relaxation, molecular tumbling is ineffective for nuclear
relaxation and the correlation time is:
(12- 36)
We have a further source of relaxation that is relevant under certain
conditions. Let us return to the consideration of dipolar coupling in the absence
of chemical exchange. Whatever the correJation time, we have assumed that the
population of the Zeeman levels is equal. Correction for the Boltzmann popuJation
difference does not change our conclusions regarding the mechanisms previously
discussed. H owever, t his effect introduces a value of <Sz ) different from zero
giving rise to a permanent magnetic moment according to equation (12- 13). This
small magnetic moment is seen by the nucleus as fluctuating with a correlation
time equal to 'r' If the correlation time for dipolar nuclear relaxation is also ',.,
the effect of the ex ces S population is negligible. When the correlation time for
dipolar relaxation is dominated by ' s' 'r is much longer, and the unpaired electron
(or a fraction oC it) is reorienting with a time constant 's' O n the other hand, the
permanent magnetic moment due to <Sz) fluctuates, around the nucleus, with a
time constant 'r (Fig. 12- 15). The quantity <Sz) is proportional to Ba [Equation
(12-15)] and when 'r is large, as with macromolecules in solution at high magnetic
fields where the ex ces s Boltzmann population of the aligned state increases, tbe
latter rotation leads to an tItlcient relaxation mechanism. The relaxation
mechanism is a1so called Curie relaxation.
FIGURE 12- 15 Rotation 01 the
molecular trame holding the permanent
magnetic moment < 5
z
> and the
nucleus together causes nuclear
relaxation. T is the rotational correlation
r
time (et. Fig. 12-13).
l
Equations lor Contaet Re/axation
Nuclear relaxation in the case of contact relaxation can be simply visualized in
the absence of chemical exchange. The transition between Zeeman levels of the
electron (i.e., the spin change) may cause nuclear reorientation. The transition
frequency required by the coupled eJectron- nucleus system is J
I
- J ' This
s
frequency must be provided by the lattice. The equation for the longitudinal
relaxation(S8) is:
= SeS + 1) (Afe)2 ___
(12-37)
1 + (J I - J.)r/
where the subscript M indicates the paramagnetic contribution, Ae is proportional
to the interaction energy involving the spin density, equation (12-19), SeS + 1)
introduces the square of the intensity of the electro n spin angular momentum,
J
I
is the nuclear Larmor frequency, J
s
is the electron Larmor frequency, re is
given by equation (12- 36), and (J
I
- J )2 can be approximated by J/.
s
The transverse reJaxation is given(58) by:
(12-38)
In contrast to T; t, T; I contains a term differing from equation (12-34) in that
i t contains J = Oin the denominator because near zero frequencies affect T
2
.
Equations lor Dipolar Re/axallon
For electrons localized on the metal ion and a resonating nucleus at a distance
r, the energy given in equation (12-22) averages to zero with time under any
modulating mechanism that is dipolar in nature. As mentioned before, E
2
does
not average to zero. The correlation time re is given by equation (12- 35). The
equations for reJaxation are:
(12-39)
where gN.t / f is .tI of equation (12- 22) and g.tB/ f is 112' The frequency J
I
corresponds to the nuclear Larmor frequency and J is the electron Larmor
s
frequency. The latter is a n approximation of J
I
- J (as in the contact ter m) and
s
of J
I
+ J ' The difference in frequency corresponds to the simultaneous fl ipping
s
of both spins, for instance, one decreasing by one unit in m, and the other
increasing by one unit in mI ' The transition is called a zero-quantum transition
a nd corresponds to W
o
of Sect ion 8-6. The sum in frequency corresponds to an
equal change in mI and ms' Tl is a double-quantum transit ion and corresponds
\1
g
fl
1:
ef
( 1
can
whe
wil
for a
for :
the
when
when
line \
with 2
r lS su
term i
1
s
,1
7)
al
1 )
m,
is
38)
hat
ilnce
any
does
The
to W
2
. As usual, T; 1 contains a non-dispersive term without J and corresponds
to near zero frequency oscillations.
Similar equations can be derived for spin densities at specific atoms in the
molecule other than the metal ion.(55- 57) These would be the equations for
ligand-centered relaxation, which would require knowledge of the spin density
distribution in the molecule and the introduction of cross terms with the
metal-centered relaxation equations.
Equations lor Curie Relaxation
We have already seen that a paramagnetic molecule has a magnetic moment
given by equation (12-13). Upon rotation, this magnetic moment causes a
fluctuating magnetic field at the resonating nucleus and causes relaxation (Fig.
12-15). This mechanism differs from those aboye because it depends on (Sz). lts
effect depends on the square ofthe magnetic moment(59) and according to equation
(12-15) on the square of the applied magnetic field( 60.61) The correlation times are
-1
' e
-1
= 'In
- 1
+',
(12-41)
for the dipolar coupling and
(12-42)
for contact coupling. These equations differ from equations (12-36) and (12-37)
in that the term 's is absent. Otherwise the same considerations hold. For usual
fields and small molecules, the effect is negligible. The rotati onal correl at ion time
can be predicted for a spherical molecule through the Stokes-Ei nstein equation(2):
4nra
3
, = - -
(12-43)
, 3kT
where r is the viscosity of the solvent and a the radius of the molecule. Consistent
with this formula, " for a hexaaqua complex is about 3 x 10- 11 sec and that
for a protein ofmolecular weight 30,000 in solulion about 10- 8 seco The expression
for T
2
- 1 for the dipolar coupling between the permanent magnetic moment and
the resonating nucleus (dipolar Curie relaxation) iS(60,61):
(12-44)
where J
1
is gN fJ-NBo/li. Since the line width is proportional lo T; t,
(12-45)
where 'VC/2) is the line width at half height, the Curi e relaxation can affect the
line width. At 600 MHz, the protons within 10 of a spin S = 3/
2
metal ion and
with a " of 10 - 8 sec are broadened. They are broadened beyond detection when
r is small er than 5 .
The expression for r; 1 [equation (12 - 14)J contains in the I(,c> J) part, a
term in 'e' Relaxati on mechanisms whose correlation time is long largely affect
1
1'; l. For T ~ 1, there are only terms of the type T/(1 + (l)
2
T
2
) and for large T values
they tend to zero.(53) In both cases, if Te is smal! , the effect is smal!.
General Comments Concernlng ReJaxation
Al! the foregoing equations have been derived with the assumption that the S
manifold is not split at zero magnetic field but is only split by the magnetic field
into the 2S + 11evels of the S multiplet. However, we know from epr spectroscopy
and from magnetic su 'ceptibility measurements that lhis is rarely t he case. Zero
field splitting is usually present when S > 1/
2
, Furthermore, hyperfi ne coupling
cause ' splitting of the S manifold at zero magnetic field (see, e. g., Fig. 12- 2) and
the splitting is sizable when the coupling occurs with magnetic nuclei which bear
the unpaired electrons. These splittings do not have an effect on nuclear relaxation
as long as the splitti ng encrgy Esp is smaller(53) than fa ; l . For example, [or
T
e
- 1 = 10- 11 sec, Esp has to be smalle-r t han Lcm - l. When this is not the case,
the foregoing equations provide qualitative predictions, and when quantitative
treatments are needed the reader is referred to available literature(2.53.62-71)
As in the case of the isotropic shift, the factorization among the various
contributions is the first step in any q Ll ant itative exploi tation of the relaxation
parameters. Although the nature of the problem is complicated, we are fortunate
in this case beca use the various contributions may differ by orders of magni tude.
Therefore, in general, only one contribution is dominant and simple consideration
and sample calculati ons can show which mcchanism dominates. For example,
1'1 of nondi rectly coordi nated hydrogen atoms in paramagnetic metal complexes
is determined by dipolar contributions, which sometimes may be approximated
by a metal-centered model. Nuclei of atoms directly coordinated to paramagnetic
centers may have large contact contributions to TI and 1'2' In the case of the
proton nmr of copp r complexes, 1'1 is determined by the dipolar contribulion,
whereas 1'2' which contains the non-dispersive Te term, is determined by the
contact contribution.(7 2) In fact, the correlation time fo r contact relaxation is T"
which is ~ 10-
9
sec, whereas the correlation time for T is T" which can be as
short as 10 - 11 seco
12- 10 RELAXOMETRV
The equat ions for nuclear relaxation by unpaired electrons always contain either
or both the nuclear and electronic Larmor rrequencies. Such terms make the
nuclear rel axation magnetic field dependent. A single relaxation measurement
does not provide both the correlation time and the electron-nuclear cou pling
energy. In the ideal situation, enough experimental dala would be available at
different magnetic fields to describe the curve for the en tire field dependence of
T;)j or r ;)j.
The expected plots of 1 ~ 1 and r; 1 as a functio n of lhe applied magnetic
field are reported in F ig. 12- 16 for the contact and in Fig. 12-17 for the dipolar
relaxat ion(2.53 .58.59) Experimentally, a l the time of writing, we a re limited on the
high fiel d side to 600 MHz, whereas on the low field side the limit is the sensitivity
which is proportional to the strength of the applied magnetic field, to the nuclear
magnetic moment, and to the concent ration of nuclei. Devices exist for measuring
J
been
r,: 1 i
and t
weigl
in di<
t hen
the 0
then
that (
,
mole(
ID a r;
S

1.5, e
u
...
1

' e
...
u
1
..::-
N
0.5, e
10
6
Proton Larmor frequency (Hz)

15'e

5'e
lO'
.-::
.... u
1

10'e
1
....
.....
N
Proton Larmor frequency (Hz)
TI' and sometimes T
2
, of solvent nuclei, particularly water hydrogens, at very
low magnetic fields(2,53.73,74)
The problem ofchemical exchange as a source of nuclear relaxation has
been neglected in thischapterexceptwhen'",becomesthecorrelationtime.When
T,:1is larger than the separation in Hz(sec- 1) between the signal in the Asite
and that in the Bsite,then onlyonesignalis observed whoseshift is the average,
weighted for the occupancy ofthe two sites. The treatment is analogous to tha!
in diamagneticsystem .If <I is largerthan thedifference in both T; I and T; 1,
then the resulting relaxation values arealso a weighted average. When <I is of
theorderoforsmallerthan the relaxation ratesand thechemicalshift difference,
[hen more specialized Iiterat ure should be consulted.(2,75-78) Here we assume
that chemical exchange is fast and is averaged by the mole fraction relation.
We will treat coordination compounds in aqueous solution having a water
molecule in the coordination sphere. The water proton TI values are measured
in a rangeofmagneticfields between 0.01 and 100 MHz.First,we shallconsider
12-10 Relaxometry 525
FIGURE 12- 16 Plot 01 (A)
the f,(w, 'e) lunction in
equation (12-37) and (B) 01
the f
2
(w, 'e) lunction 01
equation (12-38) as a
lunction 01 the magnetic lield.
FIGURE 12-17 Plot 01 (A)
the f
1
(w, 'e) i n equation
(12-39) and (B) the f
2
(w, 'e)
function 01 equat ion (12--40)
as a lunction 01 the magnetic
field .
526 Chapter 12 Nuclear Magnetic Resonance 01 Paramagnetic Substances in Solulion
T
2
1
FIGURE 12-18 (o) and
T- 1 (.) 01 water protons in
6.65 x 10-
2
M Cu
2
+ solutions
as a lunction 01 Ihe proton
Larmor Irequency at 25 C.
The continuous lines
represent a litting 01 the data
according to Ihe Solomon
equations (12-40) and
(12-39) , respectively(79)
200
.,

100
-
,
'"

O
0.01 0.1 10 100 1000
Proton Larmor frequency (MHz)
the complex The experimental data reported( 79) in Fig. 12-18 are
a part of the curve reported in Fig. 12-17(A) for dipolar relaxation. By fitting
the curve with equations (12-39) and (12-40), a value of ' e of 3.0 X 10-
11
sec is
obtained at 25 C. This is a typical time constant for rotation ofa hexaquacomplex.
Since the correlation time is the rotational time, the nuclear relaxation must
depend on dipol a r coupling for onl y this effect depends on rotation. Assuming
that the measured effect is entirely due to the presence oC water in the first
coordination sphere, and that there are 12 equivalent protons, the metal- proton
distance is estimated to be 2.8 A, in agreement with the expected 2.1 A
metal-oxygen distance.
These conclusions show that the proton-metal coupling is a metal-centered
coupling for which equation (12-39) holds. The validity of the metal-centered
point dipole approximation has been shown to be purely accidental as a result
of cancellation of terms due to the delocalization of the electron within the Cu-0
6
volume and that due to spin density on the oxygen atom.(54) P roton contact
contributions in al! the water-copper(Il) interactions are negligible( 2.53)
When the solution is made more viscous by adding ethyleneglycol or when
the copper ion is bound to a macromolecule, 'r increases. For a protein of
molecular weight 32,000, such as copper-zinc superoxide dismutase (SOD
hereafter), ' r is expected to be around 3 x 10-
8
seco The rotational mechanism
does not determine ' e any more beca use 'r is now longer than either or both ' s
or 'm' Furthermore, there is a splitting of the S manifold a t zero magnetic field
due to the coupling of the electron with the magnetic nucleus of copper. Such
splitting is of the order of 10- 2 cm - I and is smaller Ihan fn
e
-
I
when 'e is
3 X 10 - II sec (equal to 0.2 cm -1). The splitting is larger than fn
e
- I when 'e is
of the order of 10-
9
seco The experimental data for an aqueous solution of SOD
are reported(80) in Fig. 12- 19. Their fitting to the dipolar coupling model,
including the coupling between the electron and the copper nucleus, has provided
a ' e of 3 X 10- 9 sec a copper oxygen distance of 2.4 Afor a single water molecule
in the coordination sphere.( 65
l
The value of ' e could correspond to the water
exchange rate, 'm ' or to the electronic relaxation time, ' s' It is reported that 'e
corresponds to 's.(6 5) Relaxometry is, therefore, a too1 to determine the electronic
relaxation times, provided that rotation is slower than elect ronic relaxation.
4
l

3
?
2
ro

e
2
e
(L
o.e
The ele
12- 7.(2
frequer
In som
nmr of
12-11
rst
on
A.
red
ult
-0
6
Itact
f
",hen
in of
SOD
,nism
)th ls
:field
Such
le is
1 le is
SOD
nodel,
)vided
,lecule
water
that le
.. 4 ,-----------------,
Ui
25'
3
e
2
ro

e
B
o::
o
0.01 0.1 10
Proton LarmorIrequency(MHz)
12-11 Electronic Relaxation Times 527
FIGURE 12-19 Water proton
relaxation data lorsuperoxide
dismutase solutions
80
The solid
line is the best-litcurve
obtained with the inclusion 01
the ellect 01 hyperline coupling
with the metal nucleus(65)
100
12-11 ELECTRONIC RELAXATION TIMES
Theelectronicrelaxation timesestimatedwith rel axometryare reported in Table
12-7.<2.53)Theya re referred toa magneticfield of2.35 T,(lOOMHz 1H resonance
frequency) becauseelectronicrelaxat ion has beenalsofound tobefield dependent
in sorne cases. These relaxation times are very relevant for understanding the
nmr ofparamagnetic molecules. In the cases of dipolar relaxation dominating
TABLE 12-7. Electronic Relaxation Rates lor Various
Metal lons and Nuclear Line Broadening Due to Dipolar
Relaxation
a
Nuclear Une
Metal Ion !,- ' (sec- ' ) Broadening (Hz)"
Ti3+ 10
9
_ 10
10

V02+ 10
8
_ 10
9

V
3
+ 2 x 10" 100
V
2
+
2 x 10
9
9000
Cr
3
+ 2 x 10
9
9000
Cr
2
+ 10
11
300
Mn
3
+ 10
10
_ 10
11

Mn2+ 10
8
- 10
9
200,000-40,000
Fe
3
+ (H.S.) 10
10
- 10" 5000-400
Fe3+ (L.S.) 10
11
_ 10
12

Fe
2
+ (H.S.) 10
12
70
C0
2
+ (H.S.) 10" _ 10
12

C0
2
+ (L. S.) 10
9
_ 10
10

Ni2+ 10
10
- 10
12

Cu
2
+ 3 x 10
8
- 10
9

Ru
3
+ 10
11
- 10
12

Re
3
+ 10" 100
Gd3+ 10
8
- 10
9

Ln
3
+ 10
12

;tronic
on. o For JH, r =500 ppm, Bo =2.35 T.
and "sbeing the correlation time, the line width of a proton at a distance of 5
from the metal is predicted from equation (12-40) and reported in Table 12-7.
From inspection of the table, it is seen that sorne metal ions, including most
of the lanthanides, give rise to little nmr line broadening. Low spin iron(TTI), high
spin octahedral cobalt(Il), and high spin tetrahedral nickel(lI) fall in this category.
Manganese(Il), gadolinium(III), copper(II), and vanadium(IV) give rise to very
broad signals. The first class of metal ions are called shift reagents because they
provide hyperfine shifts with little broadening, whereas the latter class is called
relaxation reagents beca use they relax the nuclei. In excess ligand and under fast
exchange conditions, the line broadening, or 1 enhancement, is reduced
according to the mole fraction of bound ligando Under these conditions, a ligand
nucleus can be observed in the presence of a relaxing agent yielding fruitful
information from the relaxation parameters.
Knowing the values Of"5 is a starting point to attempt an understanding of
the factors that determine clectronic relaxation in solution. Every time"r is shorter
than "" we can propose that fluctuating magnetic fields associated with rotation
cause electronic relaxation. In addition to the intensity of the magnetic moments,
the electron spin differs from the nuclear spin because the electro n spin angular
momentum is coupled with the orbital angular momentum. The angular
momentum is orientation dependent. This leads to 9 values and zero field splitting
values that are orientation dependent. We say that rotation modulates the 9
anisotropy and the zero field splitting. Such modulations are associated with
modulations of the orbital magnetic moment and cause eJectron spin relaxation.
When rotation is slower than electron relaxation, rotation cannot be the
mechanism that Jeads to electron relaxation. In this case, it is instructive to refer
to solid-state mechanisms. Indeed, lanthanides have comparable electron relax-
ation rates in solution and in the solid state, which are much larger than rotation
rates. It may be assumed that on the time scale of electro n relaxation the
surrounding solvent of a metal ion in solution can be visualized as a small crystal.
In this context, we shall discuss sorne results in solids.
In solids, there are crystal vibrations of low energy whose excited levels are
populated according to the temperature.(81) Changes in the excited vibrati onal
levels cause modulation of the metal-donor distances, which are reflected in
changes of the orbital angular momentum, which in turn lead to electron
relaxation. Differences in crystal vibration frequencies due to population or
depopulation of a given level are frequencies called phonons.(82) In crystals there
are continuous emissions or absorptions of phonons through exchange with other
properties of the solid (e.g., with the electron spin levels of a paramagnetic
substance). Around room temperature there are many phonons with frequencies
of the order of 100--1000 cm -l. Therefore, if the substance has electronic spin
levels with energy separations of this order of magnitude, electron relaxation will
be very efficient.(83)This is the case oflanthanides where the ground levels reported
in Table 12-1 are split by the aboye order of magnitude from the action of the
crystalline field.(84) The same situation holds for high spin octahedral cobalt(Il)
and tetrahedral nickel(Il) complexes.(85) The ground state is a 4T
29
and a 3T
respectively (i.e., it is orbitally triply degenerate). Low symmetry components and
spin orbit coupling give rise to six Kramers' doublets in the former case and up
to nine levels in the latter. Among these, energy separations of the order of the
phonon energies exist at room temperature. Octahedral nickel(Il) and tetrahedral
cobalt(Il) have an orbitally non-degenerate ground state so the low symmetry
c(
sfi
pI'
ca
Th
at (
req
[(F'
lim
bigl
the
Corr
l H
spin
vari,
coml
acco
H
(B)'H N
1a - (
(A)'H NI
la in
L
ofthe
balt(Il)
a 3T
1
ntsand
and up
ofthe
ral
ry
12-11 Electronic Relaxation Times 529
component and spin orbit coupling provide smaller values of the zero field LatticeSpin Lattice Spin
-r- e --r
,
splitting. It follows that electron relaxation is slower because there are fewer
,
,
,
phonons ofthat energy.
Thegeneralideais that,whenevertherearelow-Iyingexcitedstates,phonons
can provide the energy for transitions involving a change in ms (Fig. 12- 20(A)).
This mechanism is called the Orbach process. When there are no exci ted states
atenergiesaround100cm- 1, thetransitionsbetweenZeemanlevelsoccurthrough
a combination of two phonons whose energy difference matches the energy
required for electron relaxation. This process, called the Raman process(84.86)
[(Fig. 12-20(B) ,is far less efficient and accounts for the longelectr n relaxation
times of copper(IT), vanadium(JV), high spin manganese(H), etc. In t he case of
highspiniron(III), (second order)spin orbitcouplingis ratherefficient in splitting
the 6S. When there are strong anisotropies as in the case of sorne porphyrin
complexes, the splitting is ofthe order ofseveral tens ofwavenumbers and the
lH nmr signal can be observed. In general , theelectron relaxation rates ofhigh
spin iron(IlI) complexes are difficult to predict because zero field splitting is
variable.
In summary, electrons can relax through the rotational mechanisms for
compondswith slowelectron relaxation rates in solution. When rotationcannot
account for the observed values ofelectron relaxation, we should refer to the
(Cl
7
HNMR
la-d
2
in H
2
0
HOO
H H
N/ 2 . ~ N 3 5 H
, /0-. /
f ..... ,cu, 4
E
Ny:Or3
,
"'" m
CHJ ____________~ ~ ___J,____________
40 30 20 10 O
ppm
x
(Bl'HNMR
la-d
2
in 0
2
0
3
~
x
(Al' HNMR
lain 0
2
0
. llH3 m
3
HOO
2' '4 .
~ . .'
Ji
184Hz
30 20 10 O
ppm
rl
,
+.-
,
, ,
, ,
, ,
, ,
, ,
, ,
, ,
, ,
, ,
,
b ,
,
- b ,
,,
.L!... - a
J.J.. .la
,,
(A) (B)
FIGURE 12-20 (A) Orbach
and (B) Raman processes . In
an Orbach process, the
electron spin is excited to
level e by absorption 01 a
lattice phonon and then
emits another phonon to
level b. In a Raman process,
the electron spin is excited
directly to an excited level by
simultaneous absorption and
emission (scattering) 01 a
single phonon.
FIGURE 12-21 (A) lH nmr
spectra at 23 e01 the
compound shown and (B) its
partially deuterated10rrp in
0
2
0 (shaded arrow denoted
the resonance position of the
2-H signal) and (e) 2H nmr
spectrum at23 e in H
2
0.
I
type of mechanisms observed in the solid state. The presence of unpaired electrons
always causes line broadening. Equations (12-38) and (12-40) provide an estimate
of the line broadening as a function of Te; the latter may or ma y not be equal to
the electronic relaxation times. In any case, the electronic relaxation times
represent an upper limit for the broadening. For example, a proton at 5 from
copper(Il) would experience a broadening of :::: 5000 Hz at 100 MHz (Table 12-7),
if the correlation time were determined by T . This holds for macromolecules that
s
rotate slowly. In small complexes, however, Te is determined by a short T, and
therefore the tine broadening is smaller. Finally, a proper choice of the magnetic
field should be made by taking into account equation (12-44) (Curie relaxation).
A comment is also appropriate regarding the choice ofthe resonating nuc1eus.
The metal nuc1ei bearing the unpaired electrons cannot be observed because the
coupling is too strong and the line width too large. Nuc1ei with small magnetic
moments are broadened less because the coupling energy is small (although the
magnitude of the hyperfine shift decreases when expressed in Hz). lt is common
to use a deuteron instead of a proton when the linewidths uf the latter are too
large to be detected. In Fig. 12-21, the I H and 2 H spectra of copper(I1) complexes
are shown.(8 7)
12-12 CONTRAST AGENTS
NMR imaging is a new clinical technique to obtain an image that is used
particularly for the head and spine. The technique is sensitive to the protons of
tissue water and fat in both soft tissue and bone marrow, and is insensitive to
bone itself. Proton density varies only slightly among tissues. The change is not
large enough for images oC proton density alone to be c1inically usefu\. However,
the relaxation rates of tissue protons vary significant ly fr om one tissue to another,
so that contrast in the nmr image depends mainly on lhe rel axation rates, TI
and T
2
. The contrast can be optimized case by case with the appropriate weighting
of the relaxation rates. (88)
Jt is the aim of researchers in the field to improve contrast and resolution
for a given image in order to obtain a better image or a comparable image in
less time. A reasonable way involves altering relaxation rates by introducing a
paramagnetic compound into the tissue, which acts as contrast-enhancing agent.
From the inorganic point of view, a contrast agent is a complex with a
capability of dramatically increasing the proton T; I and 1. According to
equations (12- 37) to (12-40), lhe complex should have a large S and a long T
s
'
These properties are met in Gd3+ (S = 7/
2
) , Mn2+ and Fe3+ (S = %). F urther-
more, water molecules should be in fast chemical exchange conditions with the
paramagnetic center as is usually the case for water molecules coordinated to
M n2+ and Gd
3
+. T he correct approach requires measurement of TI and T
2
0f
a water solution of the complex at various magnetic fields in order to check the
relaxivity (solvent relaxat ion rate enhancement per mM solute) at the imager
frequency(89) Then the complex should be tested in tissues and the water proton
relaxation rates remeasu red direct1y at different times after the injection. Tissues
behave essentially as liquids.(88) Experiments in tissues can be made in vivo in
test animals or after surgi cal asportation of pathological samples.
T he organic part of the ligand is responsible for targeting a certain tissue
when the contrast agent is administered as a drug. At present, the contrast agent
H
H
ga
sh,
bei
12-
n,
don
the
wiO'
The
with

mole
netic
nuele
The
Ther
varia!
time.!
Sectic
coupl:
by the
where
corresl
neighb
where
the COr
Pa
r is sm
CH
2
m
s
te

es
m
7),
at
nd
tic
n).
uso
the
r

ron
too
exes
used
::lns of
:ive to
is not
wever,
lother,
,tes, TI
ighting
olution
nage in
ucing a
gagent.
;with a
rding to
long T,.
Further-
wi\h the
Inated \0
md T
2
of
check the
le imag
er
er proton
n. Tissues
in vivo in
tain tissue
trast agent
12-13 Trends in the Development01 Paramagnetic NMR 531
CH2COOH
I / CH
2
-COO
H
FIGURE 12-22 The DTPA
5
-
N- (CH
2
)2- N- (CH
2
)2 - N
anion.
HOOC-H
2
C/ CH
2
- COO
H
gadolinium (diethylenetriamine pentaacetate)2- (GdDTPA2 -, with DT PA5-
shown in Fig. 12-22)is commerciallyavailable.Othergadolinium complexes are
being investigated.(90)
12-13 TRENOS IN THE OEVELOPMENT OF PARAMAGNETIC
NMR
ne main goal in nmr is the assignment of peaks. T; 1 and T'; 1 are often
dominated by dipolar coupling and, therefore, depend at least qualitatively on
the sixth power of the nucleus-metal distance. These measurements, together
with the analysis ofthe shifts and sorne experience, can lead to an assignment.
Therelativeintensitiesofthesignalsandsubstitutionofa nucleus,often a proton,
with another group or isotope help in the assignment. NMR in diamagnetic
systems hasgonefar in establishingcrlteriaforassignmentandin relatingnuclear
properties with internuclear distances. The trends in nmr of paramagnetic
molecules parallel the applications ofthe well-established techniques in diamag-
neticsystems,withthelimitationsimposedon theparamagneticsystemfrom fast
nuclear relaxation.
The Nuclear Overhauser Effect
The nuclear Overhauser effect (nOe), in its more classical form, is the fractional
variation of a signal intensity when another signal is saturated for a long
time(91.92) This is callcd steady-state nOe (see the diamagnetic nmr chapter,
Section 8-6). Ifthe nuclei correspondingto two signals interact through dipolar
coupling,thena steady-statenOeis observedwhich,asalreadydiscussed,is given
by the equation
(12-46)
where (J is the dipolar cross relaxation and p can be taken as T j . Here, (J
corresponds to the net magneti zation transfer from the sat urated nucleus to its
neighbor under observation and is given by
(12- 47)
where J.1 and J.12 are the nuclear magnetic moments, r is their distance, and 1e is
the correlation time for their reciprocal reorientation.
Paramagnetic molecules are characterized by large p values and therefore
r is small. For protons, in the ortllO positi on ofaromat ic rings or geminal in a
eH2 moiety, the distance is small and even if p is of the order of 10
2
sec- i, r
532 Chapter 12 Nuclear Magnetic Resonance of Paramagnetic Substances in Solution
can be of the order of 1 to 5%. Therefore, nOe can be measured under high
signal-to-noise conditions. The conditions for observing nOe are best if the
magneticfield is highandTe is large.Therefore,applicationsaresuccessful1y made
in the study ofparamagneticmetalloproteins where Te is large corresponding to
the rotational correlation time, equation (12- 33). Sorne examples of nOe
experiments in different systems are shown in Fig. 12_23(93.94)
Steady-state nOe in diamagnetic molecules result in the observation of
secondary nOe through spin diffusion. Theeffect is greatly reduced in paramag-
neticsystemswhere nuclear relaxation is so fast thatsecondarynOedo not have
time to build Up(95)
Transient nOeis the fractional variationofa signal intensity when a related
signalis invertedwitha180
0
pulse.Sincetheinvertedsignalreturnstoequilibrium
witha timeconstant T ~ t, whichis largein a paramagneticsystem,magnetizaticn
transfer is small. In general, transient nOe experiments give poorer results than
steady-state nOe experiments.(95) Nuclear Overhauser effect measurements pro-
vide information on internuclear distances and, therefore, provide a unique
criterion to perform a scientifically correct assignment.
The Effect of Fast Nuclear Relaxalion on 2-D Spectra
The 2-D experiments, COSY and NOESY (see Section 8-19), are also possible
for paramagneticsystems. In thiscase, the limitis thatthe magnetization transfer
f 9
k
FIGURE 12-23 Some
examples 01 nOe dillerence
spectra 01 paramagnetic
metalloproteins. (A) Reduced
lerredoxin Irom P. umbilicalis
in
2
0 (93) (B) N
3
- adduct of
copper(II)-cobalt(ll)
superoxide dismutase in
H
2
0 . The nOe's are typically
of a few percent.
b
S
n
O
S(
e)
e)
1 -
2-
3-
-
5-
~
6-
LJ
120
3
4
5
II
35
f 9
x ~
9
III II III
30 25
h
ox
ox
~
x5
II I I I I I I I II III I I III I I
15 10
ppm
(A)
2
m
I
~

5 O -5
I
12-13 Trends in the Development of Paramagnetic NMR 533
,gh
the
lde
to
lOe
of
lag-
lave
ated
rium
ition
Ihan
pro-
nique
)ssible
ransfer
n. P
-

-
o
orredistribution responsible ror cross peaksshould occur before the spin system
returnstothestartingequilibriumsituation.Thereturntoequilibriumisgoverned
by the relaxation times TI and T
1
, which, as we have said, may be very short.
Sometimes, TI and T
2
are so short that there is not enough time to alter the
magnetization ofthe loupled spins. Recent experiments have shown that ror TI
or T
2
of the order of 50 msec, 2-D experiments are feasible with millimolar
solutions. The results are useful if other conditions, Iike a long L, for NOESY
experiments or large J values ror COSY experiments, are satisfied(96-99) One
example is reported in the following section.
G
e
R
A
1---"'-
o
2--_

A
FIGUR E 12-23 (continued)
e

e
l

M
6

LP R
I I I
120 90 60 30 o -30
8(ppm)
(B)
12-14 SOME APPLlCATIONS
Planar- Telrahedral Equi/ibra n Nckel
Oneoftheearlyapplications of1H nmrto paramagneticcomplexes involved bis
N-substituted aminotroponeiminate nickel(II) complexesYoO) A chemical equi-
librium exists between planar, diamagnetic, and tetrahedral, paramagnetic
species(IOI) Peak assignments were performed on the basis ofchemical substi-
tution and on the analysis ofthe first-order Jsplitting that is observed when the
diamagneticspeciesis dominant.Theshiftsontheringarealternating,asexpected
for a 7[ delocalization pattern(l02) A large variety ofsubstituents,R, on nitrogen
were investigated. When R is aliphatic, the shiftsdecreasewith thedistance from
the paramagneticcenter,whereas in the case ofaromaticsubstituents largeshifts
are also observed for protons very far away (Table 12_8)(103)
Since the planar-tetrahedral equilibrium is fast on the nmr time scale, the
isotropic shift depends on the molar fraction of the paramagnetic species. The
equilibrium constant is expressed as
[P] IX
K= - - -
[D] 1- IX
TABLE 12-8. lH Contact Shifts or R Groups in N-
substituted Nickel Aminotroponeiminates
a
(103)
R
CH} 3.36
CH
2
-CH} CH
2
3.24
CH} 0.21
-O
CH
2
-CH
1
CH
3
CH
2
3.44
CH
2
0.23
CH
3
0.12
o -0.36
m 0.38
p -0.51
o -0.37
m 0.37

CH} 0.63
o -0.37
m 0.38
o -0.037
-0-0 m' 0.051
p' -0.059
o - 0.39
m 0.34
o' -0.01
--Q--o--O
m'
p' - 0.01
\\1
is
po
m

Stl
Th
R,
mH
eq
del l
Dast,
N-alk
the
"Theshiftsarerelativeto theshiftofhef3 protonofthetroponeiminate
ring, ip. Such shifts are in he 20 to 30 ppm range.
obser'
shifts
is
1-
ie
l-
e
d
en
m
fts
he
he
where [P] is the concentration ofthe tetra hedral paramagnet ic species a nd [O]
is the concentration ofthe planar diamagnetic species.<36) The molar fr action of
paramagnetic species is given by a:
)obscr ved
rY. =
(L1 V)fully pa ramagn elic
When ofthe fuJly paramagnetic species is not available, one should rely on
the validity ofequation(12-17) for estimating such a value(l04)
Diastereoisomerism
Bis-N-substituted salicylaldiminatesalsoundergoplanar tetrahedralequilibria.
Studies similar to those ofthe aminotroponeiminates have been performed(105)
The bis-chelate complexes are dissymmetric and can be \ or As the
R = see-butylgroupbearsa centerofasymmetry,thebis N-sec-butylsalicyladimi-
natecomplexescanexistastwodiastereoisomers1\ +and\-,whicharepairwise
equivalent to - and +, respectively(1 06) The two diastereoisomers are
detectedthankstosharplinesandtothetwodifferentisotropicshifts(Fig. 12- 24).
act o
X=O
CH
meso
actll
/ \
00

<D
mm

X=S
TMS
/
y - \
H P\ }-Ji/2
a N
\
H CH CH
2
CH
3
/ -
CH3
p-H
Ho

O
TMS
,
00
(")trl
mo
r-- ro
+ +
a-H Cd p-H
12-14 Some Appli cations 535
FIGURE 12-24 100 MHz 'H
nmr spectra 01 mixtures 01
active and meso isomers 01
Ni(sBuPhHHb(X = O) and
Ni(sBu-SPhHH) 2(X = S) in
CDCI
3
solution at _30.
Chemical shifts are given in
Hz relative to TMS. ll06)
meso meso meso
act.
altI
I I
TI
I
I I
o o o o
LD <t trl
o 00
<D Ntrl
N <D N
<t o
trl<t
9 ''

N
+ +
Dlastereoisomerlsm and Dlastereotopism in Cobalt(lI)
N-alkyl pyridin-2-aldiminesgive rise to tris-chel ate cobalt(Il) eomplexes. Oue to
the asymmetric nature of the Iigand, cis and trans isomers are cxpected and
observed (Fig. 12_25).(1 07) The contact and pseudocontact contributions to the
shifts cad to a large difference in shift s for the various isomers. When R is
FIGURE 12-25 'H nmr
spectra at 26 01
Co(N-isopropyl
pyridin-2-aldimine)3
2
+ in
d
3
-acetonitrile (top) nd
ds-acetone (bottom)1107
1
CH)
,
O 00 O
a
p
o.X),
Hy
n

O (J to the existence of a more square pyramidal (almost equivalent groups) or more
O
a. trigonal bypyramidal (more inequivalent groups) isomers. The generalit y. of the
j inequivalence in one isomer was then shown for the bis thio analog.( 109) The
assignment of the aromatic signals was performed by varying substituents. Next,
the spectra) width was increased to include all the signalsY) Finally, TI
measurements and 2-D spectra have led to a complete assignment(96)
(Q0
,
"
N
I I I I I I
20 10 O -10 -20 -30
S(ppm)
isopropyl, the two CH
3
groups are inequivalent beca use they sense an asymmetric
center that is the metal. Two signals are expected for the cis isomer and six for
the trans isomer. Indeed, eight well-separated signals are observed. In every case
the intensity of the cis signa) is minor corresponding to a less stable isomer (Fig.
12_25)(107)
Group Inequivalence in NiSALMeDPT
The five coordinated, bis (3,3' -salicylideneiminatopropyl) methyl amino nickel(IT)
complex is asymmetric, with the CH
3
group making the two salicy)aldiminate
mOletles inequivalent when coordinated. The signals of the two
salicylideneiminatopropyl groups will differ (as seen in Fig. 12-26). This system
was first studied by LaMar and Sacconi,u8) who related the difference in shift
L
L
F'G
Eac
Ion
Ion
mve
catic
(Fig.
onto
poss
Ther
Thes
form
densi
systel
nucle
corre.
the re
where
sum (
12-14 Some Applications 537
6H
n
4H
n
6H
n
3H
~ C H
n
4H
n r>-CH
a-CH
n
I I I I I I
3-H
30 20 10 O -10
n
ppm
y-CH
y-CH n
n
CH = N
~
I I I
500 400 300 200 100 o
ppm
FIGURE 12-26 Room lemperalure lH nmrspeclra 01 5CI-NiSALMeDPT in CDCl
a
.
EachproloninIhemolecule(exceplIhemelhylprolons)givesriseloaseparalesigna!.
Ion Pairing
Ion pairs involving a paramagnetic anion and a diamagnetic cation have been
investigated through 1 H nmr.(llO,III) The protons of the tetraalkylammonium
cation experience an isotropic shift, which is probably contact in nature
(Fig, 12-27). When the pair is formed, it appears that spin density is transferred
onto the diamagnetic cation. The approach of the two anions occurs from every
possible direction, and the free ~ paired equili brium is fast on the nmr time scale.
Therefore, all the equivalent cation protons remain equivalent upon pairing,
These systems were investigated through the shifts( 110.111) and T values.( 111) The
formation of ion pairs is enough to provide orbital overlap and transfer of spin
density, Cases can be conceived where a moiety can approach a paramagnetic
system at van der Waals distance (i .e., the spin transfer is negligible, but the
nucleus still sen ses the unpaired electron through space). In this case, the
correlation time for the interaction can be the dilfusion correlation time T D and
the relaxation equations have a form of the type(112,113)
Ti
l
= (32n/405)y/y/h
2
S(S +l)(N,J1000)([M] /(d/D))' [1
2
(ws - w)
+ 31(w
l
) +61
2
(w
s
+w)] (12-48)
T;l = (16n/405)Y/Ys2h
2
S(S +l)(NA/IOOO)([M]/(dD)) [41
1
(0)
(12-49)
where N A is Avogadro's constant, d is the distance of cIosest approach, D is the
sum of the dilfusion coefficients for the two molecules, and [M] is the
l
538 Chapler 12 Nuclear Magnetic Resonance 01 Paramagnet ic Substances in Solution
FIGU RE 12-27 A contact
interaction OCCL!rs in
(NR
4
l + (MX
4
l -- ion pai rs involving
the a-CH
2
groups 01 the
cation .l'lO,ll l )
MXC;>
8-e
concentration of the molecule bearing the paramagnetic center. Under a wide
range of conditions the spectral density functions are given by
JI = J
2
= (1 + 5z/8 + z2/8)/(1 + z + z2/2 + z3/6 + 4z
4
/81 + 2
5
/ 81 + z6/648)
(12-50)
with
(12-51)
In turn, 'D is given by
(12-52)
A model of this type has been used to describe the interaction of water with
Cr(en)] 3 +.' 114)
Hemln-Imidazole-Cyanlde
T he spectrum of a heme complex (i,e., hemin-i midazole-cyanide) is an example
of a low spin (S = 1/
2
) iron(TTT) heme system. Heme complexes are present in
many proteins and studies have led to understanding of these important complex
sys tems. The spectrum of a model is shown in Fig. 12-28).<115) The four intense
signal s are assigned to the four ring methyls. Their precise assignment can be
H
aCH
2
H
I
CH
2
I
ca;
12-14 Sorne Applications 539
FIGURE 12-28 Room
temperature 600 MHz 1H nmr
spectrum of
hemin-imidazole-cyanide.
The hemin scheme is
reported in the
\Vide
'648)
12-50)
12-51)
(12- 52)
ter with
example
lresent in
t complex
ur intense
nI. can be
s-eH 3 4. 5
2'
2
meso a
6-Ha'
6-Ha
meso
meso

7-Ha
6. 7-Ha'
meso 'Y

1
16. 2-Ha
I
I4-Ha
1
5'11
4
'
I I I
16 14 12 10 s 6 4 2 O -2
made by using selectively deuterated samples. Alternatively, 2-D NOESY and
COSY spectra can be employed. In the NOESY spectra, cross peaks occur between
adjacent protons. In the COSY spectra, the cross peaks occur between signals
related by J coupling. Vinyl and propionyl group correlations are found both in
NOESY and COSY spectra, as shown in Fig. 12-29( 115) Methyl groups are
distinguished because 1 and 3 give a nOe with vinyl groups. Finally, methyls 1
and 8 give a nOe to one another. The methyl signals, once assigned, give a nOe
with the meso protons and, therefore, the spectrum is fully assigned. As far as
the imidazole is concerned, the l'-H signal disappears when the spectrum is
recorded in 0
2
0 and 2'-H as well as 4'-H have the shortest TI' Al! these spectra
were recorded at 40 mM heme concentrationY 1 5) In the case of proteins, the
concentration is about one order of magnitude lower and, as a result, sorne cross
peaks may be lost.
Spin Delocalization In Iron Porphyrins
Iron porphyrins are important molecules especially for their biological relevan ce.
Iron(111) can be high spin or low spin, a1though in sorne cases spin admixtures
are proposed. The electronic levels in the two cases are shown in the following
I
FIGURE 12-29
Two-dimensional 'H COSY
(upper left) and NOESY
(Iower right) spectra of
hemin-imidozole-cyan ideo
The labeling on the spectrum
(Iowercase = COSY,
uppercase = NOESY)
indicates the following
correspondences to the
scheme in Fig. 12-28.
alA: 8-CH
3
/7-Ha h:
blB: 8-CH
3
/7-Ha' i:
clC: 5-CH
3
/6-Ha j:
diO: 5-CH
3
/6-Ha' 1:
e: 3-CH
3
/4-Ha m:
f: 1-CHi2-Ha nlN:
g: 2-Hi2-H{3f 010:
sch,
S-CH 3 4, 5
Th
2' The
CH
3 1
5
-
2
far
mesoa
6-Ha'
6-Ha
meso
meso1)

7-Ha
6,
7-Ha'
mesoy
1
16, 2-Ha

I
I4-Ha
;oJ

, .
9 0 ' o 0.
r
-2
oro
.
O
nq
2
electr
4
comp
b. d
6NOOR 12- 3C a' .
'c
6
E
o-
o-
S
Pyrrol
10

Y (}JY2
1
12

X, G X
2
o, Z,
OW
14
16
16
ppm
2-Ha/2-H{3c
p:.
7-Ha/7-Ha' X,: 3-CH
3
/meso a
4-Ha/4-H{3f qlQ: 7-Ha/7-H{3,{3' X
2
: 1-CH
3
/meso (j
4-Ha/4-H{3c rlR: 7-Ha' /7-H{3,{3' Y,: 2-Ha/meso a
2/4,5 s: 2-H{3/2-H{3c Y
2
: 4-Ha/meso {3
6-Ha/6-Ha' t:
4-H.B/4-H{3c Z,: 3-CH
3
/4-H{3f
6-Ha/6-H{3,{3 U: 8-CH
3
/meso (j Z2: 1-Ch
3
/2-H{3f
L-L
90 80
6-Ha'/6-H{3
V: 5-CH
3
/meso .B
1
---------------------------
' _2
o
2
4
6
E
a.
a.
12
z,
14
16
scheme. H igh spin complexes have unpaired electl"ons in a-type orbitals
P
16)
Therefore, a dominant a delocalization and large downfield shifts are expected.
The pyrrole protons of meso-tetraphenylporphyrin (TPP) chloride complexes are
far downfield (Fig. 12_30).<2. 116)
+
dz2
-tt-
D4 D;h(elongaled)
High spin Low spin
Similar considerations hold for high spin iron(Il ). In contrast , the unpaired
electron is in a n-type orbital in the low spin iron(llI) TP P bis-imidazole
complex(l 16) The shifts are smal1er and the pyrroJe proton is shifted upfield (Fig.
12-30). Since low spin iron(ITT) complexes have short electronic relaxation times,
p-H
FeTPPCI (S = 5/2)
Pyrrole H
m, p-H
FeTPPlm; (S = 1/2)
pyrrole
4-H
2-H
1-H 5-H
o, m, p-H
FeTPP2-CH3-lm (S =2)
Pyrrole H
3
______________AL_____________jG2-CH
J]
m,p-H
rrOleH
,-H : F,TPPIS= 11
I I I I I I I I I
90 80 70 60 50 40 30 20 10 O -10 -20
8(ppm)
12- 14 Some Applications 541
FIGURE 12-30 Simulated'H
nmr spectra 01
meso-tetraphenylporphyrin
(TPP) iron complexes.<2
1
Chemical shilts are in ppm
Irom TMS.
the nmr signals are quite sharp. The 1 H nmr spectra of iron(III) hemin-
imidazole-cyanide, (11 S) shown in Fig. 12- 28, provides a typical example of this
class of compounds.
Cobalt-substituted Carbonic Anhydrase
Carbonic anhydrase (CA) is a zinc protein of MW 30,000. Zinc can be removed
and substituted by cobalt(Il) without loss of activity. Cobalt(IJ) in CoCA is high
spin. Three histidine imidazoles and a water molecule are coordinated. One of
the imidazoles is coordinated to the metal through its Nl nitrogen, whereas the
other two are coordinated through their Nc2 nitrogens. If is added to the
CoCA solution, it binds cobalt giving rise to a five-coordinate deriva ti ve where
one oxygen of nitrate adds as a fifth ligandoThe spectrum i shown in Fig. 12-31
as an example of a spectrum of a metalloprotein.<117)
Four signals are observed far downfield. Three of them disappear when the
spectrum is recorded in D
2
0 and these are assigned to the exchangeable NH
protons of the t hre coordinated histidine rings. The non-exchangeable signal at
71 ppm is of similar line width, and is thus assigned to the H2 proton of His-119,
the only one not acljacent to a coordinating nitrogen. This signal gives an nOe
with the NH signal at 80 ppm, which is therefore its neighbor (Hc2) on the
imidazole ring of His-lL9. (118) The other signals between +30 and - 20 ppm
belong to protons that are al! close to cobalt and the shifts are al! dipolar in
origino Their assignment(118) is a challenge with implications of paramount
importance for further investigation of proteins.
ni!
an
whe
maE
the
beld
nucl
we
valu
This
elecl

as in
is
ed
gh
of
-H
reas the
d to the
'e where
g. \2-31
"hen the
able NH
signal at
His-119,
. an nOe
~ 00 the
- 20 ppm
ii polar in
aramo
unt
12-15 The Investigation 01 Bimetallic Systems 543
100 80 60 40 20 o -20 -40
8(ppm)
FIGURE 12-31 Room temperature 1H nmr spectrum al the
nitrate adduct al cobalt(lI) substituted carbonic
anhydrase(117.
118
1 The shaded signals disappear in Dp.
12-15 THE INVESTIGATION OF BI METALLlC SYSTEMS
We now consider the consequences of magnetic coupling in bimetallic systems
(see Chapter 11) on nmr. For simplicity and without loss of generality, consider
that one nucleus senses only one metal ion of the couple. If tbis were not the
case, the effects of each metal ion, calculated separately, would be added. O ur
working scheme is therefore
N ---- M ---- M
2
wbere N is the nucleus and M and M 2 two metal ions. Also consider tha t
magnetic coupling between M and M
2
is a weak perturbation with respect to
the energy and distribution of electrons of the moieties to which M and M
2
belong in the absence of magnetic coupling. This means that spin density on
nucleus N is not affected by the existence of magnetic coupling. Furthermore,
we can also consider that the electronic relaxation time of metal 1 changes its
value in a perturbative fashion when interacting with the electron of metal 2.
This consideration is not fuJly justified, since it is arbitrary to refer to only one
electronic relaxation time of a metal ion. * In principie, there is an electronic
relaxation time for each level arising from magnetic coupling. Nevertheless, this
reasoning leads to the conclusion that for homodimeric systems there is no change
* Electronic relaxation time is treated as a single transition ; when there are several transitio ns
as in the case of zero field splil leveJs, it is appropriate to assign a reJaxation time for each transition.
l
544 Chapler 12 Nuclear Magnetic Resonance 01 Paramagnetic Substances in Sol ution
of electronic relaxation times, whereas in heterodimetallic systems one metal ion
will have larger electronic relaxation times than the other. In the latter case, the
slow relaxing metal ion will take advantage of magnetic coupling, and its electrons
will relax with the mechanism of the fast -relaxing metal ion. Thus, magnetic
eoupling causes a shortening of the electronie relaxation time of the slow-relaxing
metal ion. These conelusions are consistent with observations. Equations and
discussions are available in the literature that relate the extent and nature of J
with the values of electron reJaxation timesf 53. 11 9)
The 1H nmr olDimeric Complexes
The following ligand
H H
H
indieated as PMK, provides a nice frame for bimetaIlic sys tems where antiferro-
magnetic coupling is established between the two metal ions. The systems studied
inelude CoCo, NiNi, CuCo, and CuNi.(l20) With Zn being diamagnetie CuZn,
CoZn, and NiZn represent the blank.(70,121) The J value is relatively small (i.e. ,
<% kT at room temperature). Consequently, all the energy Jevels arising from
magnetic eoupling are almost equally popuJated. The isotropie shift experienced
by eaeh proton is the sum of the eontributions of the two ions (i. e., the
TABLE 12-9. 200 MHz I H nmr Shift and TI Values at 300 K lo r the Isotropieal ly
Shilted Signals in the CU
2
C0
2
SOD Derivative Together with Their Assignment
(signal labeling relers to Figs. 12-33 and 12-34)
Signal b, ppm Ti> ms Assignmenl
A 66.2 1.5 His-61 H2
B 56.5 7.8 Hi s-118 H l
e 50.3 4.2 His-44 He2
o 49.4 3.8 His-69 H 2
E 48.8 4.6 Hi s-78 H2
F 46.7 2.1 His-78 He2 (His-69 He2)
G 40.6 3.5 His-44 H2
H 39.0 1.8 Hi s- 118 He!
1 37.4 1.7 Asp-81 H,lH (Asp-81 Hf32)
l' 35.6 1.7 Asp-81 Hf32 (Asp-81 Hf31)
J 35.4 d His-69 He2 (His-78 He2)
K 34.5 8. 0 His-46 H1
L 28.4 4.3 His-46 H2
M 25. 3 2.7 His-44 Hd
N 24.1 2.9 His-118 H 2
o 19.6 1.9 His-46 Hel
p
18.7 1.6 His-44 Hf31
Q(R) -6.2 2.4 His-69 Hf32
R(Q) - 6.2 2.4 His-44 Hf32
sun
far
for
wh
nu
rel 2
this
IH

are
CU2
The
ana
supe
with
hi5ti
bOlll
One
with
sensi
prot
IOns
with
thosl
the l
shan
sincE
ofth
sum of the shift of a given proton in the MIZn and the ZnM
2
complexes). As
far as the line widths are concerned, those of the CuZn complex are very large
for those protons sensing copper because T, 10- 9 sec and 'e is given by 'r'
which is 10-
11
sec(120) Such a relatively long value of 's provides a short
nuclear T
2
[equatioll (12-38)]. In the CuCo system, cobalt(I1) has an electronic
relaxaiion time of 10-
12
sec (see Table 12-9) and the 1s of copper
this value, becoming much shorter than the value of the uncouplcd system. The
IH nmr signals are now quite sharp(121) (Fig. 12-32).

-CH
3
ICo)
10.5 ms
5-0
ICo)
32ms
-----
4-H

ICu)
-CH
3
4-H
120
ICu)
ICo)
ms
3 ms
70 ms
3-H 5-H
(Co)
(Cu)
24ms
40ms
ICo)
3-H
6--H (Co) 6--H
26 ms
1.9 ms ICu)
3.2 ms
).

'---
I
140 120 100 80 60 40 20 o
FIGURE 12-32 1H nmr spectrum 01 CuCo (PMKb
4
+ in D
2
0. Peaks 01 CO
2
(PMKb
4
+
are indicated with an asterisk.l
121
)
CU2C02 Superoxide Dismulase
The enzyme CU
2
C0
2
SOD, where SOD refers to superoxide dismutase, is
analogous to the bimetallic systems. SOD catalyzes the dismutation of the
superoxide ion. One common enzyme is a dimeric protein of MW equal to 32,000
with a MW of 16,000 in each subunit. In each subunit, zinc is bound to three
histidine nitrogens and one oxygen of an aspartate(l22) (Fig. 12-33). Copper is
bound to four histidine nitrogens and is exposed to solvent (see Figure 12-33).
One histidine is in common to the two ions, bridging them. The protein rotates
with 'r 10-
8
sec, whereas 's of copper(I1) is 2 x 10-
9
sec.l6 S) The protons
sensing copper(I1) have such a broad nmr line that they escape detection. The
protein can be manipulated to substitute zinc with cobalt. The copper and cobalt
ions experience antiferromagnetic coupling througb the bridging imidazoJate
with J = 17 cm - 1.0 23) The electronic relaxation times of copper(I1) approach
those of cobalt(TI), which are of the order of 10 - 12 seco The 11-1 nmr signals of
the ligands of both metal ion s can now be observed since they are relatively
sharp.(48,124) Through nOe it has been possible to propose a full assignment(125)
since several interproton distances could be ca\culated and compared to those
of the x-ray structure (see Table 12-9 and Fig. 12-34).
!
I
1
1
546 Chapter 12 Nuclear Magnet ic Resonance 01 Paramagnetic Substances in Solution
His-80
F,J
FIGURE 12-33 Scheme 01 the metal sites in Cu Zn SOD.(122)
2 2
K
B
FIGURE 12-34 ' H nmr
spectr um at 300 K and pH 5.6
acetate buffer 01 the
A
Cu
2
C0
2
SOD derivative.
O,R
o
80 60 40 20 o -20
1H nmr Speclra 01 F e ~ 2 Ferredoxlns
The Fe
2
S
2
ferredoxins are electron transfer proteins of low molecular weight
~ 10,000) con taining the following bimetallicmoiety.
Cys-S S S-Cys
" F
e
--- "f
' e
/
Cys-S/ "S' " S-Cys
The
forrn
lons
groll
ShO\l
mag
an u
the
very
of tt
enve
60
40
20
HC-
'"
/
He
'"
/
Oxid
Redu
12-15 The tnvestigat ion 01 Bimetallic Systems 547
The oxidized form of the protein contains two iron(llJ) ions, whereas the reduced
form contains one iron(IlI) and one iron(I1), Jn the oxidized form, the two iron(I1I)
ions are antiferromagnetically coupled with J = 400 cm - t, giving an S' = O
ground state. The energy levels, calculated according to equation (11-40) are
shown in Fig. 12-35. Since J kT, only part of the Jevels are occupied and the
magnetic susceptibility of the system is reduced with respect to that expected for
an uncoupled system. The electronic relaxation times of iron(I1I) are long and
the lH nmr signals of the ,IJ- CH
2
(se e the foregoing scheme) are expected to be
very broad. Although still very broad, they are observed in the dimer because
of the reduced magnetic susceptibility. Al! eight protons fall insi de a broad
envelope (Fig. 12-36).
6000
4000
,
E

w
2000
O
Fe(lll)- Fe(lll) Fe(11) - Fe(lIl)
SI = 5/2 S2= 5/2 S,= 2 S2 =5/2
------- So = 5
5J
FIGURE 12- 35 Energy
levels lor Fe
2
S
2
dimetal l ic
S' =4 centers calculaled lor
L
J = 400 cm-
1
i n the oxidized
lorm and J = 200 cm-
I
in Ihe
4J
reduced lorm(l 26)
SO=9/2
So = 3
-*
9/2J
3J
S' = 7/2
--+--- S'=2
7/2J

__+I_2J__ S' = 1
5/2J
S' =3/2
3/2J
_ ---L..tJ__ = O
So
S' =1/2
/
HC-CH
2
-S",,- S /S-CH
2
- CH
/ Fe/ 'Fe ""-
/ "'- / ""-
" / CH 2-S S S-CH
FIGURE 12-36 IH nmr
"
HC
/
speclra 01 ox idized and
reduced lorms 01 Fe
2
S
2
/ L
lerredoxin Irom
Oxidized
sp i nach(I26.127)The signals
. ..,...,..-"
marked with aslerisks belong
,hl
lo impurities.
x4
L
I I G I
140 120 100 80 60 40 20 O -20
o(ppm)
l
,
l
.
:
548 Chapler 12 Nuclear Magnetic Resonance 01 Paramagnetic Substances i n Solution
In the reduced case, iron(I1) has short electronic relaxation times and the
whole system becomes more suitable for nmr investigation. The spectrum is
shown in Fig. 12_36( 127) The J value is now 200 cm - 1 and the energy levels are
reported in Fig. 12-35. The ground state is given by S' = 1/
2
(i .e., by S' = SI - S2
where SI refers to iron( IfI ) and S2to iron(I1)). Ifol.ly this level were populated,
the isotropic shifts of iron(I1I) would be far downfield (beca use ( S IZ> is negative
according to equation (l2- 11) and the spin density for (J delocalization is positive
[see equations (1 2- 15) and (12- 20)]. The isotropic shifts of iron(IJ) would be
upfield because of a negative S2leading to a positive (S2z >' The four signals far
downfield are assigned to the two p-CH
2
protons of ligands bound to iron(ITI).
Figure 12- 37. Signals F, G, H, and 1 are assigned to the P-CH
2
of ligands bound
to iron(I1). They are slightly downfield because of population of excited S' levels.
The assignment is based on the temperature dependence of the shifts. The signals
assigned to iron(I1I) are expected to follow a Curie dependence (i.e., their shifts
decrease with increasing temperature because the contribution of iron(II I) to the
magnetic susceptibility of the system decreases with increasing temperature as
seen qualitatively with the Curie Jaw [see equation (12-12)]. In the case of
iron(II), the temperature increase causes an increase in the population of the
states with positive Sz' since the highest S' level is given by SI +S2' Accordingly,
the downfield isotropic shift increases with increasing temperature. In Fig. 12-37,
the experimental temperature dependence of the isotropic shifts is shown together
with expectations from considering the energy levels of Fig. 12-35
P
26,12 7 ) These
results show that upon reduction of the oxidized protein only one localized iron
of the pair is reduced and a mixed valent system does not resultY 26) NOE studies
have suggested that the reducible iron is the one c10ser to the surface of the
protein.(128)
Pe
Pal
coe
sys
Co
Shll
Ran
larg
theSi
and
prot
cone
(CH
com
A fin
Note
(E)
(O)
(C)
(A)
Ra
S.R. As i
with an
che late
CHC(O
larger sH
dealing
caused a
140
130
120
110
E100
o.
o.
iO
40
30
20
10
~
~
SQ---
E
F
Gti:::::--------
I J
3.3 3.5 3.7
~
s---
:...----
O
E
~
J
K
3.3 3.5 3.7
1/T(K-'X10
3
)
(A) (B)
Fe(I1J)
200
E
o.
o.
O
iO
-200
O 2 4 6 8 10
1/T(K-'X10
3
)
(C)
FIGURE 12-37 Temperature dependence 01 the isotropicshilts 01 the 'H nmr
signals in reduced spinach (A) and P. umbilica/is (B) lerredoxin.The predicted
behavior is shown in (C).I'26)
i
Perspectives in Cluster Invesligations
Paramagnetic polymetallic systems 2re becoming more readily ava'ilable from
coordination chemistry and metalloproteins. Extension of the theory of dimetaJlic
systems(126) allows the iwestigation of more complex systems (e,g., Fe
4
S
4
, Fe
3
S
4
,
e
C0
4
S
4
clusters). The reader is referred to specialized literature.(126.129- J3 3)
e
e
r
Shift Reagents
l.
Rare earth tris-chelates of f3-diketonate derivatives are Lewis acids and cause
large pseudocontact shifts in Lewis bases that are added to solutions containing
;.
these complexes. The resulting resonances for several of these ions (e.g., europium
s
and praseodymium complexes) are relatively sharp. In Fig. 12-38, the lOO-MHz
ts
proton magnetic resonance spectra ofCDCI
3
solutions of cis-4-butylcyclohexanol
le
containing varying amounts of Eu(dpmh [dpm is dipivaloylmethanato,
\ S
(CH
3
hCC(O)CHC(O)C(CH
3
)3J are shown(l34) to illustrate this behavior. The
of
complex pattern obtained for the pure alcohol is shown in the bottom spectrum.

A first-order spectrum with all resonances well separated is obtained in curve D.
y,
Note that the spin-spin couplings are still intacto
7,
el"
se
) 0 ICH,),C
H,oq H,. H,u H,ot
es
OH H, I I I I tt.
FIGURE 12-38 100-MHz pmr
b.e
,1 Jl) 1M
'
spectra 01 cis-4-tert-
(E)

butylcyclohexanol
. 53.83 19.78 H,ox Ql:CH'),C.
OH H, H,oq H,.. 1H,ot tt. (20 mg, 1.28 x 10-
4
mol) in
I I COCI
3
(0.4 mi) containing
(D)

various amounts 01

h,oq H - tt. ICH,),c Eu(dpmh: (A) 0.0 mg ; (B)
OH I
10.3 mg; (C) 16.0 mg; (O)
33.1 mg; (E) 60.2 mg.
(C)
[Reprinted with permission
H,oq
Irom P. V. Demarco et al., J.
H, "- H... tt.
OH I 1 I I
Am. Chem. Soc., 92. 5734
(1970) . Copyright by the .J. IU
- -----' +10
",' 11""'"
(A)
/11...-------
_ JJlL +10 __--.J,---_
//"'''"' 1""" "."",.",1"""",,-,,, .. .. . . 1.,,,, ,,,, 1., . .. ,1.1, 1.,,,,,,,."""".!."!!!,,",,,W!!'"'''''' 1e""""I'II",,,,1
U M U U U U H W
Rare earth complexes that exhibit this behavior are called( 13 5) shift reagents,
S.R. As is usually the case with these systems, the S.R. complex is in fast exchange
with an excess of the Lewis base. The Janthanide complexes of the fiuorinated
chelate 1,1,1 ,2,2,3,3-heptafiuoro- 7, 7-dimethyl-4,6-octanedione, (CH 3)3CC(O )-
CHC(O)CF2CF 2CF3' abbreviated as fod, are stronger Lewis acids and produce
Jarger shifts.( 136) Since these early reports there have been hundreds of papers
dealing with applications of shift reagents.(137) High field spectrometers have
caused a decrease in inlerest in shift reagents. Here, we shall deal with examples
(B)
H
OH
550 Chapler 12
FIGURE 12-39 Delinilion 01
lhe variables in a shift
reagent determination 01
molecular structure.
Nuclear Magnetic Resonance 01 Paramagnetic Substances in Solution
of sorne different types of applications and discuss sorne of the potentiaJ
complications encountered.
One use of a shift reagent iovolves simplifying second-order (i.e., J;:::: ~
spectra. Different protons in the molecule are shifted by different amounts upon
complexation. Thus, as the shift reageot concentration is increased, ~ becomes
greater than 1. This behavior is seen io Fig. 12-38.
A second potentially exciting application of shift reagents involves their use
in determining geometries of molecules in solutionD 38) This experiment is usually
done in the fast exchaoge region. The proton nmr spectral shifts induced by shift
reagents are assumed to be almost exclusively dipolar in origino Otherwise,
[actorization is needed. Ideally, a structure would be assumed for the molecule
and equation (12-23) would be used to calculate the expected dipol a r shifts at a
large number ofvarious nuclei in the molecule whose structure is to be determined.
The assumed structure of the molecule would be varied to produce a best fit of
the experimental shifts. Since the structure of the molecule being investigated and
that of the complex in solution are not known, nor are the magnitude and position
ofthe magnetic dipole ofthe metal center in the complex, there are eight unknowns
in the system. These unknowns are bes t seen by looking at Fig. 12-39, where the
example ofa rigid Iigand such as pyridine complexed to a S. R. is illustrated. Four
parameters are needed to fix the orientation of the molecule being studied relative
to the shift reagent: (1) the metal-donor atom distance, r; (2) the ligand
atom-donor atom-metal bond angle, a; (3) {J, the angle between the Iigand's
molecular plane and the magnetic xy-plane of the metal ; and (4) ,,/, the angle
z
/fJ;.
x
In
pa
th
afi
be
of
it i,
ma
ind
slm
pre
sym
the
v .
J'
and
the :J
wor
often
2
the a
affinit
with I
3
the a\
a rela
4
dipola
studiel
5.
known
6.
is only
'5
avail;:hle
measuring the twist of the Iigand 's molecular plane around the nitrogen-
para-carbon axis. In addition, two angles are needed to define the orientation of
the magnetic axis with respect to the metal-donor bond. Two additional unknowns
are needed to account for the anisotropy in x. To complete our discussion of a
rigorous solution of this problem, we should consider the possibility of having
significant amounts of both 2: 1 and 1: 1 complexes in solution. (Most shift
reagents are potentially diacidic, having two acid si tes.) Tf neither the 2: 1 nor
the 1: 1 complex is the predominant species in solution, both K 1 and K 2 must
be known as well as two sets of the unknowns mentioned before, one set for each
of the two complexes. However, it is obvious from the preceding discussion that
it is not simple to determine geometries of molecules in solution in a rigorous
manner. Thus, to gain any information about geometries in solution, more
independent information is needed, such as the relaxation rates, and sorne
simplifying assumptions must be made.
Tf threefold or higher axial symmetry and the presence of only one
predominant species are assumed, the problem becomes tractable. With axial
symmetry, equation (12-25) can be used instead of equation (12-25). By taking
the ratio of all the observed nmr shifts with respect to the largest observed shift,
~ V j equation (12-53) can be derived from equation (12-25):
(12-53)
and the magnitude of the magnetic anisotropy in the complex is eliminated from
the problem. (This is possible only if one ignores the chelate ligand protons and
works only with the coordinated Lewis base.)
The complications to obtain structures in solution include:
1. The stoichiometry of the adduct in solution must be determined but is
often assumed.
2. The treatment assumes that there is only a single geometrical isomer of
the adduct in solution. Many are possible. Furthermore, lanthanides have a high
affinity for water, which if present in the system can compete for Lewis acid sites
with the substrate, producing even more complexes in the system.
3. When the substrate is involved in a dynamic, intramolecular process,
the average conformation of the molecule is determined, and this might represent
a relatively unstable one.
4. The complex is gene rally assumed to be axially symmetric, so that the
dipolar shifts can be evaluated with a 1 - 3 cos
2
0)/r3) termo Those systems
studied to date do not possess axial symmetry (however, see reference 139). *
5. The location of the principal magnetic axis in the complex is often not
known relative to the su bstrate ligando
6. When the substrate is a complex one, it is necessary to assume that there
is only one binding site.
* Sorne more accurate studies were possible in proteins where many experimental data are
available, and in this case no assumption of this type is needed(2.139)
(
l
552 Chapter12 Nuclear Magnetic Resonance of Paramagnetic Substances in Solution
In spiteofthesecomplications,themethodis capableofdistinguishinggross
structural featuressuchas thosethatexistin manydifferent isomericcompounds.
For example, the compounds
and
H OH
H OH
are readily di stinguished, (134)as are (141)
H
OH
)-----+-OH )--------+-H
and
H
H
Shift reagents have been used to differentiate between internal and external
phospholipid layers in membranes(142) They have also been employed in
conformationalstudiesofnucJeotides in solution(143)andin othermetalloprotein
systems.(l44) one must always be concerned with the problem that coordination
ofthe shift reagent may affect the conformation ofthe biomolecule.
Another interesting application involves the use of optically active shift
reagent s to determine optical purity. The idea is similar to that discussed in
Chapter 8, in which optically active solvents were employed. Bere, different
stabiJity constants for forming the different diastereoisomeric adducts exist,
leading to different mole fraction averaged shifts for the enantiomeric bases.
Several reports ofdifferent opticallyactiverare earthcomplexes thatcan be used
for this application have appeared(145-147)
I
9
10
11
12.
13.
14,
15.
16.
17.
18.
19.
20.
21. I
22. \
23.
24. R
25. \1
26. E
27. J.
28.
29. W
In
30. J
31. H.
32. E.
33. M.
34. E.
De
35.0.1
36. " NI
R. 1
37. R.\
38. 1. B(
39. R. 1-
40. a.
b. 1.
41. 1. Be
42. G.
43. J. A.
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556 Chapter 12
EXERCISES
Nuclear Magnetic Resonance 01 Paramagnetic Substances in Solution
130. 1. Bertin, F. Brgant , and C. Luchnat , Inorg. Chm. Acta, 175, 9 (1990).
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142. S. B. Andrewsel al., Proc.Na!. Acad. Sci.USA,70,1814 (1973)and references therein.
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144. R. A. Dwek el al, J. Biochem., 21 , 204 (1971).
145. G.M. Whitesides and D.W. Lewis, J. Amer. Chem. Soc., 92, 6979 (1970);93, 5914
(1971).
146. H. L. Goeringel al , J. Am. Chem. Soc., 93, 5913 (1971).
147. R. R. Fraser el al. , Chem. Commun. , 1450 (1971).
1. Foreach ofthefoIlowing,statewhetherthecontactcontribution to the isotropicshift
in the proton nmris cJose lO zero. AIso statewhether the pseudocontact contribut ion
is zero. Explain al! answers .
a. N{@)6
2
+ (octahedral about Ni).
b. The n-butanol adducl ofEu(dpmh, where dpm is
2. The following v(iso) values are reported ror Ni(C
6
H
s
CH
2
NH
2
)62+: NH
2
, -105
CH z, 34.7; phenyl protons: 0 , - 1.3;m, 1.6; p, -1.4(ppm). Interpret these shifts in
terms ofdeJocalization mechanisms.
3. Thestablefree radical iIlustratedgivesa sharpthree-lineesrsignalin benzenesolution
at room temperature with a concentration ofabout 10-
4
M. The nmr signal is too
broad to be detected. On increasing radical concentration, the esr signa] broadens
and is barely discernible at the 1 M leveJ, though now the following nmr signal is
seen a t 60 MHz.
4.
5.
e
6. a
tf
UI
th
di
a.
b.
c. (
Exercies 557
12
Relative
intensity: 2
1\ A ~
TMS
r---
A
---1
1-2000Hz -----1
a. Explain the [ow concentration esr signal and the high concentration nmr signals.
ic
b. Why does the esr signal disappear with increasing concentration while the nmr
signal grows with concentration?
4. Four-coordinate complexes of Ni(Il) may be (1) low spin (S = O) square p[anar, (2)
high spin(S = 1) tetrahedral,(3) an intermediateDld geometry with singlet and triplet
in.
state close in energy, or (4) situations (1) a1d (2) in equilibrium and interchanging
1.
with arateconstant on the order of 10
7
sec-
1
~ 4
a. Describe what result you would expect lo oblain for each ofthe aboyecases if Ihe
magnetism were studied as a function of lemperature (i.e., Curie-Weiss behavior
or nol, and why).
b. Could cases (3) and (4) be distinguished by employing infrared, nmr, or esr
speclroscopy? (Indicate what is expected, and why, for each ofthose lechniques.)
c. Describe what you would expect to see from a study ofthe nmrspectrum and its
temperature dependence for each ofthe aboye four cases.
5. Waterhasone(J MOcapableofn-bondingwith the t
2a
orbitalsin octahedral hexaqua
complexes. Predict Ihe order of 1H hyperfine shifts in the d
l
-d
9
series.
6. Oxygen-17 nmrhas been observed in aqueous solutions ofparamagnetic ions. Water
ulion
.shift
that is coordinated to a paramagnetic ion has an
17
0 resonance that is shifted far
up- ordownfield in relation to uncoordinated water. An aqueous solution containing
the paramagnetic ion Dy3+ has only one
17
0 resonance. Aqueous solulions of the
diamagnetic ion AI
3
+ exhibit two
17
0 resonances. See diagram ofspectra.
a. Briefly explain why one
17
0 resonance is observed in aqueous Dy3+ solutions,
while two are observed in AP+ solutions.
b. A solution containing 0.1 mole of Dy3+ and 10.0 mofes of water has an
17
0
resonance 190 ppm upfield from uncoordinated water. Addition of 0.2 mole of
anhydrous A1
3
+ causes Ihis peak to shift lO 216 ppm. Explain.
c. Calculate Ihe number ofwater molecu[es in the coordination sphere ofA1
3
+
-105
'hirts in
I I
Oppm 200 ppm
558 Chapter 12 Nuclear Magnetic Resonance 01 Paramagnetic Subslances in Solulion
7. CaleuJate the eontaetshift ofa proton in a metal eomplex ofaxial symmetryif(a) the
isotropie shift is 103 ppm, (b) the metal eoordinates are x =O,Y =O, z =O, and the
proton eoordinates are x = 3.51, Y = 2.76, z = 1.12 , (e) the magnetie suseeptibi lity
anisotropy is 2.3 x 10-
8
m
3
mol-
I
, (d) the direetion eosines of the z-axis of the
x-tensor are a =0.128, b =0.692, e =0. 710.
8. Are TI and T
2
ofaprotonat 300 MHzmainJyeontaet,mainlydipolar,orbotheontaet
and dipolar in origin if the eontaet shift is + 173 ppm, the metal- pro ton distanee is
4.20 , T, is 7 x 10- II see and the eleetron relaxation time is
a. 10 -
1 2
see?
b. 10- 8 see?
9. Determine the magnetie field at whieh the ne width,expressed both in Hz and ppm,
is sharpestfora protonat5.2 from a metalwithfive lInpairedeleetronsi n a eomplex
having T, = 3 X 10-
8
see and T
s
= 10-
11
see. Negleet the eontact eontribution.
10. Prediet and expJain the orderofthe electron relaxation times for the following metal
ions: ClI2+, Co2+ (H.S.), Yb
J
+
11. Prediet the relative easeo fobservingCOSYand NOESYeross peaks at 200 and 600
MHz between two signals in the paramagnetieeomplex ofexereise 9. Remember that
during the bui ldllP of the eross eorrelation, the COSY intensities deerease with T
2
and the NOESY intensities deerease with TI'
12. Calculatethedistaneebetween two protonsAand Bin a paramagnetieeomp[ex with
T, = 10-
9
seekoowingthat, by irradiatingAin a steady-stateexperimentat 500 MHz,
a nOe of2.5% on Bis obtained and the TI ofBis 25 msee.
13. Explainwhy I H nmrsignals from themetalligandsin a antiferromagnetieallyeoupled
nickeJ(II)-copper(II) system are sharper than io the analogous zinc(II)-copper(IJ)
system.
14. Are the nmr Iines ofa copper(1I) complex broadest
a. in the presence ofantiferromagneticeOllpling with a high spin cobalt(lI) complex?
b. in the presence offerromagnetic coupling ofequal magnitude?
c. in the absence ofmagneticcoupling?
-
13-
Thl
as t
is b
cha
inro
acce
sysli
111a n
give
orbi
anis(
cm
syste
eJect
oral
be g
muse
This
shou
eJect
l 1m
bye .
regio
For
lO 1
areg
sysleE
epr J
impo
y
le
::1
IS
n,
Electron Paramagnetic
Resonance Spectra 01
Transition Metal
Ion Complexes
13-1 INTRODUCTION
al
This chapter is an extension of Chapter 9; the principIes covered there, as well
as those in Chapters 10 and 11 , should be well understood before this chapter
is begun. It is for this reason that the presentation of the subject matter in this
al
1
2
chapter did not follow Chapter 9 directly.
The epr spectra of transition metal ion complexes contain a wealth of
information about their electronic structures. The additional information and
lh
accompanying complications that are characteristic of transition metal ion
[Z,
systems arise beca use of the approximate degeneracy of the d-orbit als and beca]!';\.;
many of the molecules contai n more than one llnpaired electron. These properties
give rise to orbital contriblltions and zero-field effects. A, a reSlllt of appreciable
ed orbital angular moments, the g-values for many metal complexes are very
JI) ani sotropic. Spin-orbit coupling also gives rise to large zero-field splittings (of 10
cm -! or more) by mixing ground and excited states.
An important theorem that summarizes the properties of multi electron
systems is K ramers' rule .' !) This rule states that if an ion has an odd number of
electrons, the degeneracy of every level must remain at least twofold in the absence
of a magnetic field. With an odd number of electrons, mJ quantum numbers will
be given by 1/
2
to 1. Therefore, any ion with an odd number of electrons
must always have as its lowest level at least a doublet, called a Kramers' doublet.
This degeneracy can then be removed by a magnetic field, and an epr spectfllm
should be observed. O n the other hand, for a system with an even number of
electrons, mJ = O, 1, ... J. The deg neracy may be completely removed by
a low symmetry crystal field, so only singlet levels remai n that could be separated
by energies so large rilat an epr t ransition would not be observed in the microwave
region. This di scussi on is ilI ustrated by the energy level splittings in F ig. 13-l.
'' or the even electro n system, the ground state is non-degenerate and the J = O
to 1 tramition energy is qui te frequently outside the microwave region.
A kw additional comments relative to sorne experimental procedures (others
are given in Chapler 9) are in order in t he way of introduction to transition metal
systems. A number of fa:ctors other than those (hat are instrumental, affect the
epI line width. As in mmr, spin-Iattice, spin-spin, and exchange interactions are
important.
Broadeni1itg due to spin-lattice relaxation results from Ihe interaction of the 559
I
'
i
560 Chapter 13 Electron Paramagnetic Resonance Spectra of Transi ti on Metal Ion Complexes
!!2L
4T
2
J
5 / 2

(6) 5 / 2 1 / 2

-3/2
-5/ 2
3p
mJ
-q-
3T
-2
r;

-1
(9)
1
a
s
-1
s
e
- -O
d
Gaseous
Oh Spln-orbil Magnetic Gaseous Spin-Orb/t Magnetc
11
Ion Crystal Couplng
Eield Ion Crystal Coupllng Fleld
Fleld (Zero-field) H Fleld (Zero-fleld)
H
(A)
(B)
FIGURE 13-1 The splitting of the gaseous ion degeneracy of (A) C0
2
+ and (B) V
3
+
by the crystal field, spin-orbit coupling, and a magnetic field. The T slate is
regarded as having an effective L, called L' , equal lo 1; for an A state, L' = o. Then
J = L' + S, ... , L' - S. Only the zero-field and magnetic field splittings of Ihe
ground state are shown.
paramagnetic ions with the therma! vibrations of the lattice. The variation in
spin-Iattice relaxation times in different systems is quite large. For sorne
compounds the lifetime is sufficiently long to allow the observation of spectra at
room temperature, while in others this is not possible. Since these relaxation
times generally increase as the temperature decreases, many of the transition
metal compounds need to be cooled to liquid N 2 or liquid He temperatures
before welI-resolved spectra are observed.
Spin-spin in teraction results from the magnetic fields that originate in
neigh boring paramagnetic ions. As a result of these fields, the tot al field at each aXt
ion is sJightly altered and the energy leveIs are shifted. A distribution of energies axi
results, which produces a broad signaL This effect varies as (1/ ) 3) . (1 - 3 cos
2
8),
where ris the distance between ions and 8 is the angle between the field and the
symmetry axis. Since this effect is reduced by increasing the distance between
paramagnetic ions, it is often convenient to examine transition metal ion systems whl
by diluting them in an isomorphous diamagnetic host. For example, a copper fiell
compJex could be st udi d as a powder or single crystal by diluting it in a host abs
lattice of an analagous zinc complex or by examining it in a frozen solution. ass(
Dilution of the solid isolates the electron spin of a given compJex from that of mo
another paramagnetic molecule, and the spin Jifetime is lengthened. (RecalI our pro
:
n
in
\O
eh
.ies
diseussion of the speetra in F ig. 9-25.) Ifa frozen solution is used, it must form
a good glass; otherwise, paramagnetie aggregates form, whieh lead to a speetrum
with broadened lines. ltis often necessary to remove O
2
from the solvent beca use
this can lead to a broadening of the resonance. Even in a weJl-formed glass, one
cannot usually detect hyperfine splittings small er than 3 or 4 gauss.
Li ne widths are alt ered considerably by chemical exchange processes. This
effect can also be reduced by dilution. Irthe exchange occurs between equivalent
paramagnetic species, the lines broaden at the base and become nar rower at the
center. When exchange involves di ssimila r ions, the resonances of the separate
Iines merge to produce a single line, which may be broad or narrow depending
upon the exchange rateo Such an effect is observed for CuS0
4
' 5H
2
0 , which has
two distinct copper sites per unit cell
f2
)
In single crystals the anisotropy in the esr parameters can be obtained.
Informat ion about the ani sotropy in the system can also often obtained in powders
and glasses, because the resulting spectra are not those of a motionally averaged
system. We wi1l next consider why anisotropic information is obtained from the
spectra even though the molecules in a glass or powder sampl e exi st in an
extremely large number of possible orientations relative to the applied field.
Consider a molecule with a threefold or higher symmetry axis, which can be
described by a gil and a 91. ' As can be seen from Fig. 13-2, there are many axes
FIGURE 13-2 The gll- and
'----- gil some g1.-axes in a crystal
with a threefold or higher
axis.
that could be labeled 91. . In a bulk sample containing many orientations for the
assemblage of crystallites, there are more possible orientations that have the 91.
axes aligned with the applied field than there are orientations that have the 9il
axis aligned. The g-value for any orientation is given by:
(13-1)
where eis the angle that the principal axis (i.e., the 9 11 axi s) makes with the applied
field. Since a1l orientations of the crysta1lites in a solid are equally probable,
absorption will occur at al! fields between that associated with 9 11 and that
associated with g1. . Since many more crystallites have g1. aligned than 9 '1, the
most intense absorptM wi'l'r cor respond to 9.1 . Wlien one cons1ers lhe
p rooabl ities of the various orlen al ions and the transition probability corre-
562 Chapler 13 Electron Paramagnetic Resonance Spectra 01 Transition Metal Ion Compl exes
FIGURE 13-3 ideal ized
absorption (A) and derivative
(B) spectra for an unoriented
system with S = ' /2' axial
symmetry. and no hyperfine
interaction (gl > gil )'
Hinc. _ Hinc._
(A) (S)
o
s.
el
~
~
co
FIGURE 13-4 Powder epr
spectra of S = '/2 systems.
(A) An orthorhombic system
with 1= O; (8) isotropic 9
with 1= '/2' gl > gil ' and
AII > Al' In the lalter cases .
accurate g- and A-values are
available on ly from computer
simu lation .
(A)
g
I 1'1
:\J\(
A. I I I
Av
I I
A
I
\
I
'N
I
\
I I
Az .\
I
(B)
FIG
gl
(B)
I
froz
I AII reori
Al
gu
one
(e)
and U
Amer
orient the liquid crystal molecules (and, in turn, the solute molecu1es) and is the.1
cooled. This is schematically illustrated in F ig. 13-5(B). The epr spectrum(4a) in
(Cl
(A)
(O)
Liquid crystal
Co(meacacenl
(El
(B)
H- H
sponding to each of these, the absorption spectrum shown in Fig. 13-3(A) is
predicted. This is con verted to the derivative spectrum in Fig. 13-3(B). This is
an idealized example, and often one finds that the overlapping features generated
by gl. and g.1 make it difficult to obtain their values.
When the system is orthorhombic and g, > yy > gz, the powder spectrum
obtained for [ = Ois like that in hg. 13-4(A). When 1 = 1/
2
and the system has
nearly isotropic g-values, but Az > A y> Ax, the spectrum in Fig. 13-4(B) is
expected. The spectrum for a complex with axial ymmetry and 1 = 1/
2
, in which
g.1 > gil and An > Al., is illustrated in Fig. 13-4(C). Ot her systems become quite
complex, and the possibility for misassignments becomes very large. O nly in the
relatively simple cases can the g- and A-values be determined with confidence.
Computer programs are available to simulate powder epr spectra for simple
systems.
Liquid crystal nematic phases can also be used(3) to orient a molecule for
epr work. The molecule to be studied. which is the solute, cannot be spherical;
as an example, consider the molecule Co( Meacacen) in Fig. 13-5(A). The liquid
crysta1 solution of this 10w spin Co(Il) comp1ex is placed in a magnetic field to
_
FIGURE 13-5 The epr spectra (4) of Co(Meacacen) at 77 K. (A) Structural formula ;
(B) orientation of the molecule in a frozen oriented liquid crystal; (C) unoriented
frozen solution; (D) frozen liquid crystal oriented as in (B) ; (E) frozen liquid crystal
reoriented 90 from (B). The phasing in this spectrum is inverted relative to what
one normally employs. [Repr inted with permission from B. M. Hoffman, F. Basolo,
and D. L. Diemente, J. Amer. Chem. Soco95, 6497 (1973). Copyright by the
American chemical Society.]
564 Chapler 13 Electron Paramagnetic Resonance Spectra 01 Transition Metal Ion Complexes
2 ~ T 2 ~ ~ ____ 2Eg
28
2g
Gaseous
ion
FIGURE 13-6 Splitting of
the 20 state by Oh and D
4h
fields (z-axis compression
in0
4
h)
(O) is for the sample oriented relative to the magnetic field as shown in (B), while
in spectrum (E) the sample is rotated 90 around the z-axis (i.e., y parallel to the
field) relative to the magnetic field. Upon rotation, the portion of the spectrum
corresponding to g2 is enhanced, but that for gl is no!. O ne could easily make
the mistake of assuming that this is an axial system with gJ assigned to the z-axis
(i. e., gil , the axis perpendicular to the plane) and g2 and g3 assigned to gJ., where
gx and gy are similar. However, with the molecular coordinate system as defined
in Fig. 13-5(A), gz must be assigned to g3' gx to 9 l' and gy to 92 These assignments
have subsequently been confirmed by a single crystal epr study.(4bl Oifficulties
can arise in this application if care is not taken to demonstrate that the liquid
crystal is not coordinating the complex being studied.
13-2 INTERPRETATION OF THE g-VALUES
Inlroduction
In contrast to organic free radicals, the g-values of transition metal ions can differ
appreciably from the free electron value of 2.0023. Such deviations provide
considerable information about the electronic structure of the complex. Oifferent
g-values arise because spin-orbit coupling is much greater in many transition
metal ion complexes than in organic free radicals (vide infra). Thus, spin-orbit
effects beco me essential to an understanding of esr.
The value of 9 for an unpaired electro n in a gaseous atom or ion, for which
Russell-Saunders coupling is applicable, was given earlier by the expression
J(J + 1) + S(S + 1) - L(L + 1)
(13-2)
9 = 1 + 2J(J + 1)
In condensed phases, first row transition metal ion systems not only do not have
g-values in accord with this expression, but they often deviate from (he spin-only
value. In condensed phases, the orbital motion ofthe electron is strongly perturbed
and the orbital degeneracy, if it existed before application of the chemical
environment, is partly removed or "quenched." lf the electro n has orbital angular
momentum, the angular momentum tends to be bolstered by being weakly coupled
to the spin. There is therefore a competition between the quenching effect of the
ligands-the "crystal field "- and the sustai ning effect of the spin-orbit coupling.
Were it not for spin-orbit coupling, we should always observe an isotropic g-value
of 2.0023.
These effects can be illustrated by considering the infiuence of a crystalline
d
1
field on a ion as shown for O h and D
4h
(z-axis compression) in Fig. 13- 6.
Equation (13- 2) would dcscribe the 2D gaseous ion. The octahedral crystal field
splits 2D into 2 T
29
and 2 E9 states. The degenerate T
2g
state may be further split
by distortion (e.g., Jahn-Teller effects) or by a tetragonal ligand field into E and
B
2
levels. Spin-orbit coupling, on the other hand, tends to preserve a small amount
of orbital angular momentum, so, in the tetragonal complex, the orbital angular
momentum is not completely quenched. One gene rally refers to this as mixing
in of a nearby excited state by spin-orbit coupling. When the amount of spin-orbit
coupling is small compared to t he tetragonal distortion (i.e. , in the case of large
distortions), the mixing can be treated by perturbation theory. In an octahedral
e
t
e
S
T
is
o
di
Fe
tet
fin
IOC
TIH
Ue.
w/ j
of t
thal
We
mixl
eq u
fune
(13-
to ,e
\Vit /
i.L 3
Zeerr
open
effect
way,
wher
states.
In an
by re
n
it
h
2)
13--2 Interpretation 01 the g-Values 565
complex, spin-orbit coupling is present in the ground 2T
29
state; in order to
obtain the accuracy needed to understand the epr spectrum, this situation cannot
be adequately treated with perturbation theory. Recall that such a treatment was
employed in Chapter 11 on magnetismo
s = Sysfems wifh Orbita/Jy Non-degenerate Ground Stafes
The fun Hamiltonian for our system with spin-orbit coupling in a magnetlc field
is given by
H = H(Z eman) + H(SO) = f3H' (L + geS) + ,L S (13- 3)
One of the effects of spin-orbit coupling is to modify the simple one-electron
d orbital wave functions. This is described by the J.J' Sterm in the Hamiltonian.
For example, the spin wave function for the ground state 2B 29 of a dI ion in a
tetragonal complex is modified by the spin-orbit interaction ),L S. From
first-order perturbation theory, the wave function for the Kramers' doublet 1 )
including spin-orbit effects is gven by:
(13-4)
The term 10) is the 2 B 29 ground state before spin-orbit effects are considered
(i.e. , for dI with a tetragonal compression, this one electron is in the d
xy
orbital),
while the summation indicates the contribution made by spin-orbit admixture
of the excited states. In this example, the t:..E term in the denominator indicates
that the 2 E state will make the largest contribution of all the states that mix in.
We can see from this expression that when there is no orbital angular momentum
mixed into the ground state, 1 ) = 10). Evaluation of the matrix elements in
equation (13-4) gives the coefficients necessary to write the appropriate wave
functions. These functions are then used with the Zeeman Hamiltonian in equation
(13-3), i.e.,
to set up the 2 x 2 matrix involving 1+ ) and 1- ). Note that we have worked
with the fulJ Hamiltonian in equation (13-3), using the two parts separately. The
),L S term modified the wave function on which we are now operating with the
Zeeman Hamiltonian. The problem is solved by using the raising and loweri ng
operators. Energies are obtained which are expressed as gf3Hm ' where g is the
s
effective g-factor in the direction of the field component H (i = x, y, z). In this
way, using L
z
' Sz, and the Zeeman Hamiltonian, we obtain
= 2.0023 + 2,1, L
(13- 5)
gz "E(O) - E(n)
where 10) is the ground state wave function and 1n) is that of one of the n excited
states. Since the ground and excited states corresponding to electronic transitions
in an S = 1/
2
complex with small spin-orbit coupling are adequately described
by real orbital occupations, the state and orbital designa tions can be used
;
566 Chapter 13 Electron Paramagnet ic Resonance Spectra 01 Transiti on Metal Ion Complexes
in terchangeably. The g-value is thus seen to be ery dependent upon the mi xing
in of the excited state by spin- orbit coupling.
The maCrix elements <O I Lz I n) are non-zero only when che m( value of 10)
equals che mI value of In) . In a real orbit al basis set with
dxl_ y' = (fi}l+ 2) -1- 2)
and
dx y = - ~ } I + 2) +1- 2)
we will have non-zero matrix elements for <d
x
_ .r21 Lz 1d
xy
)' (Thi s can be seen 2
from the tri ple product r
X
'-y2 x r
L
, x r <y.) For a di complex, where we can use
one-electron oribital nstead of states, an evaluation of aIl the matrix elements
leads t o
8(
gz = 2.0023 + -::-:---:-:-:- (13-6)
E(O) - E(n)
where }, = +/2S fora shell that is less than half-filIed. The symbol repre nts
t he one-electron spin-orbit coupling. When tbe shell is more than half-fi lI ed, we
generally think in terms of formaton of the posi t ive hol es that accompany the
elect roni c transi t ions. The sign of the second t rm, 8/ [E(0) - E(n)l, is changed
by changing the denominator to E(n) - E(O). When the shell is less than half-filled,
spin-orbi l effects reduce 9 from 2.0023 ; bul when the shelI is more tha n ha lf-filled,
spin-orbit effects increase 9 aboye Yo' E(O) and E(n) are the energies of the ground
and excited st ates, respect ively.
In a tetragonal complex we have
gx = 2.0023 + --"-------- (13- 7)
E(O) - E(n)
where gx = gy . These matrix elements a re evaluated by using the raising a nd
lowering operat ors, so matrix element s are non-zero only when the ground and
excited sta te mI values di ffe r by 1. For a di tetragona l complex (Fig. 13- 6) we
have:
2
gx = 2.0023 + --- (13- 8)
Exy - E
xz
The result s of the evaluat ion of matrix el ement by this procedure can be
summarized by writ ing the following general expression for the g-values of S = 1/
2
systems:
= 2 n
(13-9)
Y .0023 + E(O) _ E(nJ
The values of n are obtained from the so-called magic pentagon shown in Fig.
13- 7, which summa rizes the results ofthe evaluation of matrix elements <O 1 L 1 n) .
\
u
(i
o
b
c
v
Si
\V
an
Th
lhe
ane
rep
111;
em]
is v
elen
ti or
pre
cap
COl11
the
111; =
e
e
d
d
7)
tncl
nd
\Ve
!- 8)
I be
L11
r / 2
3-9)
Fig.
11/ )
13-2 Interpretation 01 the g-Values 567
o
1
FIGURE 13-7 The " magic pentagan "
lar evaluating n al equatian (13-9).
2
We will repeat the prob1em discussed earlier (the di tetragonal field) with the
use of this pentagon. We first determine that, for an electron in an xy orbital
(i.e. , an xy ground state), only electron circulation into the X2 - y2 orbital could
give orbital angul ar momentum along the z-axis. The quantity gz then has
contributions only from xy and X2 - y2, which is seen in Fig. 13-7 to have lhe
vaJue n = 8. Equation (13-9) then becomes :

gz = 2.0023 + _ E 2 ,
(13- 10)
E xy x-y
Since gx has non-zero matrix elements only when 10) and In) differ by AmI = 1,
we obtain

gx = 2.0023 +----=-- (13-11)
E xy - E
xz
and
2e
gy = 2.0023 + - (13-12)
E'J' - Eyz
These formulas in effect tell us what orbitals permit electron circulations about
the respective axes; that is, X2 - y2 and xy about z, xy and xz about x, or xy
and yz a bout y. The "magic pentagon" is easily constructed. The three rows
represent orbitals possessing diffe rnt m( values ; the top row corresponds to
mI = O, the second row to mI = 1, and the third row to mI = 2. It should be
emphasized that this whoJe treatment arises from a perturbation assumption and
is valid only when - E( n)] is small compared to the diagonal Zeeman
elements. When second-order perturbation theory is pertinent, a term propor-
tional to is added.
Before concluding this section, an application of the use of g-values will be
presented. In Fig. 13-8, the crystal field splittings are indicated for tetragonal
copper(I1) complexes with a metal-ligand distance on the fourfold (z)-axis that is
compressed [part (A)] and elongated Epart (B)] along this direction. In (A),
the unpaired e1ectron is in d 2 with mI = O. There is no other orbital with an
z
mI = Ocomponent, so gz = 2.0023. The value of gx = gy is given by

gx = 2.0023 + --=--- (13- 13)
Eyz - E=,
)
;
568 Chapter 13 Electron Paramagnetic Resonance Spectra of Transition Metal Ion Complexes
Z2
x2 _ y2
-+- -+-
x2 _y2 Z2
FIGURE 13-8 The d-Ievel splittings -H- -H-
lor a tetragonally compressed
-4-t- 44r- xz,yz -4+-
xy
complex (A) and a tetragonally
elongated complex (B).
-+lo-
xy
4{.-
-4+- xz,yz
(A) (B)
Note that we haveswitched theorderoftheenergies in the denominatorbecause
the shell is more than half-filled. On the otherhand, for a tetragonal elongation
[ Fig. 13-8(8)] , with the unpaired electron in d
x
' _ )'" we obtain
8
(13-14)
9z = 2.0023 + -------
Ex"" - E x2 _ y2
The value of9x = gy is given by
2'
9x = 2.0023 +---- (13-15)
Eyz - E.<, y'
Thus,the9-valuescan be used todistinguish the two structures. Complexeswith
a tetragonal compression are very rare, but elongated ones are common.
Copper( IT) porphyrin(5l complexes have been reported with g-values of9z = 2.70
and gx =2.04.
Theg-values in some six-coordinatecopper(lI)compJexesexhibitinteresting
behavior. As mentioned in Chapter 9, when the single crystal epr spectrum for
[Cu(H
2
0)I;]SiF6' diluted with the corresponding diamagnetic zinc salt, was
obt ained at 90 K, the spectrum was found to cODsist of one band with partly
resolved hyperfine structureand a nearly isotropicg-value.(6lJahn-Tellerdistor-
tion is expected, but there are three distortions with the same energy that will
resolve theorbitaldegeneracy.Thesearethreemutual1y perpendiculartetragonal
distortions (elongation or compression along the three axes connecting trans
ligands). As a result, three distinguishable epr spectraare expected, one for each
species. Since only one transition was found, it was proposed that the crystal
field resonates among the three distortions (a so-called dynamic Jahn-Teller
distortion). When the temperature is lowered, the becomes anisotropic
and consists of thl';e sets of lines corresponding to three different copper ion
environmentsdistorted by three different tetragonaldistortions.(8)Thefollowing
parameters were reported for CuSiF6'6H
2
0 :(9)
90 K 20 K
911 =2.221 0.005 9z = 2.46 0.01
91. = 2.230 0.005 9x = 2.10 0.01
A = 0.0021 0.0005 cm- 1 9 = 2.10 0.01
v
1
B = 0.0028 0.0005 cm- 1 A
z
= 0.0110 0.0003 cm-
A } _
x < 0.0030 cm 1
Av
e
G
d

u.
(l.
lel
e
th
ar
H
th
n
1m
ca
of
Bl
to
SYi
Wh
the
dI,
The

n.
o
13-2 Interpretati on of the g-Values 569
Other mixed copper salts have been found to undergo similar transitions: (Cu,
MghLa2(N03)1224D20 between 33 and 45 K, and (Zn, Cu)(Br0
3
)2 6H
2
0,
incomplete below 7 K.
A similar behavior (i.e., a resonating crystal field at elevated temperatures)
was detected in,lIO) the spectra of sorne tris cmplexes of copper(lI) with
2,2' -dipyridine and 1,l0-phenanthroline(l1) as well as with trisoctamethyl-phos-
phoramide.(l2) This latter ligand, [(CH3)2NJ2P(O)OP(O)[N(CH3)2J 2' is a biden-
tate chelate in which the phosphoryl oxygens coordinate. The complex can be
studied without having to dilute it in a diamagnetic hos!. A complete single
crystal epr study and an x-ray diffraction study are reported on this system
P
2)
At 90 K, the spectra indicated that at least three different magnetic sites exist,
each of which is described by a g-tensor. Analysis of the spectra indicates that
these sites correspond to distortions along the X -, y-, and z-axes, respectively, in
effect locking in the various extremes in the dynamic Jahn-Teller vibrations
occurring at room temperature. The interesting problem of determining the
chirality of the molecule in a single crystal epr spectral analysis has also been
discussed(' 2)
In single crystal epr studies on transition metal ion systems, it is com-
mon(13-1S) to find complexes in which the g- and A-tensors are not diagonal in
the obvious crystal field coordinate system. An axis that is perpendicular to a
refiection plane or hes on a rotation axis must be one of the three principal axes
of the molecule. The g-tensor of the molecule and the A-tensor for any atom
Iying on the axis must have principal values along this coordinate. If a molecule
contains only a single axis that meets the aboye requirements, the other two axes
used as the basis for the crystal field analysis will not necessarily be the principal
axes of the corresponding tensors of 9 and A; i.e., selecting these axes may not
lead to a diagonal tensor. For example, bis(diselenocarbamate) copper( lI ) has
symmetry.(13,14) The twofold rotation axis is one of the axes tht diagonalize C
2h
the corresponding g- and A-tensor components, but the other two components
are not diagonal in an axis system corresponding to the axes of the crystal field.
Had the molecule possessed D
2h
symmetry, the three twofold rotation axes of
this point group would have been the principal axes for both the A- and g-tensors.
Thus, epr studies can provide us with information about the symmetry of the
molecule. For a molecule with no symmetry, none of the molecular axes need be
coincident with the axes tbat diagonalize the g-tensor or A-tensor.* As a matter
of fact, the axis system tbat diagonalizes A may not diagonalize g. In vitamin
B 12' for example,(l S) the angle between the principal xy-axis system that leads
to a diagonal A-tensor and those that lead to a diagonal g-tensor is 50
0
Syslems in which Spin-Orbit Coupling /s Large
When spin-orbit coupling is large, perturbation theory cannot be used to give
the appropriate wave functions; i.e., equation (13-4) does not apply. An octahedral
dI complex with a 2T
2g
ground state is a case in which spin-orbit coupling is
For Jow symmetry moJeeuJes, the g- and A-tensors may in faet be asymmetric (Le., axy # ay, ).
The g2-tensor will always be symmetrie.
l
570 Chapter 13 Electron Paramagnetic Resonance Spectra 01 Transition Metal Ion Complexes
large. When the spin-orbit operator (L Sopera tes on the sixfold degenerate real
orbital basis set
tft =
tf4 = 1
1
,
tfz = (1/fi)( ll, -1-

2
,
Vis =
tf6 = 1-
1
,
(the wavefunetions are expressed as IM
L
, M
s
), the result is a new set of orbitals,
appropriate for d
t
systems with a arge amount of spin-orbit eoupling. T hese are
obtained by evaluating the 6 x 6 determinant eontaining matrix elements
<tfi I S I tf) to obtain the energies. The energies are subst tuted baek into the
seeularlike equations to obtain the eigenfunetions (Pi Iisted below.
qJ=(I / fi)( 2tft+tf6)
qJz = (1/)3)( - fi tfz + tf3)
qJ3 = tf4
qJ4=tfS
qJs = (l /)3)(tfz + J2tf3)
qJ6 = (1 /)3)(tf t - fitf6)
The eorresponding energies are EJ = - 02, Ez = E3 = - /2, E4 = - a 2,
Es and E6 We see from this analysis that pi n-orbit eoupling has
removed the sixfold orbital degeneraey 01' the T tal e, giving a twofold set of
levels and a lower-energy fourfold set, eorresponding to ['7 and ['8 in the O'
double group* Next, we need to determine the effeet of the magnetie field. Sinee
systems with Oh symmetry are magnetieally isotropie (x, y, and z), it is only
neeessary to work out the effeet of Hz . T he Hamiltonian operator, H (parallel
to z) is [J(Lz + geSz)Ho ' T he res ulting energies were derived in C hapter 11 and
are indieated in F ig. 13- 9. The splitting in the low-energy set is very small, being
second order in H (i.e., H
2
). W hen one sol ves for g( t::.E = g[JH), the result
g[JH = or 9 = 4f3 1l/ 3 O is obtained for lhe lowest level.t Wi th
appreciable separation of [' 8 and ['7 (e.g., = 154 cm - J for Ti 3+), pr will not
be deteeted unless the 7 state is populated. Sol vi ng the expression for g[J H for
these levels as aboye results in a g-value of 2.0. This state j I! be populated at
room temperature, but the large amount of spin-orbit coupling gives rise to a
short Te and no spectra are observed. Liquid helium temperatures are needed to
lengthen Te' but then only the 8 sta tes are populated. " hus, the inability to
observe epI' speetra on these systems is a direet predietion of erystal field theory.
* The f7 and f8 states correspond to J = 1/
2
and J = 3/
2
, respectively, for the free ion. These
designations are derived by factorin g. the product of T
2
' (orbital part) and E
2
' (1
6
[or spin = 1/
2
) in
the O' double group.
t [n some systems. [ra nsit ions with very small g-values have been detected.
(
1:
ee
In
sh
9.
rO
Wl
In
int
eRe
las
int,
sys

syn
Ha
km
Hyperfine Cauplings and Zera Field Splittings 571
r
e
2.
las
of
O'
ee
11 y
lel

I
lI1g
,ult
ith
not
ror
dat
(1 )
E= +13Hz +
r
7
(2)
(1 )
E= - 13Hz +
2T
2
(4) r (2)
E=
(2)
E= -(U2) -
OhFeld Spin-Orbit H
Coupling
13- 3 HYPERFINE COUPLlNGS ANO ZERO FIELO
SPLITTINGS
HyperfineandZero-FieldEffects on the SpectralAppearance
Transition metal systems are rieh in information arising from metal hyperfine
eoupling and zero-field splitting. Figure 9-1 4 illustrates the rieh eobalt hyperfine
interaction in C0
3
( )9Se. Before eontinuing with this discussi on, the reader
should review the seetion on "Anisotropy in the Hyperfine Coupli ng" in Chapter
9, as well as that on " The epr of Triplet States," ifnecessary. The spin Hamill onian
for a single nueleus with spin 1 and a single effective elect ronic spin S can be
written to inelude these extra effects as
(13-16)
In the previous section, we discussed the 3"' g'S term and the complications
introduced by orbital contributions. The next term incorporates the zero-field
effects previously described by the dpoJar tensor, D, which has a zero trace. The
last two terms arise when 1i= O.
In Chapter 9, we discussed zero-field effects that arose from the dipolar
interaction of the two or more eJectron spin moments. rn transiti on metal ion
systems, thlis term is employed to describe any effect that removes the spin
degeneracy, ineluding dipolar interactions and spin-orbital splitting. A low
symmetry crystal fie ld oft en gives rise to a large zero-field effect.
In an axi all y symmetric field (i.e., tetragonal or trigonal), the epr spin
Hamiltonian that can be used to fit the observed spectra for effective spin systems
lower than quartet takes the form
H
sPi n
= D[Sz 2- S(S +1)J +9I1 fJI-l };z +gl3(HxSx +HyS)+
AII S)z+Al(S)x +SJy)+f
1
/ - 1(1 +1)J - y3N
H
O
1
FIGURE 13-9 The influence
of spin-orbit coupling and an
applied magneticfield on a T
state.
The first term describes the zero-field splitting, the next two terms describe
the effect of the magnetic field on the spin multiplicity remaining after zero-field
splitting, the terms in A 11 and Al measure the hyperfine splitting parallel and
perpendicular to the main axis, and Q' measures the small changes in the spectrum
produced by the nuclear quadrupole interaction. All of these effects have been
discussed previously (se e Chapter 9). The final term takes into account the fact
that the nuclear magnetic moment f.1N can interact directly with the external field
f.1N H o= ')' /3N Ho . 1, where ')' is the nuclear magnetogyric ratio and /3/\ is the nuclear
Bohr magneton. This is the nuclear Zeeman effect, which gave rise to transitions
in nmr. This interaction can affect the paramagnetic resonance spectrum only
when the unpaired electrons are cuoled to the nucleus by nuclear hyperfine or
quadrupole interactions. Even when such coupling occurs, the effect is usually
negligible in comparison with the other terms.
In the case of a distortion of lower symmetry, there are three different
components gx' gy' and gz, and three different hyperfine interaction constants
A
x
' Ay, and A z . Two additional t e r m ~ n e e ~ to be included: E(S/ - S/) as an
additional zero-field splitting and Q"(I/ - 1/) as a further quadrupole interac-
tion. The symbols P and P' are often used in place of Q' and Q", respectively.
The importance of the spin Hamiltonian is that it provides a standard
phenomenological way in which the epr spectrum can be described in terms of
a small number of constants. O nce values for the constants have been determined
from experiment, calculations relating these parameters to the electronic con-
figurations and the energy states of the ion are often possi ble.
The splitting of the 6S state of an octahedral manganese(ll) complex is
illustrated in Fig. 13-10(A). Here we have the interesting case in which al Mn
2
has a 6Ag ground state, which is split by zero-field effects. Spin-orbit coupling
mixes into the ground state excited 4T
2
states that are split by the crystal field,
and this mixing gives rise to a small zero-field splitting in M n
H
. The dipolar
interaction of the elect'on spins is small in comparison to the higher state mixing
in this complex. The orbital effects are very interesting in this example beca use
the ground state is 6S, and thus the excited 4T
2
state can only be mixed in by
second order spin-orbit effects. Thus, the zero-field splitting is relatively small,
for example, of the order of 0.5 cm -[ in certain manganese(JI) porphyrins
06a
)
As indicated in Fig. 13-10, the zero-field splitting produces three doubly
degenerate spin states, Ms = 5/2' 3/2' [/2, (Kramers' degeneracy). Each of
these is split into two singlets by the applied field, producing six levels. As a
result of this splitting, five transitions (- 5/2 -+ - %, - 3/2 -+ - 12' - [/
2
-+ [/
2
,
[/
2
-+ %, %-+ %) are expected. The spectrum is further split by the nuclear
hyperfine interaction with the manganese nucleus (I = %). This would give rise
to thirty peaks in the spectrum.
In contrast to hyperfine splitting, t he terro fine splitting is used when an
absorption band is split because of non-degeneracy arising froro zero-field
splitting. Components uf fine splitting have varying intensities: the intensity is
greatest for the central Iines and smallest for the outermost Iines. In simple cases,
the separation between lines varies as 3 cos
2
() - 1, where () is again the angle
between thedirection of the field and the molecular z-axis.
In Fig. 13-11, the inftuence of zero-field splitting on an S = 1 system is
indicated for a fixed molecular orientation. (Recall that there is no Kramers'
degeneracy.) In the absence of zero-field effects [Fig. 13-11 (A)], the two Il'lms I = 1
transitions are degenerate and onl y one peak would result.
(8:
in t
st at,
splil
!}/'(n
spec
,
I
l
1,
.r
e
"
Ir.
a )
Iy

a
ar
se

is
s'
,[
13--3 Hyperfine Couplings and Zero Field Splitt i ngs 573
+-i /
FIGURE 13--10 (A) Spli tting
/-\---
01 the levels in an octahedral
// ,=====
Mn(ll ) spectrum. (8)
/
/
Spectrum 01 a single crystal
/
01 Mn
2
+ doped into MgV
2
0
6
,
/ + 1.
/ 2 ,=====
showing the live allowed / /---'---
/ /
/ // transitions (Iine structure),
/ /
/ / each split by the magnanese
/ //
nucleus (1 = 5/
2
) (hyperfine / / +...!.
+ 2. / ".,/' ___
2D - 2 //// _-- structure). At 300 K,
65_ _ ---
g, = 20042 0.0005,

gy = 2.0092 0.001, and
40 ...!. _ _ 1
gz = 2.00050.0005; Az =
2 "
Ay '= A z = - 78 5 G; and
"
""
" ,
O, = 218 5 G,Oy = - 87 5
"', 3
" " - - ---
Gm abdO
z
= -30620 g.
[Modilied Irom H. N. Ng and
" ''':::-. __2_//=====
" "
C. Calvo, Can.J . Chem., 50,
" _2. 1=====
"" 2 1 ___
3619 (1972). Reproduced by
\
permission 01 the National
Zera field Appli ed Nuclear Finestructure ResearchCouncil01 Canada.]
levels f ield splitting transitions
---\---
(Al
- -H
(8)
1 :"
II
+1
ms=-I , O,+1
hu"

m.=O hv'
- 1
I ..
O Inc.fleld o Inc.field
strenglh
(A)
(8)
Forthe spl ittingshown in F ig. l3-11(B), two transitions would be observed
in the spectrum. A specific example of this type of sy.tem is the 3A29 ground
stateofnickel( lI)in an Oh field. Spin-orbitcouplingmi xes inexcited states,which
split the configuration. Recall that zero-field splitting is very anisotropic, 3A
29
providing a relaxation mechanism for the electron spin state. Accordingly, epr
spectraofNi(lI) Oh complexes aredifficult to detect , and when they a re studied,
FIGURE 13--11 The energy
level diagram and transitions
lor a molecule or ion with
S= 1, (A) in the absence 01
and (8) in the presence 01
zero-field splitting.The
system in (8) is aligned with
the z-axis , lor the ellect is
very anisotropic.
liquid nitrogen or helium temperatures must generally be employed. At room
temperature, nmr spectra can be measured. In so me systems, sharp double
quantum transitions (1 L1m I = 2) can be seen in the epr spectrum( 16b)
s
As mentioned in Chapter 9, the zero-field splitting can be so large that the
L1m = 1 transitions are not observed. For example, in y3 + (d
2
), L1m = 1
s s
transitions are not detected, but one observes a weak L1m
s
= 2 transition
(-1 -> +1) split into eight lines by the nuclear spin of 51 Y (I = 7/
2
). The
mechanism whereby the L1m
s
= 2 transition becomes allowed is the same as that
discussed for organic triplet states in Chapter 9.
The next topic to be discussed is the definition of the term effective spin, S'.
We have already been using this idea, but now formally define it to describe how
some of the effects that we have discussed are incorporated into the spin
Hamiltonian. When a cubic crystal field leaves an orbitally degenerate ground
state (e.g., a T state), the effect of lower symmetry fields and spin-orbit coupling
will remove this degeneracy as well as the spin degeneracy. In the case of an odd
number of unpaired electrons, Kramers' degeneracy leaves the lowest spin state
doubly degenerate. If the splitting is large, thi s doublet will be well isolated from
higher-lying doublets. T ransitions will then be observed only in the low-Iying
doublet, which behaves like a simpler system having S = 1/
2
. We then say that
the system has an effective spin S' of only 1/
2
(S' = 1/
2
). An example is C0
2
I . The
cubic field leaves a 4F ground state which, as a result of lower symmetry fields
and spin-orbit coupling, gives rise to six doublets. When the lowest doublet is
separated from the next by appreciably more than kT, the effective spin has a
value of 1/
2
(S' = 1/
2
). instead of 3/
2
. A spin Hamiltonian can be written in terms
of S' rather than S.
It should be clear that all of the effects discussed aboye can have a pronounced
influence on the spectral appearance. The qualitative interpretation of the epr
spectra of transition metal ions by inspection is thus not trivi al. Proficiency is
obtained by looking at many spectra and drawing analogies to known systems
when dealing with new systems. Practice will be afforded in a later section where
the representative spectra of different d
n
systems wiU be considered, and also in
the exercises at the end of the chapter.
Confribufions fo A
The hyperfine coupling interaction has contributions to it from Fermi contact,
di polar nuclear spin-electron spin, and nuclear spin-electron orbit mechanisms.
These effects have been discussed in Chapter 9. The reader is referred to equation
(9-25) and the subsequent discussion of it for a treatment of the dipolar
contribution. The trace of the tensor in equati on ( 9-25) is zero, so information
about the dipolar contribution can be obtained onl y from ordered 01' parfiall y ordered
systems. As mentioned in equations (9-34) and (9-35), where the traceles s tensor
components of A were indicated by T, the contribution to dipolar hyperfine
coupling for an electron in a Pz orbital is given by
with
(13-17)
F
Si
q\
to
rel
f[(
fig
as
ro
fie
T"
m<
to
r ~
l'
\.
/
\
,
g
e
s
b
a
:d
pr
IS
ns
:rc
ID
el.
ns.
on
lar
iOIl
red
sor
l n ~
-17)
13-3 Hyperfine Couplings and Zero Field Splittings 575
TABLE 13-1. Contributions to the Dipolar Hyperfine
Coupling from Electrons in d orbitals
Orbital Tzz(Pdl Txx(Pdl Tyy(Pdl
4/7 _2/7 - 2/7
~
_4/7 2/7 2/7
dx'-r'
dl"
2/7 - 4/7 2/7
d
xz
2/7 2/7
- %
_4/7 2/, 2/7
d"
Foran electron in a Pzorbital, we have
T_(4)p
xx - :5 p
Similar expressions can be derived for an electron in one ofthe d orbitals. The
quantitites in Table 13- 1 must be multiplied by
(13-18)
to obtain the dipolar contribution. The signs and magnitudes can be easily
remembered. The orbital is located in the 3 cos
2
e- 1 plot of the lines offlux
from the nuclear moment, as shown in Fig. 13-12 for the dxz orbital. In this
figure, the z-axis ofthe molecule is aligned with the z-axis ofthe field to give 1'.%
asa small positivenumber. Next rotatetheorbitalcounterclockwise90,without
rotating the cone, so that the x-axis of the molecule is aligned parallel to the
field (which is still along the z-axis shown in Fig. 13-12) to give a small positive
T
xx
' Next,start with Fig. 13-12and rotate the moleculeso that the z-axis ofthe
molecule is perpendicular to Ihe page and the y-axi s of the molecule is parallel
to the field (i .e., the z-axis in Fig. 13-12). Nowthe tobes ofd are in the negative
xz
regionoftheconeanda targenegativeYyy isexpected.Theserotationscorrespond
z
.,....,...------- --------
' ""
\ + )
~ - - - ~
,,---- ----- /"
' " ,/
- - - - - - - - - - ~ ~ ~ ~ ~ - - - - - - - - - - - - x
./ "-
,/ - ------ ',
/-- - - - - ~
\ + ~
""
---
-----------
- -""
/
FIGURE 13- 12 Orientation of the
d
xz
orbital relative to the 3 cos
2
O- 1
cone.
;
to the three mutually perpendicular orientations of the molecule relative to the
neldo With information on the signs and magnitudes of the components of t he
hypernne tensor, one can obtain information about the atomic orbitals in a
complex that make the principal contribution to the molecular orbital containing
the unpaired le trono
The Fermi contact contribution has been discussed in detail in Chapters 9
and 12. Unpaired spin density is felt at the nucleus by direct admixture of the
5 orbitals into t he m.o. containing the un paired electron and by spin polarization
of fill ed inner s orbi tals by unpaired lectron density in d orbitals. When the
45 orbital of the met al is empty, it can mix into the largel y metal d- antibonding
orbital ; and if trus m. o. contains unpaired spi n, Ihe electron partly occupies the
metal 45 orbital.
Spin polarization can have two different res ults. When an inner 15- or
25 orbital is spi n-polarized by a-spin io a 3d orbital, an excess of f3-spin res ults
at the nucleu . When t he fi ll ed 35 orbital is spin-polarized by an electron with
a-spin in a 3d orbi tal, a-spin results at the oucleus. The effect of direct
delocali zation into the 45-orbital can be shown by comparing Fermi contact
hypernne values (AF.CJ determined for various cobalt(H) complexes. It has been
found(17a) that A
F
.
C
for sixfold coordination falls in the -30 to - 45 G region,
for fivefold coordination in the - 5 to - 25 G region, and for square planar
fourfold coordi nation in the O-G region. O ne can write an equation summarizing
cootributions to A
F
.
C
.:
(13-19)
where A
4s
is the direct hyperfine interaction of one unpaircd electron in a 4s
orbital, 1320 G x gf3; and A3d is the hypernne interaction arising from spin-
polarization of filled 5 orbitals by an unpaired electron in a 3d orbital , - 90
G x gf3. Appl ying this equation to the sixfold, fivefold, and fourfold cobalt(lI)
complexes, one obtains x = 3 to 4 %, x = 4.5 to 6%, and x = 6.5 % respectively,
for admixture of 45 into the m.o. containing the unpaired electron.
The nuclear spin-electron orbit contribution to the coupling constant is
related to the pseudocontact contribution discussed in Chapter 12. The Hamil-
tonian is
(13- 20)
Here the nuclear moment is interacting not only with the spin moment (discussed
earlier), but al so with the orbital moment. The nuclear interaction with the spin
moment is a traceless tensor, but the interaction with the orbital moment is not.
Since it is not , a pseudocontact contribution is observed in the nmr spectrum in
solution.
13--4 L1GAND HYPERFINE COUPLlNGS
Hyperfine splittings rrom ligand atoms have contributions from a Fermi contact
term, F.C. ; dipolar contri butions from the metal, DIP; di polar contributions from
electron density in p orbit als of the ligands, LDP; and the metal pseudocontact
(
T
h
(1
st
C(
x-
UI
Ji
(1
va
eq
wl
In
dis
po
Val
whi
rati
the
by
11
13-4 Ligand Hyperf ine Couplings 577
contribution at the ligand, LPC, which results fr om the interaction of the orbital
angular momentum of the unpaired electron with the Jigand nuclear spin. When
Iigand hyperfine structure is resolved. this latter term is generally small comparcd
to the other contributions. When there is extensive spin-orbit coupling, a large
pseudocontact contribution would be expected, but relaxation effects lead to
difficulty in observing the e')r spectrum and consequently the ligand hyperfine
splittings. The AII and Al values are given by equations (13-21) and (13-22):
(13-21)
(13- 22)
These equations refer to the parallel and perpendicular components of the ligand
hyperfine tensor. When an investigator measures the Iigand hyperfine interaction
(A l) from the fine structure of a metal hyperfine peak (e.g., nitrogen superhyperfine
structure on a cobalt hyperfine peak), difficulty will arise if the two hyperfine
coupling tensors are not diagonal in the same coordinate system. Single-crystal
x-ray diffraction and single-crystal epr studies are necessary for complete
understanding of these systems. lf one carries out a solution epr study with the
ligand hyperfine structure resolved, A
F
.
c
can be measured directly. Equations
(13-21) and (13-22) cannot be sol ved for A
D1P
and A l.Dp , However, a reasonable
value for A
DIP
can be calculated from a knowledgc of the structure, by use of
equation(l3-23) :
(13-23)
where a is the metal -Jigand distance. Equation (13-23) is derived for circumstances
in which the metal-ligand distance is large compared to the metal nucleus-electron
distance. Where this approximation is poor, other equations have been re-
ported.(l S) The A
F
.
C
and A
LDP
values are related to the s orbital contribution as
and p orbital contribution a
p
to the molecular orbital by the following equations:
.)
16n 2 2
A
F
.
c
= - 3- 1'f3f3N11/1(0) 1 as
(13-24)
n
(13-25)
Values of A
F
.
C
. and A
LDP
are reported(l 9) for one electron in s and p orbitals from
which the %s and %p character can be calculated. From these equations, the
ratio %sj% p can be determined to indicate the "hybridization of the ligand" in
the complexo This treatment tacitly assumes that delocalization occurs mainly
by a direct mechanism ; i. e., spn polarizaton contributons are ignored.
The application of these ideas will be illustrated with a few brier examples.
The epr spectrum(20) of
2 -
indicates A t4N)/ gf3 = 15.6 G, A
1
t4N )/gf3 = 12.7 G, and A
i so
= 13.7 G. Values
of A reported for a full electron in s and p orbitals are A//gf3 = 34.1 G and
A
s
o/ gf3 = 550 G. This leads to a rati o of % p/ %s of about 1, which indicates an
sp hybrid and a linear Fe-N-O structure. O n t he other hand, the ratio of pis
for the nitrosyl nitrogen(21) of Fe(CN)s N0
3
- is 1.6, consistent with a bent
metal-nitrosyl structure (an S p2 hybrid would have had a ratio of 2).
Recently, phosphorus hyperfi ne couplings were observed(22) in the epr spectra
of (C
6
H shP and PF3 adducts of tetraphenylporphyrin cobalt( JI). The pi s ratio
was reported as 2.7 in the former case and 0.47 in the latter.
13-5 SURVEY OF THE EPR SPECTRA OF FIRST-ROW
TRANSITION METAL ION COMPLEXES
In this section, we shall briefly survey sorne of the results of epr studies on various
d" complexes. For a more complete discw.sion, the reader is referred to references
23 a nd 24. Before beginning this survey, we should mention that spin-orbit coup/ing
provides the dominant mechanismfor electron relaxation in these systems. In your
reading, you wiU find statements like "zero-field plitting causes rapid relaxation"
or "g-value anisotropy leads to a short electron spin lifetime," etc. It is to be
emphasi zed that these are all manifes tations of the effects of spin-orbit coupling
in the molecule. We have previously di scussed the relationship of spin-orbit
coupling to these effects. Second and third row transition metal complexes become
increasingly more difficult to study by the epr technique beca use the spin-orbit
coupling constants are much larger.
d
1
The results of studies on ions with the elcctronic configuration dI can be fit with
the spin Hamiltonian:
( 13-26)
In an octahedral ligand field, the ground state is 2T and there is considerable
29
spin-orbit coupling in this ground state. AII of the Kramers' doublets from the
2 T
29
term are close in energy and extensively mixed by spin-orbit coupling. This
leads to a short Te' In a tetrahedralligand field, an 2E ground state (x
2
- y2, Z2 )
Wilh no first-order spin-orbit coupli ng results. I n this geometry, admixture of lhe
r
s.
IS
d
d
IS
as
H
gro
C
13-5 Survey 01 the EPR Spectra 01 First-Row Transition Metal Ion Complexes 579
nearby exci ted states into the ground state by second-order* spin-orbit 2T
2g
coupling provides a mechanism leading to a short spin relaxati on time fo r the
electron and broad absorption lines. The complexes usually must be studied at
tempera tu res approaching tha t of liquid helium. The 2 T excited state is split by
spin- or bit coupling. W hen the ligand field is distorted (e. g. , in Y0
2
+), the ground
state becomes or bitall y singlet and the excited states are well removed. Sharp
epr spectral lines result even at highe r temperat ures.
Equati ons have been derived(24) using the di wave functions a nd the
appropriate spin Hamiltonian, to relate the g-value in a trigonally di storted
complex to the amount of di lo rtion. T he distorti on is expressed in terms of O
(cm - 1), the splitting of the 2T state. A large di sto rtion with (5 = 2000 to 4000
cm - 1 is found in lris(acetylacetonato) titanium(HI). As a result of this splitting,
the electron spi n lifetime is increased and one is able to detect the epr spect rum
at room temperature.
Yery few examples of epr spectra of these ions in octahedral complcxes have been
reported beca use of the extensive spin-orbit coupling in the 3T
I
gro und state.
Tetrahedral complexes have an 3 A
2
ground state, so we woul d expect longer
relaxation times and more readily obscrved epr spectra. The spectra of these
sys tems can be fitted with S = 1 and the spi n Hamilt onian
(13-27)
y
3
+ in an octahedral environmentf
25J
in an Al
2
0
3
lattice gave (j u = 1.92, g.L = 1.63,
D = +7.85, a nd A = 102. An example of a Y" complex that has been studied(2 3)
is y
3
" in a CdS lattice. At liquid N
2
temperatu re, a g-va lue of 1.93 and O of
1 cm - I are observed .
d
3
Octahedral d
3
complexes have an 4A
2
ground state, which must have a Kramers '
doubl et lowest in energy. When the zero-field splitting is small , as showl1 in ig.
13-13(A) three transitions can someti mes be detected a nd the ze ro-fiel d parameter
can be obtained from the two affected transitions. When t he zero-fi cld spli tti ng
is large compared to lhe spectrometer freq uency, only one line will be observed,
as shown in Fi g. 13- 13(B). In general, the pectra can be fi lted to the spin
Ha mi lt o nian as foll ows:
f = gz{3 H}; z + g"{3 H,,};,, + gy{3HySy + o[S/ - ~ + E[S/ - S/J
+ AIIS) Z + A.L [S)x + SJ ..J (13-28)
* In second-order perturbati on lheory, the E-componen! of thi s , plit state is mixed int o the
ground sta te.
:
580 Chapter13 Electron Paramagnetic Resonance Spectra ot Transi t ion Metal Ion Complexes
1%>
l-t>
I I I I I
O
I
2 I
3 4 5 6 7 'A 1
--':' 1
kG \
(B)
\
I I I I I I I
I
Zero I
O 2 3 4 5 6 7
Oh
field
I
kG
I 1- -t>
1
H
I
I
I
I
I
1-%>
I
I
I
I
I
I
I
(A)
(D)
FIGURE 13-13 (A) Small zero-lield and magnetic l ield splitting 01 the 4A
2
ground
state (field along z) for a cf3 case and the resulting spectrum.
(B) Trans-[Cr(C5H5N)4121+ in DMF, H
2
0, CH
2
0, CH
3
0H glass(33) at 9.3 GHz. O > 0.4
cm-
l
, E < 0.01.
(C) Trans- [Cr(C5H5N)4CI 21+ in DMF, H
2
0, CH
3
0H glass(33) at 9.211 GHz.
(D) Computer simulation(33) 01 (C) with gil = g1. = 1.99, 0 = 0.164 cm-
l
, E= O.
[Reprinted with permission from E. Pedersen and H. Toftlund, Inorg. Chem., 13,
1603 (1974). Copyrightby the American Chemical Society.1
Itis difficult to recognize " typical patterns " for Cr
3
+ in sorne systems(26) The
spectrumshownin Fig.13-13(D)wascalculatedbyacomputer,usinganisotropic
g, D = 0.164 cm- 1, and E = Ocm- 1. Reference 26 contains many spectra of
tetragonal Cr(III) complexes and a detailed analysis ofthem.
The d
3
system has been very extensively studied, particularly Cr
3
+. In
octahedralcomplexes, the metal electrons are in t
2g
orbitals,so Iigand hyperfine
couplings are usually smalL The g-value for this system is given, according to
crystal field theory, by
8),
g = 2.0023 - 4 4 (13-29)
~ E T
29
- A
2g
)
Theground state, being 4 A
2g
, has no spin-orbit couplingand a small amount is
mixed in va the 4T
29
state. Equation (13-29) differs [rom those presented earlier
in two ways.The spin-orbitcoupling is described by},(which can be positive or
negative) and characterizes a state. With more than one unpaired electron, the
energy differences also must be expressed in terms of the energy differences of
theappropriateelectronicstates.Calculatinggfor V(H20)6 2+ using E = 11,800
cm- 1 and ). = 56cm-1 givesa valueg = 1.964,which isc10se to theobserved(27)
value of 1.972. For Cr(H
2
0 )6
3
+, ~ E = 17,400 cm-
l
, }, =91 cm-
l
, and the
g
e
a
a
ti
o
Fi
FI
th
In
co
ep
be
d-{
ca
5tH
Th
co
SP)
IS I
11
'he
pie
of
In
loe
. lo
-29)
1t is
rlier
e or
the
:s of
,800
d(27)
lhe
13-5 Survey of the EPR Spectra of First-Row Transition Metal Ion Complexes 581
predicted g-value is smaller than the experimental value(28) of 1.977. In the case
of Mn
4
+, the discrepancy is even brga, wilh a Ga lcul ated g = 1.955 and an
experimental value of 1.994. This is in keeping with the fact that the crystal field
approximations are poorer and covalency becomes more important as the charge
of the central ion increases.
There are very few epr spectra reported for this d-electron configuration. The
ground state .in this syslem, in a weak crystalline Oh field, which is 5 E, has no
orbital angular momentum, so S is a good quantum number. Zero-field splitting
of the 2, 1, and Olevels leads to four transitions when the splitting is small,
as shown in Fig. 13-14, and none when the splitting is large. J ahn-Teller distortions
and the accompanying large zero-field splittings that are expected often make it
impossible to see a spectrum.
For low spin d
4
complexcs, the reader is referred to the d
2
section (recall
the hole formalism).
+2
+1
Ms
- 2
5E
- 1
O O
Oh
Zero
-1
F/eld Field
-2
FI GURE 13-14 Zero-field and magnetic field splitting 01
the sE ground state (Iield along z) lor a d
4
case.
d
5
Low Spin, S = ~
1na strong li gand field of octahedral symmetry, the ground state is 2 T
2
. Spin-orbit
coupling splits thi s term int o three closely spaced K ramers' do ublets ; however,
epI' spectra can be seen only a t temperatures close to those of liquid helium
because of the la rge amount of spin-orbit coupling present. Since there are five
d-electrons in these systems, the situation is analogous lo di , except that in this
case we are working wi th a posi tive hole. Jahn-Teller forces tend to distort sys tems
n
such as MX
6
-, so the g-values contained in equation (13-9) are rarely observed.
The splitting of the free ion doublet state by an Oh field, a DJ distorti on, spin-orbit
coupling, and a magnetic fi eld are shown in Fig. 13- 15. Since we have non-integral
spin, the double group representations are employed when spin-orbit coupling
is considered, and primed symbols are employed for the representations. Ir one
,
l
582 Chapler 13 Electron Paramagnetic Resonance Spectra01 Transition Metal Ion Complexes
FIGURE 13- 15 Energy level
diagram for a low spin d
5
system in an Oh field and a
0 3field, followed by
spin-orbit coupling and the
magnetic field-induced
splittings. With spin-orbit
effects included,thedouble
group 0 3' representations are
employed (primed values).
8
NTN
( e )
N I N

I
globin
formula for hemoglobin.
2/ E'
2T En
2P
E'
"A LS H
Oh
3
definesa distortion parameter,b,as in Fig. 13- 15,equationsfor theg-valuescan
be derived(29):
+2b)
(13-30)
gil = [( +2W+ - 1
(2b - 3( )
(13-31)
g1. = +2b) 2 +8er/
2
+1
Note that as b-+O, both gil and g1. -+O, in accord with the equations in Fig.
13-9. For example, Fc
3
+ in K) Co(CN)6 exhibits() O) an epr spectrum with
gil =0.915 and g1. ::::: 2.2. Substituting into equation (13-30) and employing
= -103 cm-1 for the free ion produces a value ofb ::::: 200 cm-l.
Large deviations from octahedral symmetry cause an orbitally singlet state
totie lowestin energy,well removedfrom orbitallynon-degenerateexcited states.
Longerelectron relaxation times result,andeprspectracanbeobservedathigher
temperatures. Examples of such a system are low spin deriva ti ves of ferric
hemoglobin(31) (Fig. 13-16), which possesses a large tetragonal distortion as a
result of the heme plane. Examples of bases, B, that produce a low spin
environmentareN3- ,CN - ,andOH- o Experimentalg-valuesfor theN
3
- species
are gx = l.72, gy =2.22, and gz = 2.80. The large anisotropy in gx and gy is
thought to arise from interaction of a specific ron d orbital with a nitrogen
n orbital from the coordinated histidine group that ties the globin to the heme
unit. EPR spectra(32) of bipyridyl and phenanthrolene complexes of iron(III),
rutheni um(lII ), and osmium( JIT) are analyzed in terms of an energy diagram
similarto Fig. 13- 15, bulonein which thedistortion producesthe 2 A statelower
in energy than 2E; i.e., b is negative. Spin delocalization onto the ligand was
studied as a function ofthe metal in this series.
al
se
E
s
1
SI
o
d
3
a
Ir
al
T
q.
c(
te
5/
H
, n
30)
31)

,ith
mg
ate
tes.
her
me
!s a
pIn
cies
)" IS
gen
:me
[[ 1),
ram
\Ver
was
d
5
HIgh Spin
This d-electron configuration has been very thoroughly studied. The high spin
complexes have 65 ground states, and there are no other sextet states. T he 4T
1
is the cIosest other term, and second-order spin-orbit coupling effects are needed
to mix in this configuration, so the contributions are smal!. Thus, the electron
spin lifetime is long and epr spectra are easily detected at room temperature in
a11 symmetry crystal fields. Furthermore, with an odd number of electrons,
Kramers' degeneracy exisls even when there is large zero-fie1d splitting. The
results for high spin complexes a re fit by:
The higher-power terms in Sarise beca use the octahedral crys tal field operator
couples states with M, values differing by 4, leading to a more compl ex basi
set and more non-zero off-diagonal matrix elements.
The splitting ofthe energy levels and the spect l'll m expected for a n undi lorted
octahedral iron(I1I) complex are shown in Fig. 13-17. Zero field leads to the
degenerate 1/
2
and %states and a non-degenerate 3/
2
state at lower energy by
3a' . The magnetic field further remo ves the degeneracy gi ving rise to t he transitions
and spectra shown in Fig. 13-17. This spectrum is observed for iron(Tll ) doped
into SrTi0
3
. T he iron is coordinated with an undistorted oct ahedron of oxygen
atoms.
In iron(nI ) complexes with sma11 tetragonal distortion, D <:g hv and E = O.
T he energy levels and expected spectrum are illustrated in Fig. 13- 18(A). O bsel'ved
g-values are ver y cIose to 2.00 beca use of the extremely small amount of spin-orbit
coupling. This fact also a110ws easy observation of epr spectra at room
temperature. I n zero field, the 1/
2
state is lowest with 3/
2
, higher by 2D, and the
5/
2
state aboye the %state by 5D. With small distortions relative to hv a11levcls
are populated and five transitions are seen with relative inten ities of 5: 8 : 9: 8: 5.
U D :> hv, the situation shown in Fig. 13-18(B) exists, and only one peak is
seen in the epl' corres ponding to the t ransition between 1+ 1/2 > and 1- 1/2>
Even if t he higher level s a re populated, !':J. M i= 1 fol' the possible transition and
s
no spectral bands are observed. The g-val ues can be calcul ated, u. ing onl y 1 %,
J/
2
> and 1 %, - 1/2> as a basis set and employing the Zeeman Hamiltonian,
f = gll ' f3H
z
Sz + gl 'f3( H ,Sx + HySJ When H is parallel to z, we have
5
1
5
/2, 1/
2
> 1 / 2, _J/
2
>
fj = e/2, 1/21 11 /2gef3 Hz
(13-33)
1 <5/
2
, - J/
2
O I
Solving eqllation (13-33) leads to !':J.E = gef3Hz and 9 11 = gc.
584 Chapter 13 Electron Paramagnetic Resonance Spectra 01 Transit ion Metal Ion Complexes
H--
(B)
12 )
2

FIGURE 13-17 The splitting 01 the energy levels (A) and the
spectrum (8) expected lor an octahedral iron (111) complex (H
parallel to a principal axis 01 the octahedron).
For H parallel to x, after using S = Sx Sy we obtain
1
5
/2, 1/
2
) 1
5
/ 2' _1/
2
)
H= <5/2 , 1/ 2 1 1 O
<5/
2
, -1/2 1 3/zfePHx
I
(13-34)
Diagonalization of equation (13-34) leads to I'lE = 3g
e
{3Hz and g1. = 3g
e
;::; 6.0.
Such a situation is well represented by Fig. 13-16, where B is a weak field
ligand such as F- or H
2
0, which lead to a high spin complex. The zero-field
1- +)
)
!
,
. )
34)
0.0.
Jeld
ield
13-5 Survey 01 the EPR Spectra 01 First-Row Transiti on Metal Ion Compl exes 585
1- %)
1-- -})
H-
(A )
(8)
splitting pa ra meter, D, has been measured for several systems of this type by
examining the far infrared spectrum in a magnetic field. Values ranging from 5
to 20 cm - 1 are found for various complexes'<33) A sample epr spectrum of this
system is that of a frozen aqueous solution of the acid form of ferrimyoglobin
shown in Fig. 13-19.
The final case to be considered is one in which a geometric distortion occurs
in a complex that removes the axi al character. In this case, the rhombic complex
is described with the parameters D and E not being zero. If E/ D O (E O)
represents axial symmetry, an increase in E/ D represents a departure toward
rhombic symmetry. The maximum possible di stortion is E/ D = 0.33, Jeading to
three equall y spaced Kramers' doublets. This Hamiltonian again produces three
Kramers ' doubJets, as shown in Fig. 13-20. Solving this Hamiltonian matrix,
FIGURE 13-18 Energy
levels and expected
spectrum lor a d
5
ion in a
weak (A) and strong (B)
tetragonal lield (H parallel to
the tetragonal axis) . [From G.
F. Kokoszka and R. W.
Duerst, Coord . Chem. Rev. ,
5, 209 (1970) ]
FIGURE 13- 19 The X-band
epr spectrum 01 a Irozen
aqueous solution (77 K) 01
the acid lorm 01
lerrimyoglobin. A similar
spectrum results lor
cytochrome C peroxidase
(pH = 7.0 at 4.2 K) .
586 Chapter13 Electron Paramagnetic ResonanceSpectra 01 Transition Metal Ion Complexes
~ (g' = 0.61,9.7,0.96)
FIGURE 13-20 Kramers '
doublets in rhombic
symmetry (Oand E not equal
to zero) lorhigh spin E <r: (g' ~ 4.29, 4.29, 4.29)
iron(III) .The three principal
components are listed in
parentheses.
<r: (g' ~ 9.7,0.61,0.86)
o H------7
usi ng the wave functions that diagonali ze it , we find each of the three Kramers'
do ubl ets to be a linear combination of I%,%>, 1%, %), and 1%, 1/2>
Thus, transitions within each Kramers' doublet are allowed; the corresponding
g-values are indicated in Fig. 13-20. The separation between lhe Kramers'
do ubl ets is large enough that transitions between different ones are no t observed,
but at mos! temperat ures aH three are significantly populated, and ma ny
resonances are o bserved. An example( 34a) of this situation is Na[F (edta)] . 4H
2
0
(where edta is ethylenediamine tetraacetate) diluted in a single crystal of the
anal ogous Co( lII) complex. The spectrum, Fig. 13-21, shows one almosl isotropic
transi ti on at 9 = 4.27 and two very anisot ropic ones wit h principal g-values of
9.64 and 110, respectively.
g =9.48
I
g =4.64
g = 9 1 ~ ..A n
g =1.33
I
)c.....
I
~
FIGURE 13-21 EPR powder spectrum at 77 K 01 Fe(lll) in Co( l l l) OTA.The analysis
01 these spectralorOand E provides inlormal ion on the exlent 01 dislortion. Cases
in which Ihe distortions are smal l produce spectral appearances differenlIrom
those shown here.The reader is relerred l o relerence 34 lor more delails.
This system has not been st udied extensivel y. Low spin complexes are diamagnetic
and high spin Oh complexes are similar to d
4
High spin iron(lI) has a g-value
of 3.49 at 4.2 K and a li ne widt h of 500 gauss even at this low temperature.
Spin-orbit coupli ng in the ground state is very large and therc are nea rby exted
states that can be mi xed in. With a J = 1ground state, two transitions would
be obser vcd if zero-field effects w r smal!. In a distorted octa hedral field, zero-field
el
SI
re
re
p
h
sil
th
fa
st
nI
01
al
s ~
ar
re
In
eh
ax
TI
Uf
ov
sp
ha
31
pe
lig
un
5
'5
tic
ue
effects are large and no epr spectrum is observed. Deoxyhemoglobin is such a
species, and no one has obtained an epr spectrum on this system.
The ground state for an Oh high spin d
7
complex is 4Tg(F). With extensive
spin-orbit coupling, epr measurements are possible only at low temperatures.
With S = 3/
z
and three orbital components in T, a total of 12 low-Iying spin states
result. Low temperatures are needed to observe the epr spectra, because of spin
relaxation problems. Only the low-Iying doublet is populated, giving a single
peak, with a g-value of 4.33 from an effective S' = I/Z ' Spectra of these systems
have been reviewed.(35)
In tetrahedral symmetry, cobalt(II) complexes with "Az ground states are
similar to tetrahedral d
3
except that the 4T
z
excited state is closer in energy to
the 4Az state in cobalt. With more spin-orbit coupling, broader lines are found
for cobalt(ll).
[n square planar, square pyramidal, and tetragonal complexes, the ground
state becomes a doublet , S = 1/
2
state. With little spin-orbil coupling and no
nearby states with spin-orbit coupling, electron spin lifetimes are long, allowing
observation of t he epr at room temperature. The X-band spectra of
Co(OPGB)z ' CH
3
0H (-C2H2-)2S at 25 'C in CH
2
Cl
z
/toluene and in a
CH
2
Cl
2
/toluene glass at -180" C is shown(37) in Fi g. 13- 22. The DPGB is an
abbreviation for a BFz capped bis-diphenylglyoximato ligand system. An isotropic
spectrum results at 25 producing an average g of 2.129. At low temperatures,
an anisotropic spectrum result s in the frozen glass. The cobalt hyperfi ne is nicely
resolved in the parallel region.
The spin Hamiltonian for the low spin d
7
system is usually given as:
In the cases of the five- and six-coordinate tetragonal d
7
systems, the unpaired
electron resides in the dZ2 orbital . Fo[ this electronic configuration, assuming
axial symmetry,
gil = 2.0023 (13-36)

g.1 = 2.0023 - (1 3- 37)
uE(z - xz, yz)
This fact has been used(Z5) to study the adduct formation of coordinatively
unsaturated cobalt complexes with varieties ofaxially coordinated bases, B. Good
overl a p bet ween the donor lone pair and d
Z
2 causes readil y observed hypcrfine
splitting from bases coordinat ing via nitrogen or phosphorus at oms. Wayland
has utili'zed the large gyromagnetic ratio (and hence large hyperfine coupling) of
31 P to obtain hybridization rat ios for vari et ies of PX
3
donors with Co(tetraphenyl-
porphyri n)(22) and Co(sal en).(36)
As shown in Fig. 13- 23, the epr spectra of adducts containi ng nitrogen donor
ligand orbitals that can mix wi lh the d
z
orbital of cobalt(I1) (collt aining t he 2
unpaired electron) possess nitrogen hyperfine. Three-line hyperfine is seen in the
3150
I
<g> = 2007
I
IAI
3200 3500
I I
3350
I
FIGURE 13-22 The X-band
spectra 01
Co(DPGBh ' CH
3
0H .
(-C2H2-)2S, (A) At 25 C in
solution; (B) at -180 C in a
Irozen glass.
g ll=2.007
( 8)
A(eo)
f----1
complex in Fig. 13-23(A), which contains one acetonitrile and one methanol on
the z-axis and five lines (2!: 1 + 1) are seen in tbe complex in Fi g. 13-23(B)
containing two pyridine ligands on the z-axis. T hese spectral differences have
been used to probe site isolation in polymers con laining basic nitrogen functional
groups by adding a solution o[ Co( DPGBh' 2 H
3
0H to the polymer. (38) A
three-line nitrogen hyperfine indicates that two nitrogens coordinate and the
complex binds to one site. A five-line pattern indicates that the donor si tes are
not isolated. Polymer mobili ty can permit even a dilute concentration of sites to
behave in a non-isolated manner. The complex Co(DPGB)2' 2CH
3
CN can be
used to study basic sites of nuclei with 1 = O.
The ground state of the planar, low-spin, four coordinate complexes is more
complex(39;40) with ground states of d reported
l40
) for symmetrical porphyrins 2
z
and d
yz
for unsymmet rical Schiff bases(40)
Many five-coordinate cobalt(TI) complexes reversibly bind O
2
forming an
end on the 0 2-bound adduct. Tbe unpai red electron in the mainly do' orbital of
the square pyramidal cobalt(lI) complex spin pairs with one of t he unpaired
el
a
a
O
re
eh
w
P(
or
or
thJ
13-5 Survey of the EPR Spectra of First-Row Transition Metal Ion Complexes 589
3200 3600
I I
A(Co)
FIGURE 13-23 Frozen glass,
X-band epr 01 (top)

Co(DPGB)2' CH
3
0H 'CH
3
CN;
(bottom) Co (DPGB) 2' 2C
s
H
s
N.
A(59
CO
)
f---------1
3100 3350
I I
electrons of O
2
formng a sigma bond. Ths bonding description is referred to
as the spin-parng model(41) The resulli ng adduct has one unpaired electron in
an adduct molecular orbital thal is composed essentially of oxygen a.o. 's. In the
O
2
adducts, gil > 91. as seen in Fig. 13-24, making adduct formato n easy to
recognize. This type of spectrum with gil > g1. will arise independentIy of the
charge on 0
1
, The charge is determined by the coefficients in the bonding m.o.,
which contains a pair of electrons. The cobalt hyperfine arises mainly from spin
polarization of the par of electrons in the Co-0
2
sigma bonding molecular
orbital. Usng an approach similar to that described for spin polarization of
organic radicals (Chapter 9), an analysis(41
1
of a series of O
2
adducts indicates
that the partal negative charge on the bound O
2
varies over a range of 0.1 to
FIGURE 13- 24 X-band epr
spectrum 01 a cobalt(lI)
dioxygen adduct in a lrozen
glass.
on
I(B)
ave
.nal
lA
the
are
sto
1 be
! an
1I of
red
I
~ 0.8. A detailed analysis(42) of confli cting interpretations of the cobalt hyperfine
in these sys tems supports the spin-pairing model.
d
8
Hlgh Spin
The ground state of the gaseous ion is 3F with an orbital singlet state lowest in
an octahedral field. The d-sllell is more than half-filled, so spi n-orbit coupli ng
leads to g-val ues greater than the free electron value. The zero-field splitting
ma S it difficult to detect epr spectra except at low tempera tures. The g-val ues
found are usual1y close to isotropic.
d
9
T he d
9
configuration has been very extensively studied. In an octahedral field,
the ground sta te is 2 Eg. A large Jahn-Teller effect is expected, making observation
of the epr spectrum a t room temperature pos, ible. In tetragonal complex " the
ground state is el
x
' _ y' (x- and y-axes pointing at the ligands) and sha rp lines
result. Note tha t the quadrupolar interaction of the copper nucleus (see Chapter
9)can be determined from this experiment. The epr results fi! the spin Hamiltonian
fJ = P[gz H= Sz +gx Hx Sx +gyHySJ +AzS)z +AxS)x
+ AySyly +Q'[l/ - ~ I(I +1)J - gNPNH'] (13-38)
g = 2.223
g = 2.057
9.9 11.5 13.1
Field (kg)
200 3000 3200 3400 3600 (B)
FlELD (G)
(A)
FIGURE 13-25 "Typical" epr speclra lorcopper(ll)
complexes. (A) A typical solut ion spectrum lor a square
planar Schiff base ligand. [From E. Hasty, T.J. eolburn, and
D. N. Hendr ickson, Inorg. ehem , 12, 2414 (1973) .] (8) Glass
or powder sample run al O-band Irequencies on an ax ial
complex . (e) Glass ordoped powder speclrum 01 Ihe
complex in (A) run at X-band Irequencies.
o:X 2850 3050 3250 3 4 5 ~
FlELD (GI
~ i
--.-/'
~
I
I ~
I
I
I
I
(e)
e
1
c
S ~
\V
e
WI
T
fo
the
as
sys
13-6 The EPR of Metal Clusters 591
Sorne typical copper(I1) spectra are shown in Fig. 13-25. In (A), an isotropic
solution spectrum is shown. Both nitrogen and proton ligand hyperfine structures
are seen on the high field peak, but not on the low field peaks. This is attributed
to differences in the relaxation times for the transition, which depend upon the
m-value associated with the transition(43) The solvent employed influences the
molecular correlation time, which in turn also influences the spectral appear-
ance(43)
In (B), an anisotropic spectrum isshown at Q-band frequencies. Such spectra
are observed in glass or powder samples of copper complexes diluted in hosts.
The low field gil and high field gl peaks are well separated. With the higher
microwave energy, the individual peaks are broader so the super-hyperfine
splitting is not detected on the gil peak. In the spectrum in (C), at X-band
frequencies, the gil and gl transitions overl a p, but much more ligand hyperfine
structure is detected. As mentioned earlier, the temperature dependence of the
spectra 01' ma ny systems has been interpreted in terms of Jahn-Teller
effects.
13-6 THE EPR OF METAL CLUSTERS
EPR studi es of molecules containing two or more metal ions have provided
considerable information on indirect (superexchange) exchange mechanisrns. The
spin Hamiltonian is given by(44)
(13- 39)
where J is a matrix connecting the two spin operators SI and 52 of metal atoms
1 and 2. In the common case of a weak bonding interaction involving isotropic
exchange interactions of the same transition metal ions we can write
(1 3-40)
As mentioned in Chapter 8, JS 1 .5
2
groups the energy levels according to
(13-41)
with energies
(13-42)
The coefficients indicating the contributions of the spin Hamiltonian parameters
for g and A are ca\culated
(45
) by projecting the spin Hamiltonian parameters of
the individual ions onto the S manifold. For example. q, in the coupled system
as well as ACI and AC2 ' the hyperfi ne coupling of meta l s 1 and 2 in the coupled
system, is given by<46)
(13-43)
(13-44)
(13-45)
1
1
592 Chapler 13 Electron Paramagnetic Resonance Spectra of Transition Metal Ion Complexes
where g l' g2 ' Al ' and A
2
refer to the g- and A-values of the metals 1 and 2 in
an analogous complex containing one paramagnetic center, i.e., an M , -Zn(lI) or
Zn(IJ)-M
2
complexo The coefficients el and e
2
are given by
el = IS(S + 1) + SI(SI + 1) - S2(S2 + 1)1 / 2S(S + 1) (13-46)
e
2
= IS(S + 1) + S2(S2 + 1) - SI(SI + 1)1 / 2S(S + 1) (13-47)
Expressions for the zero-field splitting contributions have been reported(40) For
two S = 1/
2
metal ions interacting (S I = 1/
2
, S2 = 1/
2
, S = 1), values of el = 1/
2
and e
2
= 1/
2
result. For an SI = 1/
2
atom interacting with an S). = 1 atom, two
Sstates result , S = %and S = 1/
2
, For Ihe former, the coefficients a re el = 1/
2
and
= 2/ 3 and for S = 1/
2
, they are el = _1/3 and e
2
= 2/ 3'
For dimers, in which Ihe two metal ions are identical, e.g., Cu-Cu, the g-values
are identical lO the values for a single ion, e. g., Cu-Zn. For praclice, one can
calculate Ihe g-values and Acu for a Cu-Mn (S = 2) pair using g'2 = 2. 32, gx = 2.08,
gy = 2.06, and A
2
= 139 for a Cu-Zn pair in a Cu-Zn(py-O)C\4(H
2
0 )2 com-
plex(46, 47) assuming 9 = 2 for the manganese ion. Values of l.95, l.99, 1.94, and
23 should result. Note the greatly reduced copper hyperfine.
The spectrum of a polycrystalline sample of a molecule containing two copper
atoms is iJluslrated in Fig. 13- 26. The main peaks al 2500 and 3700 gauss are
assigned lO Iwo g-t components. The seven copper hyperfine componenls [two
Cu (l = 3/
2
) nucIeiJ are seen in the low field 9 peak. The other high field ~ peak
is not seen, for it is out of the spectrometer range. The peak at ~ 3200 G is
assi gned lO a !o.m = 2 transition. The origin of the doublet will be understood
e
2
s
a fter discussion of Ihe spin Hamiltoni a n. The single crystal spectra(48) of moJecules
containing Iwo copper(ll) aloms with S = 1 are fitted lo the spin Hamiltonian
(13-48)
z
t
1000 2000 3000 4000
Field (G)
(A) (B)
FIGURE 13-26 (A) A schematic representation 01 a dimer ic copper adenine
complex ; (B) the pOlycrystalline epr 01 this complex.
1
d
J
o
P
I
tr
tr
tI)
s=
s
/
2
In
or
46)
47)
For
1
two
and
lues
can
_. 08,
com-
and
pper
, are
[two
peak
1 G is
stood
cules
nian
3- 48)
The EPR 01 Metal Clusters 593
The results for dimeric copper(I1) acetate are(49) Oz =2.344, gx =2.053,
Oy = 2.093, D= 0.345 cm-
I
, E = 0.007 cm-
I
, Az = 0.008 cm-
I
, and A x,
Ay < 0.001 cm- l.The inftuence that the J, D,and E parameters ha ve on theepr
spectrum is ilJustrated in Fig. 13-27. With IJ 1=260 cm-1 in Cu
Z
(AOC)4'
transitionsfrom theS= OtoS= 1statearenotobservedin theepr.Theexchange
interactiongives rise to a lowerenergy S= Ostate,so theintensity ofthesignals
decreases with decreased temperature. This temperature dependence indicates a
J of - 260 cm- 1, corresponding to a separation of the S=Oand S= 1states
of 2J or 520 cm- l . In the powder spectrum di scussed earlier, split gHand g.l
peaks arise from the two I1Ms = 1transitions averaged over the orientations.
In the relatively rare situation where the exchange parameter J is smaller than
the available microwave energy of the epr experiment, it is possible to see epr
transitions between the S=1and S= Oelectronicstatesofa copperdimer. The
first exampleinvolvedacopperdimerandwasreported(50) for the" outer-sphere "
S=1T
2J
s=oJ....
111>

S(O)-
S(1)
ILlMsl=1

S(1)-
S(O)
11 -1)
U--
1000
FIGURE 13-27 The inlluence 01 J interactions and zero-lield effects on the energy
e
levelsandsingle-crystaleprspectrum01 amoleculecontainingtwod
9
copperatoms.
dimers in [Cu2(tren)2X2](BPh4)2' where X = NCO- and NCS- and tren is
2,2' ,2"-triaminotriethylamine. The "outer-sphere" dimeric association occurs
between two Cu(I1) trigonal bipyramids by virtue ofhydrogen bonding between
the uncoordinated O(S) end o[ OCN-(SCN-) nitrogen bonded to one copper
andan N-Hproton ofthecoordinated tren. In thecaseofX-bandepr,}-values
of ~ 0 1 5 cm-1 to ~ 0 0 5 cm-1 can be gauged by the observation of singlet-
to-triplet transitions as illustrated in Fig. 13-27.
13- 7 OOUBLE RESONANCE ANO FOURIER TRANSFORM
EPR TECHNIQUES
Consider an experiment in which the epr transition is broadened by coupling to
an
17
0 nucleus.If onesweepsthenmr
17
0 frequenciesin adecouplingexperiment
and monitors the epr intensity, a plot of this intensity produces the
17
0 nmr
spectrum. This is referred to as an E DOR experiment(SI) (electron-nucleus
double resonance) and combines the inherent sensitivity of the epr experiment
withthe resolution ofthenmr. One generallyperforms thisexperimentalseveral
different epr frequencies (i.e., g-values) to maximize the information obtained. A
recent report!S2) involved iron-sulfur cluster interactions with a 170-labeled
substrate. A broad epr peak at 9 = 1.88 is monitored as the
17
0 frequency was
swept over ~ 10 MHz. Ten peaks corresponding to two five-line patterns from
non-equivalent
17
0 Ii gands (l = 5/
2
) are seen in the ENDOR spectrum even
though no
17
0 hyperfine is observed in the epr.
ELDOR is a double-resonance experiment in which the epr is examined
while anotherelectron spin transition is saturated.This application is similar in
concept to the nmr decouplingexperiment. Intensity increases from the nuclear
Overhauser effect can result.
Fourier transform epr provides sorne of the advantages of FTNMR. The
measurement ofelect ron spin lifetimes is possible. The irradiation time must be
significantly shorter than TI and T
2
. Using available pulses as short as 10
nanosecondscoupledwithadeadtimeallowanceof50to 100nanosecondspermit
the measurement of T
1
-val ues of10 -
6
to 10-
7
seconds.(S3)
A second application of TEPR is electron spinecho envelope modulation
spectroscopy( S4) One selects a field (i.e., g-value) in t he epr spectrum and, wi t h
a sequence ofmicrowave pulses,generates a spin echo. The intensity ofthe echo
is modulated as a function of the delay between pulses due to the magnetic
interaction of nuclear spi ns coupled to e\ectron spins. ourier transform leads
to an ENDOR-like spectrum containing nuclear hyperfine and quadrupole
spli ttings. In a three-pulse(54C) sequence it is possi ble to suppress one nuclear
modulation frequency enabli ng one to eli.m.i nate undesired hyperfine co uplings
and focus on those ofinterest. Fo!" example, one can see deuterium modul ation
whilesuppressingprotonmodulation whenbothnuc\ ei arepresentin asample.
1:
L
l
t ~
It
17
18
19
20
21.
22.
23.
24.
25.
26.
27.
211.
29.
30.
31.
32.
33.
34.
REFERENCES 1. See M. Tnkham, "Group Theory and Quantum Mechancs," p 143, McGraw- Hill ,
35.
ew York (1964).
36 ..
CITED
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3. 1. P. Fackl er and 1. A. Smith, J. Amer. Chem. Soc., 92, 5787 (1970); J. P. Fackl er, 1.
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D. Levy, and 1. A.Smith, ibid., 94, 2436 (1972).
39. I
4. a. B. M. Hoffman,F. Basolo,and D. L. Diemente,1. Amer.Chem.Soc,95,6497(1973).
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5. P. T. ManohanonandM.T. Rogersin"ElectronSpinResonanceoC MetalComplexes,"
ed. Teh Fu Yen, P!enum Press, Ncw York, 1969.
6. B. Bleaney and D. J. Ingram, Proc. Phys. Soc., 63,408 (1950).
7. A. Abragam and M. H. L. Pryce, Proc. Phys. Soc., 63, 409 (1950).
8. B. Bleaney and K. D. Bowers, Proc. Phys. Soc., 65, 667 (1952).
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10. H.C.Allen,Jr. .G.F. Kokoszka,andR. G.1 nskeep,J.Amer.Chem.Soc.,86,1023(1964).
11. For other examp1es, see F. S. Ham in "Electron Paramagnetic Resonance," ed. S.
Geschwind, Plenum Press, New York, 1972.
12. R. C. Koch, M. D. Joesten, and 1. H. Venable, Jr. , 1. Chem. Phys. 59, 6312 (1973).
13. R. Kirmse et al. 1. Chem. Phys., 56, 5273 (1972).
14. E. Bu1uggiu and A. Vera, 1. Chem. Phys., 59,2886 (1973).
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16. a. Yonetoni et al., J. Biol. Chem., 245, 2998 (1970).
b. J. W. Orton et al., Proc. Phys. Soc., 78, 554 (1961).
17. a. M. C. R. Symons and 1. G. Wilkerson, 1. Chem. Soco (A), 2069 (1971).
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4580 (1964).
18. B. A. Goodman and 1. B. Raynor, Adv. Inorg. Chem. Radiochem. , 13, 135 (1970).
19. P. W. Atkins and M.C. R.Symons, "The Structure oC 1norganic Radicals," EIsev ier,
New York, 1967.
20. W. V. Sweeney and R. E. Coffman, 1. Phys. Chem., 76,49 (1972).
21. D. A. C. McNeil, 1. B. Raynor, and M. C. R. Symons Proc. Chem. Soc., 364 (1964).
22. B. B. Wayland and M. E. Abd-Elmageed, 1. Amer. Chem. Soc., 96, 4809 (1974).
23. R. M. Golding, "Applied Wave Mcchanics," Van Nostrand, New York (1969).
24. B. R. McGarvey, "Electron Spin Resonance oC Transition Metal Comp1exes," in
" Trans ition Metal Chcmistry," Vol. 3, pp. 89- 201 , ed. R. L. Carlin. Marcel Dekker,
ew York (1967).
25. S. Foner and W. Low. Phys. Rev., 120, 1585 (1960).
26. E. Pedersen and H. Toftlund, Inorg. Chem., 13 , 1603 (1974).
27. R. H. Borcherts and C. Kikuchi, J Chem. Phys., 40, 2270 (1964).
28. C. K. Jergensen, Acta Chem. Scand., 8, 1686 (1957).
29. A. Carrington and A. D. McLachlan, " Introduction to Magnetic Resonance,"
Harper & Row, New York, 1967.
30. W. C. Lin, C. A. McDowell, and D. 1. Ward, 1. Chem. Phys., 49, 2883 (1968).
31. D. J. E. Ingram, "Biological and Biochemical Applications of Electron Spin
Resonance," Ple num Press, New York, 1969,
32. R. E. DeSimone and R. S. Drago, 1. Amer. Chem. Soc., 92, 2343 (1970).
33. G. C. Brackett , P. L. Richards, and W. S. Caughey, 1. Chem. Phys., 54,4383 (1971).
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c. R. D. Dowsing and 1. F. Gibson, J. Chem. Phys., 50, 294 (1968).
d. J. R. Pilbrow, J. Mag. Res, 19, 308 (1975).
e. 1. Peisach"FrontiersofBiologicalScience,"ed. P. L. Duttonetal.,Vol. 2,Academic
f. M. Sato and H. K n, Chem. Phys. , 12, 199 (1976).
35. F.S. Kenedy el al., Bi ochem. Bi ophys. Res. Comm., 48, 1533 (1972).
36. B. B. Wayland, M. E. Abd- Elmageed, and L. F. Mehnc, submitted.
37. B. Tovrog, D. 1. Kitk o, and R. S. Drago, 1. Amer. Chem. Soc., 98, 5144 (1976).
38. R. S. Drago and 1. H. GauJ, (nog. Chem., 18,2019 (1979).
39. r . Urbach, 1. Amer. Chem. Soc. , 96, 5063 (1974).
40. a. B. R. McGaryey, Can. 1. Chem., 53, 2498 (1975).
b. V. Malatesta and B. R. McGarvey Can. 1. Chem., 53,3791 (1975).
c. A. Reuyeni, V. Malatesta, and B. R. McGaryey Can. 1. Chem., 55, 70 (1977).
41. R. S. Dragoand B. B. Corden,Acct s.Chem. Res., 13,353 (1980)and references therein.
42. T. D. Smith and 1. R. Pilbrow, Coord. Chem. Rey. , 39, 295 (1981).
43. W. B. Lewis and L. O. Morgan, " Transition Metal Chemistry," Vol. 4, p. 33, ed. R.
L. Carlin, Dekker, New York, 1968.
44. T. Maryia in "Magnetism" eds. G. T. Rado and H. SuhJ, Vol. 1, Academic Press,
New York, 1963.
45. J. Scaringe, D. J. Hodgson, and W. E. Hatfield, Mol. Phys., 35, 70 1(l978).
46. a. D. Gatteschi " TheCoordination Chemi stryofMetalloenzymes," eds. 1. Bertini , R.
S. Drago, and C. Luchinat, D. Reidel , Holl a nd, 1983.
b. L. Banci, A. Bencini, and D. Gatteschi, Inorg. Chem. , 20, 2734 (1981).
47. J. A. Paulson, D. A. Knost , G. L. McPherson, R. D. Rogers, J. L. Atwood, Tnorg.
Chem., 19,2519 (1980).
48. G. F. Kokoszka and R. W. Duerst , Coord. Chem. Rev., 5, 209 (1970).
49. B. Bleaney and K. D. Bowers, Proc. Roy. Soco (London), A214, 45J (1952).
50. D. M. Duggan and D. N. Hendrickson, Inorg. Chem., 13,2929 (1974).
51. 1. S. Hyde, R. C. Sneed,and G. H.Rist ,1. Chem. Phys.,51,1404 (1969) and references
therein.
52. J. Telser, M. H .Emptage,H.Merkle, M. C. Kcnnedy, H. Beinert,and B. M. Hoffman,
1. Biol. Chem., 261 , 4840 (1986).
53. a. R. Orbach and H. 1. Staplet on, "El ectron Spin-Lattice Relax.ation," in "Electron
Paramagnetic Resonance" ed. by S Geschwind, Plenum Press, New York 1972.
b. H. J. Stapleton, Mag. Reson. Rey. 1, 65 (1972).
54. a. L. Kevan in " Time Domain Electron Spin Resonance," eds. L. Kevan and R. N.
Schwartz, Wiley-Interscience, New York, 1979.
b. L. Keyan,1. Phys. Chem. , 85, 1628 (l981).
c. L. Keyan, Accts Chem. Res., 20, 1(1987).
d. W. B. MimsandJ. Pei sach,1. Biol. Mag. Reson. ,Vol. 3,eds.1. BerlinerandJ.Ruben,
Plenum Press, New York, 1981.
ADDITIONAL
REFERENCES
J. E. Wertzand J. R. Bolton,"ElectronSpin Resonance," McGraw-Hill , , ew York, 1972.
A. AbragamandB. Bleaney,"EPRofTransitionlons,"ClarendonPress,Oxford, England,
1970.
1. W. Orton, "Electron Paramagnet ic Resonance," Gordon and Breach, ew York, 1968.
R. M. Golding," Applied Wave Mechanics," Van Nostrand, New York , 1969.
J. S. Griffith,"TheTheory ofTransition-Metal lons," Cambridge University Press, N<::w
York, 1961.
A. Carrington and A. D. McLachlan, "Introduction to Magnetic Resonance," Harper&
Row, New York, 1967.
C. P. Poole, "Electron Spin Resonance," lnterscience, New York, 1967.
B. R. McGarvey,"ElectronSpin ResonanceofTransitionMetalComplexes," in " Transition
Metal Chemistry," Vol. 3, pp. 89-201, ed. R. L. Carlin, Dekker, New York, 1967.
G. KokoszkaandG. Gordon,"TechniqueofInorganicChemistry,"Vol 7, pp. 151-271,ed.
H. B. Jonassen a nd A. Weissberger, Interscience, New York, 1968.
B. A. Goodman and 1. B. Raynor, Ady. lnorg. Chem. Radiochem., 13, 135 (1970).
R. Bersohn, "Determination ofOrganic Structures by Physical Methods," Vol. 2, eds. F.
C. Nachod and W. D. Phillips, Academic Press , New York, 1961.
A. Carrington, Quart. Rey. , 17, 67 (1963).
A. Carrington and H. C. Longuet-Higgins, Quart. Rev., 14, 427 (1960).
2.
Exercises 597
t.
s,
R.
g.
;cs
\n,
on
2.
N.
1. Below is a typical Cu
2
+ solution spectrum. It can be characteri zed by U = e/
3
Ju
+ %gl. and A = l/3A u+ 2/3 Al. '
60
-
40
30
3200 2800
H(gauss)--
a. Determine g and A.
b. This is an X-band spectrum (9.4 x 10
9
Hz). Why should A be expressed in Hertz?
A
2. Readers often find ir difficult ro understand why the epr spectrum of a powder or
frozen solution should yleld (in an axially symmelric compound , for example) 9 ,Ul.,
rr
and Al.. "After all," the argument goes, "you are looking al a superposition of
all possible orientations. At intermediate orientalions you have an average g and A,
e.g. U
2
= g/ cos
2
() + Ul. 2 sin
2
e. Thus, the speclrum should be very broad with few
features,." This argument is correct as rar as it goes, but il ignores the ract thal we
are Jooking at a first derivative. For example, suppose that a compound has ~ = 2.0
and gl = 2.1. Recalling that there are many more perpendicular directions than there
are paralleJ ones, (he absorption spectrum should appear in (he ideal case as in (A):
2.0 2.1
(A) (S)
EXERCISES
Because oC line broadening, the real absorption curve resembles that in (B).Thefirst
derivative will then be
A 2.1
~ 2 . 0 v _ _ _ _
4.
Theargumentisfurthercomplicated,butessentiallyunchanged,by includinghyperfine
coupling.
Below is the powder spectrum of copper diethyldithiophosphinate (for E3C U,
1 = 3/
2
), Explain as many Ceatures as possi ble. Hint: A11(ClI) ~ 5A
1
(Cu). What other
nuclei might give hyperfine splitting?
5. I
3. The solution spectrllm below is typical for a vanadyl complex (fo r V, I = 7/
2
),
Explain the splitting pattern.
I VO(glycolatel
2
) 2- inH
H_
Exercises 599
O
2
4. Below are the frozen solution (top) and room temperature (bottom) spectra of a
vanady\ complex of d,l-tartrate (only one species is present ). What can you deduce
about the structure ofthi scomplex? (Tartaric acid has the formu la
H H
I I
HOOC-C-C-COOH.)
I I
OH OH
250G
/ DPPH H
I I I H
1000 2000 3000 4000
--1 f-
100G
r
100G
f--j
H ---
/ integrated
5. Diphenylpicry\hydrazyl (OPPH) is a common reference in epr spectroscopy. Its
structure is
600 Chapter 13 Electron Paramagnet ic Resonance Spectra of Transi t ion Metal Ion Complexes
In powder or concent rated xylene soluti on, it gives a sharp one-line pattern shown
at top left. In a 1O-
3
-M xy!ene solut ion, it gives the pa ttern shown at the left. How
does this spli tt ing pattern ar ise? Why is it present only in dilute solution?
6. eopper(J l ) tetraphenylporphyrin [euTPp; see part (D) below.] has a square planar
structure with the copper lying in the plane of the four equivalent porphyrin
nitrogens. EPR spectra ofa sample ofeuTPpdoped into the free ligand are shown
H---- below. Thissample is 100 % 63eu. Natu ral abundance copperis 69 % 63euand 31 %
65e u, and 1 = 3/
2
for both isotopes.
D
4h
H __
67 .6 G
'---------'
(A )
(D)
o
(B)
/
o
a. Spectrum (A) is a powderspectrum obtained a t a frequency of9.4 GHz (X-band),
wh)e spectru m (B) was obtained at 35 GHz (Q-band). Why are ga a nd gJ. weIl
separa ted in (B) compared with those in (A)?
b. Explain the source ofthe number ofpeaks observed in the g'l region in spectrum
(B). AIso explai n the spli tting patlern found for each peak [see insert (e)].
7.
8.
Exercises 601
c. What is the crystal field splitting diagram ror a square planar complex? How is
observation or the splittings in insert (C) consistent with the orbital occupancy
predicted ror a Cu(II) complex by your crystal field diagram?
d. Qualitatively, ir this copper compound did not have a threefold or higher axis of
symmetry, what would the powderspectrum look Jike?
e. Ir natural abundance copper were used, what effect would this ha ve on the
appearance orinsert (C)?
Note that insert (C) is obtained by increasing the gain ror the set orlow-field lines.
7. Below is a spectrum orcobal! phthalocyanine(rorCo, 1 = 7/
2
),a D4h Co(II)porphyrin
similar to the copper porphyrin in problero 6.
8
e
.2
6
5
magnetic dilution 1 : 1000 .
4
o
1 2 3

'O
> "

l'2' 3' 4' S' 6' 7' 8'
"
(9
auss
)
a. What are the values org l , gJ., A'I, and A l. ? What is the origin or the observed
hyperfine structure?
b. Dissolvingcobalt phthalocyaninein 4-methylpyridineproducesal:1adduct. The
rrozen solution spectruro at 77 K is shown below. Utilizing the splitting D
4h
diagram ror low spin Co(II), state what orbital the unpaired electron occupies.
Why is each orthe eight upfield coroponents split into three lines?
e
.2
.

'O
>
"

Q;
"
(9Ouss)
c. Whydoyouseesuper-hyperfineinteractionrrom thepyr-idine nitrogenbutnotrrom
the rour phthalocyanine donor nitrogen atoros?
llld),
well 8. Predict the nurober orspectraJ Iines ror
:trum
1
2 ,.
high field lines with amplification
increased five times
602 Chapter 13 Electron Paramagnet ic Resonance Spectra 01 Transition Metal Ion Compl exes
Indi cate howzero-fleld spli tting a nd Kra mers'degeneracy appli es in theseexampl es.
9. Thefo llowingeprdataonaseriesofhigh-spinoctahedral metalhexafluori decomplexes
a re taken from Proc. Roy. Soco (London), 236,53 5 (1956):
A melal AF
Complex x 10' cm
1
x 10' cm -
1
9 ' melal Temp.
MnF
6
..-
?Ix =gy =gz = 2.00 96 17 sSMn =s/z 300
0
K
CoF
6
..-
gx =2.6 Av =43 A, = 20 59CO =7/
2
20
0
K
gy = 6.05 Ay =217 A = 32
..
go-,4.1 Az =67 Az = 21
CrF
6
3-
y = 2.00 A = 16.2 A =3
53Cr= 3/
2
300
0
K
9 = 1.98 A = 16.9 A = l
3
a. Why do CrF
6
- and MnF64 - gi ve sharpepr at room temperature whi le COF6
4
-
does so only at 20 K ? What effec t or effects cause these differences in a bi lity
to obse rvetheepr?Whi chofthesecomplexeswould bebestfor a room temperalure
nmr study ?
3
b. Why aretheCrF
6
- and MnF64 - g-va lue fairJy isotro pi c a nd close to 2.0 while the
CoF64- va lues are anisot ropic and deviate from 2. 0 ?
lJ
10. TheNovember, 1973,issueofInorgal1 ic Chemistryreportstheliquid and so lid solution
eprspectra ofsome 10 '3 M va nadyl dithiophosphinate complexes:
liquid
salid
a. xplain the liquid spectrum, for which R = CH
3
. (T he lower one is a co mput er
simul ati on.) Wha l paramet ers a re needed to characterize il? V has 1 = 7/
2
,P has
1 = 1/
2
,and H has 1 = 1/
2
,
b. Expl ai n the so lid soluti o n spectrum, for which R =phenyl. What pa rameters are
needed to characteri ze it?
Exercises 603
C. Whatshould be the mathematicalrelationship between theparametersin partaand
those in part b?
JI. Thespectrum beJow is thatofanaxiallysymmetric Cu2+ complex in afrozen solution.
Jt is a d
9
system.Assume 100% abundancefor 63Cu (f = 3/2 )' The followingconstants
will be needed: f3 = 9.27 X 10-
21
erg/gallss; h = 6.67 X 10-
27
ergsec;v= 9.12 X 10
9
Hz for the spect rometer on which the spectrllm was obtained.
a. How many parameters are required to explain thi s spectrum? What features of
the spectrum suggest these parameters?
b. Suggest why the high-field halfofthe spectrum (.1 region) is more intense.
c. What is the absoJute value of91?JlIstify the terms in the equation you use.
12. Assllme that the square pyramidal complex Cu(hfac)2PU":
6
H
s
h(for 31 P, 1 = 1/2; for
63ClI, 1 =3/2) can exist as either of the following isomers [J norg. Chem. , 13, 2517
(1974)]:
axial basal
What might be learned to aid in distinguishing the isomers by Jooking at
a. the electronic spectrum')
b. the infrared and Raman spectra (answer in a general way; .e., don' t work out the
total representation)0
c. the epr spectrum?
d. an 170-labeled epr spectrum (for 170 , 1 = 512 )?
e. the nmr spectrum?
l
Nuclear Quadrupole
Resonance
Spectroscopy, NQR*
14-1 INTRODUCTI ON
When a nucleus with an electric quadrupole moment (nuclear spin [ ~ 1; see the
second paragraph of Chapter 7 and Fig. 7-1) is surrounded by a non-spherical
electron distribution, the quadrupolar nucleus will interaet with the eleetrie field
gradient from the asymmetric eJectron cloud to an extent that is different for the
various possible orientations of the elliptical quadrupolar nucleus. Since the
quadrupole moment arises from an unsymmetric distribution of electric charge
in the nucleus, it is an electric quadrupole moment rather than a magnetic
moment that concerns uso The allowed nuclear orientations are quantized with
21 + 1 orientations, described by the nuclear magnetic quantum number m,
where m has values +1 to - 1 differing by integer values. The quadrupole energy
level that is lowest in energy corresponds to the orientation in which the greatest
amount of positive nuclear charge is closest to the greatest density of negative
charge in the electron environment. The energy differences of the various nuclear
orientations are not very great, and at room temperature a distribution of
orientations is populated in a group of molecules.
If the electron environment around the quadrupolar nucleus is spherical (as
in free Cl-), all nuclear orientations are equivalent and the corresponding
quadrupole energy states are degenerate. If the nucleus is spherical (1 = Oor J /2),
there are no quadrupole energy states even with a non-spherical electron cloud.
In nqr spectroscopy, we study the energy differences of the non-degenerate
nuclear orientations. These energy differences generally correspond to the radio
frequency regio n of the spectrum, i.e. , ~ 0 1 to 700 MHz.
It is helpful to consider the interaction of charges, dipoles, and quadrupoles
with negative electron density in order to define some terms important for nqr
(and Mossbauer spectroscopy, Chapter 15). In Fig. 14-1(A), we illustrate the
interaction of a positive charge on the z-axis with negative electron density.
The energy is given by -e
2
/r or -eV, where V = - e/r is the electron potential
felt by the positive charge located at the point r. In Fig. 14-1(B), we represent
a dipole moment in the field of electronic charge. Now the energy associated
* Several of the principIes covered in Sections 14--1 lO 14--4 are common to both nqr and
Mbss bauer speclroscopy, so these sections should be read befare Chapter 15.
+
z
(A
wi
eh;
po
COI
of
fiel
rel
(he
we
ele
qu.
cal
del
po
by
qw
po
wh
fiel
de
cm
WI
of
Th
gra
gra
604
+
I
+
+
r
z z z
(Al (81 (el
FIGURE 14-1 The
interaction 01 (A) a positive
charge, (B) a dipole, and (e)
a quadrupole with the
z-component 01 the electric
lield arising Irom a unit
negative charge 8.
with the orientation of the dipole depends upon how the potential energy
changes over the dipole. Thus, we a re interested in how the electrostatic
potential changes over the dipole or uv/oz. This is referred to as the z-
component of the electric field, Ez . In Fig. 14-1(C), we illustrate the interaction
of a quadrupolar distribution with the electric field. Now we have the electric
field from the electro n in effect interacting with two dipoles whose configuration
rel ative to each other is fixed, i.e., a quadrupole. The energy wiU depend upon
the rate of change (or gradient ) of the electric field over the quadrupole. Thus,
we are con cerned with the "change in the change" of the potential from the
electron, or the second derivative of V with respect to z, that is, 0
2
V/uz
2
This
quantity, which is also the change in the electric field component, oEz/oz, is
called the electric fi eld gradient.
In our molecule we ha ve a nucleus imbedded in a charge c10ud of electron
density. The electric field gradient is defined in terms of a time-averaged electric
potential from an electron. Furthermore, the electron field gradient is described
by a 3 x 3 tensor V, which is symmetric and has a zero trace. The nuclear
quadrupole moment is also described by a 3 x 3 tensor Q. The nuclear quadru-
pole coupling energy EQ is given by
where Q i) is the nuclear quadrupole moment tensor and V i) is the electrostatic
field gradient tensor arising from the electron di stribution. The product will
depend upon the mutual orientation of the two axis systems. For Q, it is
convenient to select a n axis system that coincides with that of the spin system.
When this is done, the cylindrical symmetry of the nucleus permits definition
of the tensor in terms of one parameter, the nuclear quadrupoJe moment Q.
The sign of this quantity must be known to obtain the sign of the electric field
gradient. An axis system can also be chosen in which the electrostatic field
gradient tensor is diagonal. This is called the principal axis system 01 (he fi eld
I

606 Chapter 14 Nuclear Ouadrupole Resonance Spectroscopy, NOR
gradienllensor, and the only non-lero elements are the diagonal elements whose
wl
magnitudes produce a traceless tensor:
m
WI
When comparing a given a tom in different molecules, it is necessary to know
the orientation of the field gradient principal axis system in the molecular
framework axis system. Three Eulerian angles (a, [J, and y) are required.
The asymmetry of a molecule a nd the direction of the z-axis of the field
gradient , qw relative to the crystal axes can be inves ti gated by studying the
nqr spectrum of a single crystal in a magnetic field. The Zeeman splitting is a
function of orientation, and detailed analysis of the spectra for different
orientations enables one to determine the direction of the z-axis of the field
gradient, qzz. This axis can be compared to the crystal axes.
When the principal axes of the coordinate system of the molecule are
principal axes of the electric field gradient tensor, the potential energy EQ for
interaction of the quadrupol e moment with the electric field gradient at the
nucleus is given by
(14-1)
We define the electric field gradient V
zz
as eqzz' where e is the electron charge
(4.8 x 10 - 10 esu). Since the trace of the electric field gradient tensor is lero, we
need define only one more quantity to specify the field gradient, and this is
done in equation (14-2):
(1 4-2)
The quantity r is called the asymmelry paramefer. The quantities V
xx
, V
yy
, a nd
V
zz
a re often written as eqxx' eqyy' and eqzz. By convention, Iqzzl > Iqxxl > Iqyyl ,
so r ranges from to 1 as a result. With a lero trace, the field gradient is
completely defined by eq and J1.
Substituting these definitions of qzz and r into equation (14- 1) and using
the fact that qzz + qxx + qyy = 0, we obtain
(1 4-3)
When axial symmetry pertains, r equals zero and EQ becomes equal to
e /4)qQzz (Note t hat Qz: + Qxx + Qyy = O.)
The classical considerations given aboye are readily expressed by a quan-
tum mechanical operator:
(14-4)
n
qu
fUI
dr
ele
a ~
thl
tio
In
nu
wl
qu
res
tra
e ~
ax
ex
ab
E
N
E
R
G
Y
14
e
a
It
d
re
) r
l e
1)
ge
/>le
IS
-2)
14-2 Energies 01 the Quadrupole Transitions 607
where the summation is over the components of the nuclear quadrupole
moments Q and the eJectric field gradients qj. In the principal axis system
with r defined as aboye, the most common form of the Hamiltonian is given by:
2
H = e Qq [3P -/(l +1) - ~ (p +P:..)]
(14-5)
Q 4/(2/ - 1) 2 +
The product e
2
Qq or e
2
Qq/h (often written as eQqzz or eQqz ) h) is called the
quadrupole coupling constant. The operator HQ operates on the nuclear wave
functions. When r = O, the terms involving the raising and lowering operators
drop out. We shall not be concerned with the explicit evaluation of matri x
elements; the interested reader can consult references 1-3. Suffice it to say that
a series of secular equations can be written and solved to give the eoergies of
the nuclear spin states io the electric field gradient resulting from the distribu-
tion of the electron density of the molecule.
14-2 ENERGIES OF THE aUADRUPOLE TRANSITIONS
In an axialIy symmetric field (1] = O), the energies of the various quadrupolar
nuclear states are summarized by the following equation:
e
2
Qq[3m
2
- f(l +1)]
E = - ---- --- (14-6)
m 4/(2/ - 1)
where / is the nuclear spin quantum number, and m is the nuclear magnetic
quantum number. For a nuclear spin of / = 3/
2
, m can have values of 3/
2
, 1/
2
,
-1/
2
, - 3/
2
. For m = 3/
2
, substitution into equation (14-6) produces the result
E 3/2 = + e
2
Qq/4. Since m is squared, the value for m = - 3/
2
wilI be identical to
that for m = + 3/
2
, and a doubly degenerate set of quadrupole energy states
results. Similarly, the state [rom m = 1/
2
will be double degenerate. The
transition energy, LlE, indicated by the arrow in Fig. 14-2, corresponds to
e
2
Qq/4 - (- e
2
Qq/4) = e
2
Qq/2. Thus, for a nucleus with a spin / = 3/
2
in an
axially symmetric field, a single transition is expected, and the quantity e
2
Qq
expressed in energy units can be caJculated directly from the frequency of
absorption e
2
Qq = 2t:.E = 2hv. The quantity e
2
Qq is often expressed as a fre-
/ ~ m =-+-1
/ - 2
E /
/ FIGURE 14-2 Ouadrupole
N
/
/
energy levels in a spherical
E
----::
,
/
/
6.E
field (Al and an axially
,
R
symmetric field (B).
G
",
,
Y
"
' ___ m =::2
1
E = - e
2
Qq / 4
(A)
(B)
quency in MHz, althoughstrictlyspeakingthi sshould be e
2
Qq/h. Fortheaboye
case, e
2
Qq would be twice the frequency of the nqr transition.
The number of transitions and the relationship of the fr equency of the
transition to e
2
Qq can be calculated in a si milar manner for other nucl ei with
differentJ valuesin axiallysymmetricfieJds by usingequation(14-6). ForJ = 7/
2
,
four energy levels (E 1/2' E 3/2' E 5/ 2' and E _7/2)and three transi tions result.
The selection rule for these transitions is L1m = 1, so the observed transitions
are E ~ 1 2 ~ E 3/2' E3/2 ~ E 5/2' and E5/2 ~ E7/2. (RecalJ that alllevelsare
populated under ordinary conditions). Substitution of J and m into equation
(14-6) produces the result that the energy of the EI 3/ 2 ~ J!. 5/2 transition is
twice that of the E 1/ 2 ~ E 3/2 transiti on. The energies of these levels and the
influence ofthe asymmetry parameter r on these energies are illustrated in Fig.
14-3. In measuredspectra,deviationsfrom the frequencies predicted when r = O
are attributed to deviations from axial symmetry in the sample, and, as will be
seen shortly, this deviation can be used as a measure ofasymmetry.
m =7/2
m = 3/2
m = 1/ 2
FIGURE 14--3 Nuclearquadrupole
energy level diagram tor 1= 7 /
2
.
1
l
l I I
00.20.40.60.81.0
1)
In a nuclearquadrupoleresonance(nqr)* experiment, radi a tion in the radio
frequency regionis employed toeffect transitionsamongthe variousorientations
of a quadrupolar nucleus in a non-spherical field. The experiment is generally
carried out on a powder. Different orientations ofthe small crystals relative to
the d. frequency direction affect only the intensities of the transitions but not
their energies. Structural information about a compound can be obtained by
considering how different structural and electronic effects influence the asym-
metry of the electron environment. One set of resonances is expected for each
chemically or crystallographically inequivalent quadrupolar nucleus. Crystallo-
graphic splittings are often small compared to splittings from chemical non-
equivalence.
Two types of osciJlators have been corr:monly used in nqr, the super-
regenerativeandthemarginaloscillator.Thesuperregenerativeoscillatoris most
common because it allows broad bandscanning in searching for resonances and
is not complicated to operate. Ithas the disadvantage ofproducing a multiplet
oflines for each resonance, as shown in Fig. 14-4(A), because ofits particular
Fo r reviews or nqr, see he Genera l Rererences.
r
a
d
3
I1i
14-2 Energies 01 the Ouadrupole Transitions 609
________1\__
(A) (B)
FIGURE 14-4 (A) Multiplet 01 peaks lor a single resonance lrom a
superregenerative oscillator; (B) single peak Irom a marginal oscillator for the
same resonance as in (A).
operational characteristics. The true resonance frequency is the center line of the
multiplet. The marginal oscillator gives a single peak for each absorption, but it
requires constant adjustment and is tedious to operate. Details regarding the
instrumentation have been published(4)
The 35C1 nqr spectrum of CI
3
BOPCI
3
is shown in Fig. 14-5. Resonances
for three non-equivalent chlorines (CI
3
POBCI
2
+CI-) are found . Two of the
resonance centers are indicated by x marks on the spectrum at 30,880 MHz
and 31,280 MHz. The center of the third resonance around 30,950 MHz is
difficult to determine accurately beca use of overlap with the resonance at
31,280 MHz.
In addition to this direct measurement of the quadrupolar energy level
difference by absorption of radio frequency radiation, the same information
may also be obtained from the fine structure in the pure rotation (microwave)
l'
l ~ ~
rY
~
J. lA
11'LI,
~
J
~
lIu !\
l'
~ 1\ r\I
J,J
''''"
r"
,
I J
Ir
Al
~
I
I
'''11
K ~ ~
~ ~ lA!lJ
,
~ lalJ
JIIrr
6 31 ,500 4 3 2 31,000 9 8 7 6
30.500
MHz MHz MHz
FIGURE 14-5 The 35CI nqr spectrum 01 CI
3
BOPCI
3
at 77 K with 25-kHz markers.
1
610 Chapter 14 Nuclear Quadrupole Resonance Spectroscopy, NQR
spect rum of a gas. The different nuclear orientations give slight ly different
moments of inertia, result ing in fine struct ure in the microwave spectrum. The
direct measurement by absorption of radi o freq uency radiati on must be carried
out on a sol id. In a liquid or even in sorne solids (especially near the melting
point ), collisions and vibrations modulate the electri c field gradient t o such an
extent that the lifetime of a quadrupole state becomes very short. This leads to
unce;tainty broadening, and the line is often not detected.
The energy difference between the various levels and, hence, the freq uency
of the transition wilI depend upon both the field gradient, q, produced by the
valence electrons and the quadrupole moment of the nucleus. T he quadrupole
moment, eQ, is a measure of the deviation of the electric cha rge di strib ution of
(h e nucleus from spherical symmetry. For a given isotope, eQ is a constant, and
values for ma ny iso topes can be obtained from several sources.<S,6) They can
be measured with a tomic beam experiments. The units of eQ are charge times
distance squared, but it is common to express the moment simply as Q in units
2
of cm For example, 35CI with a nuclear spi n 1 = 3/
z
has a quadrupole moment
10-
2 4
Q of -0.08 x cm
2
, the negative sign indicating tha t the charge di stribu-
tion is flattened relative to the spin axis (see Fig. 7-1).
The second factor determining the extent of splitting of the quadrupole
energy levels is the field gradienl , q, at the nucleus produced by the eleclron
dislribulion in the molecule. The spl itting of a quadrupole leve! will be rel ated
to the product e
2
Qq. For a molecule with axia l symmetry, q often lies along
the highest-fold symmetry axis, and when eQ is known, one can obtain the
value of q. In a non-symmetri c en vironmen t, the energies of the various
quadrupole levels are no longer given by eguation (1 4-6), beca use the fulI
Hamiltonian in equation (14--5) must be used. For 1 = 3/
z
, the following
equations can be derived(2) for the energies of the two states:
3Qq 1 + 11 2/ 3
E - - (14--7)
!: 3/ 2 - 41(21 - 1)
(J 4--8)
From the difference of equations (14--7) and (14--8) and E = hv, it is seen that
one transi tion with frequency v = ( Qq/ 2h) J 1 + 11 2/ 3 is expected for 1 = 3/
2
.
Since there are two unknowns, 11 a nd q, the value for eZ Qq cannot be obtained
from a measured frequen cy. As will be seen shortly, thi s problem can be solved
with resu lts from nqr experiments on a sample in a weak magnetic field.
T he equations for nuclei with 1 values other than 3/
2
have been reported,
and in many instances where more t han one line is observed in the spectrum,
both the asymmetry parameter, 11, and e
2
Qq can be obtained from the spect rum.
For 1 = 1, the equations are:
-2e
2
Qq
E - ----
( 14--9)
0 - 41(21 - 1)
1
fl
ti
A
(1
d
el
d
m
m
cal
tha
7/
2
a lH
14-
Wh
fiel,
nuc
Jn
on ,
ofa
---
--
14-3 Ellect 01 a Magnetic Field on the Spectra 611
and
E _ e
2
Qq(l 1])
(14-10)
1 - 4!(2! _ 1)
The corresponding energy levels are indicated in Fig. 14-6(B), where K stands
for e
2
Qql(4I(21 - 1)). The perturbation of these levels by an applied magnetic
field is indicated in Fig 1 6(C). This effect will be discussed in the next sect ion.
As can be seen from Fig. 14-6(B), there are three transitions for 1 = 1 and 1] =1 O
(labeled v+, v_ , and vol, so the two unknowns, e
2
Qq and 1], can be determined
directly from the spectrum. The energies of the levels in Fig. 14-6 are given by
equations (14-9) and (14-10). T he energies of \1+, v_, and V
o
are found by the
differences in the energies of the levels. For any two transitions, the resulting
equations can be solved for the two unknowns e
2
Qq and 1]. Itis interesting to
point out that for a nucleus with 1 = 1 in an axially symmetric field, only one
ne is expected in the spectrum [see Fig. 14-6(A)].
-
VD
V+
E == K(1 +TI) /
/
/
/
I
m== ::t: 1 (
/
\
\
\
\
\
\
E, = K(1 - TI)
",
,
,
,
",
,
'-
JJ
m=O
-- E == - 2K
(A)
(B) (C)
T he energies of the quadrupole levels as a function of 1] have been
calculated( 2) for cases other than T = 1 or 3/2' Tables have also been compil ed(3)
that permit ca lculations of1] and e
2
Qq from spectral data for nuclei with! = 5/2,
7/2, and 9/2' When 1] is appreciable, the selection rule 11m = 1 breaks down,
and spectra containing 11m = 2 bands are often obtained.
14-3 EFFECT OF A MAGNETIC FIELO ON THE SPECTRA
When an nqr experiment is carried out on a sample placed in a stat ic magnetic
field, the Hamiltonian fl M describing the influence of the magnetic field on the
nuclear magnetic dipole moment must be added to the nqr H amiltonian:
(14-11)
In weak magnetic fields (gNfJ .vH ~ e
2
Qq) the magnetic field acts as a pert urbation
on fj Q' In general, the influence of this term on the energies is to shift the energy
01 a non-degenerate quadrupoLe leve/ and sp/it a doub/y degenerate level [ i.e., one
FIGURE ~ Energy levels
lor I = 1 under different
conditions. (A) '1 = Oand
applied magnetic field
Ho = O. (B) '1 =1 Oand Ho = O
(C) '1 =1 Oand Ho =1 Obut
constant.
,
having m =1- O; see equation (14--6)]. This change in energy of the non-degenerate
quadrupolar levels is indicated in Fig. 14--6(B) and (C) for a nucleus in which
1 = 1 and 1'/ =1- O.
For a nucleus with 1 = 1, a quadrupole spectrum with two hnes can arise
from either of two distinct situations: for 1'/ =1- O as noted aboye (Fig. 14--6(B)), or
for nuclei with 1'/ = O located in two non-equi valent latti ce sites. Examination
of the spectrum of the sample in an external field allows a distinction to be made
between these two possibilities. In the former case (1'/ =1- O), two lines would again
be observed, but with different energies than those obtained in the absence of the
field ; in the latter case, each doubly degenerate level would be split, giving a
spectrum with four lines.
As mentioned earlier, the levels E 1/ 2 and E 3/ 2 are each doubl y degenerate
for 1 = 3/
2
in a non-symmetric field. As a result, e
2
Qq and 1'/ cannot be determined
directly. This degeneracy is removed by a magnetic field, with four levels resulting.
Four transitions are observed in the spectrum: + 1/
2
---> + 3/
2
, + 1/
2
---> _ 3/
2
,
_1/
2
--->+ 3/
2
, and _1/
2
--->_ 3/
2
~ I m l = +1). The energy differences corre-
sponding to these transitions are functions of H, e
2
Qq, and 1'/ [see equations
(14--7) and (14--8)J, so q and 1'/ can be evaluated(7) for this system from the spectra
of the sample taken both with and without an applied magnetic field .
14-4 RELATIONSHIP BETWEEN ELECTRIC FIELD
GRAOI ENT ANO MOLECULAR STRUCTURE
Our next concern is how we obtain information about the electronic structure
of a molecule from the values of q and 1'/. The field gradient at atom A in a
molecule, qmot, and the electronic wave function are related by equati on (14--2):
qmot = e{ I [2
B
(3 cos
2
e
AB
- 1)/R
A B
3
J - fl/J* I [(3 cos
2
eA" - 1)/ r
A
,,3JI/J dT}
B*A n
(14--12)
The molecular field gradiant qmol is seen to be a sensiti ve measure of the electronic
charge density in the immediate vicinit y of the nucleus because equation (14--12)
involves the expectation value O/r
3
). The first term in the equation is a
summation over al1 nuclei external to the quadrupolar nucleus, and the second
term is a summation over al1 electrons. If the molecular structure is known, the
first term is readily evaluated. ZB is the nuclear charge of any atom in the
molecule other than A, the one whose field gradient is being investigated ; ()AB is
the angle between the bond axis or highest-fold rotation axis for A and the radius
vector from A to B, R
AB
. The second term represents the contribution to the
field gradient in the molecule from the electron density, and it is referred to as
the electric field gradient qel' Final1y, I/J is the ground state wave function, and
eA" is the angle between the bond or principal axis and the radius vector r A" to
the nth electron. This integral is difficult to evalua te. In the LCAO approxima-
tion, we can write
(14--13)
\\
a
fe
lf
a
Ct
l
ai
q,
el
ec
th
TI
Fl
ti c
we
W
ate
Fe
or
14-4 Relationsh ip Between Eleclri c Field Gradient and Molecular Structure 613
e
e
n
e
a
e
a
re
a
}
12)
mc
12)
a
nd
he
he
IS
to
a-
-13)
where qA = (3 COSI e- l )j r
3
; u is the index over the molecular orbitals; and i
andj areindicesfor atomicorbitals. C
iu
and C
ju
represent the LC;\Ocoefficients
for the atomic orbitals (Pi and CfJj in the u molecular orbital. Thc integral may
involve one, two, orthree centers. Obviously, good wave functions are required,
and an involved evaluation of equation (14-13) is needed to interp:et 1.- Fo.r
certain atoms (e.g., N and CI), the three-center contribution is small and can be
ignored. Separating the one- and two-center terms in equation (l4-13) and
abbreviatingthe intergralsSCfJ;CIACfJj dr asqA
i
<etc., we canwriteequation(14-13)
as (14-14):
(14-14)
There have been several semi-empirical methods proposed for evaluating
electric field gradients. Cotton and Harris(8) assumed that the nuclear term of
equation(14-12) (i.e. , thefirst term) was cancelled by the partofqet arisingfrom
the gross atomic populations on the neighbor atom B; i.e. ,
This leads to
(l4-16)
Further, by assuming that the two-center integral can be formulated as propor-
tional to the overlap integral
(14-17)
we can write:
(14-18)
We see then that the field gradient is given by multiplying qA
ij
by the gross
atomic population, P [equation (3-31)J, or:
(14-19)
Foran atom A with valence sand p orbitals, the aboyesummation is over four
orbitals for which qA for the s orbital is zero, and
q
= - eq (p _- P - P )
al - 2 x 2 y
where qat is the field gradient for one electron in a p orbital. The quantity in
parentheses in equation (14-18) is just the molecular-orbital expression for the
gross atomic populat ion P ofatomic orbital <Ji' (See hapter 3.) D pending on
the relative populations of p" Px' and P.v' q can be positive or negative. If the
quadrupole couplingconstant is expressed in megahertz, we have
(14-20)
where e
2
Qqjh is the quadrupole coupling constant, and e
2
QqaJh is the coupling
constantfora single electronin the p orbital.Thepz orbitalshould becoincident
with qzz in order to apply these equations with much accuracy.
Equation (14-20) is the molecular orbital analog to the valence-bond
expression of Townes and Dailey,(9) which had been reported earlier. This
approach is based on the following arguments. Since the s orbital is spherically
symmetric,electron density in thi sorbital will notgive ri se to a field gradient. As
long as the atom being studied is not the least electronegative in the bonds to
other atoms in the molecule, the maximum field gradient at this atom, qmol' is
the atomic field gradient, qat ' for a single electron in a pz orbital ofthe isolated
atom. When theatom being investigated is moreelectronegative than the atom
to which it is bonded,thequadrupolaratom hasgreaterelectron density around
it in themoleculethanin the isolatedatom.Therel ationshipbetweentheelectron
"occupation"ofthe p orbitals ofa quadrupolara tom in a molecule, e
2
Qqat' and
the quantitye
2
Qqmol (which is determinedfrom the nqrspectrum ofthe molecule
under consideration) is given by:
(14-21)
where Qqat is the quadrupolecouplingconstantfor occupancy ofthe p orbital
by a single electron,s is thefraction ofs characteremployed by the atom in the
bond to its neighbor, d is the fraction ofd character in thi s bond, and i is the
fractionofioniccharacterin thebond(fora moleculeA- B, 1/10 = el/lA + dI/lB and
2
d
2
i = e - ). When the atom being studied is electropositive, i changes signo
Values ofe
2
Qqat and qat have been tabulat ed for several atoms(4,5.IO,II) When
TC bonding is possible, this effect must also be included. A modified form of
equation (14-21) has also been employed:(12)
(14-22)
whereTC is theextentof TC bonding,anda1l otherquantitiesarethesameasbefore.
As the amount of ionic character in a bond increases, the electronic
environment approaches spherical symmetry (where qmol = O) and e
2
Qqmol de-
creases. Hybridization ofthe p orbital with an s orbital also decreases e
2
Qqmol'
as indicated by equation (14-22). Mixing of the s orbital with the p orbital
decreases the field gradient, because the s orbital is spherically symmetric. In a
covalent molecule, d orbital contribution to the bonding increases the field
gradient.
There are several probJems associated with these approaches to the inter-
pretation of field gradients. First, even if the aboye approach were correct for
the system ofinterest, there arefour unknowns in equation(14-22) and we have
e
e

t
e
P
[1
l'
(
w
el
,.
e)
!l(
In
c
14-4 Relationship Between Electric Field Gradient and Molecular Structure 615
only one measurable quantity, e
2
Qqmol' Investigators attempting to interpret this
quantity are thus forced to assume the answer and provide a reasonable
interpretation of the data based on these models. Second, O ' Konski and Ha(1 3)
have shown that the assumption of Cotton and Harris(8) indicated in equation
(14-15) is not generally correct. When thi s equat ion does not apply, equations
(14-20), (14-21), and (14-22) are also not correct.
A semiempirical approach to the interpretation of field gradients has been
reported,( 14) which does not make the suspect approximations described above.
The reader is referred to the original literature for details of this method.
Electrostatic, E, covalent, e, and transfer, T, parameters derived from bond
g
energies are reported to provide an interpretation of chlorine field gradients( 14b)
lt
One additional factor complicating the quantum mechanical calculation and
interpretat ion of nqr and Mossbauer (vide inFa) parameters is the Sternheimer
d
effect ( 15) Thi s effect is the pol ari zation of the originally spherically symmetric
is
inner shell electrons by the valence electrons. When the core electrons lose their
,y
spherical symmetry, they contribute to the field gradient at the nucleus. This
IS
effect, like spin polarization (discussed in Chapter 12), is an artifact of not
:0
performing a full molecular orbital calculation on the whole crystal. There are
IS
two contributions to Sternheimer shielding, and these can be illustrated if we
:d
consider the ligands or ions external to the electron density of the atom as point
m
charges. The spherical expansion of the core electron density is illustrated for
ld
positive point charges in Fig. 14-7(A) amI (B). he asymmetry induced is shown
>n
in Fig. 14-7(C). We have artificially broken up the polarization to illustrate these
ld
two contributions to the Sternheimer shielding .
le
+
+
~ l
illustration 01 the
tal
Sternheimer effect. (A) A
:he
spherical shell 01 electron
the
density; (B) the radial
.nd
expansion resulting Irom two
external positive charges;
(e) the elliptical polarization
by two positive charges.
(A) (B)
(e)
The shielding for closed shell systems is usual1y expressed by the equation:
+
+
where Qqo is the field gradient calculated in the absence of any Sternheimer
effects and "I r; is the shielding parameter for the ith charge located at a distance
r from the nucl eus. The sign of "I r" is a function of t he distance. For charges
external to the core electron density of the central atom, )I r; will gene rally be
negative and is said to gi ve rise to an antishielding contribution. For charges
inside the valence orbitals of the central atom, the sign of "I ri is generally positive
,
l
and gives rise to a shielding eontribution. Shielding eonstants have been ealcu-
lated for eharges external to a large number of ions and are designated by the
sym bol y"" . The value of Yr; used to evaluate the Sternheimer effeet in moleeules
is diffieult to determine but appears to be eonsiderably below that of 1' 00 ' Most
workers in the field assume that this effeet is constan t in a similar series of
complexes.
14-5 APPLlCATIONS
NQR speetra of a number of moleeules eontaining the following nuclei have been
reported: 27 AI, 75As, 19 7Au, lB, I1B, 135Ba, 137Ba, 209 Bi, 79Br, 81Br, 43Ca,
35CI, 37CI, 59CO, 63CU, 69Ga, 71Ga, 2H, 201Hg,
127
1, 11 5In, 25 Mg, 14N, 55 Mn,
23 Na, 93Nb,
17
0, 185Re, 187Re, 33S, l2lSb, l 23Sb, l B1Ta.
The Interpretation o( fl Qq Data
As mentioned aboye, it is not possible to interpret e
2
Qq values rigorously in
terms of ionie eharaeter, n bonding, and s and d hybridization. or eompounds
in whieh there are large differenees in ionie eharaeter, the effect can be clearly
seen, as indicated by the data in Table 14-1. M ore positive e
2
Qqmol values are
obtained for ionie eompounds. Attempts have be en made to "explain" e
2
Qq data
for a Jarge number of halogen eompounds by assuming that d hybridization is
not important and estimating ionie eharaeter or s hybridization.< 12. 16)
When the differenees in ionie eharaeter are large enough to be predictable,
the e
2
Qqmol values manifest the proper trends. H owever, for systems in whieh
the differenees in ionie eharaeter are not obvious from eleetronegativity and other
eonsiderations, the interpretation of e
2
Qq differenees is usually ambiguous in
terms of the relative importanee of the effeet s in equation (14-22). O ne of the
more sueeessful studies involves a series of substituted ehlorobenzenes. A linear
relation is found between the Hammett (J eonstant of the substituent and
the quadrupole resonanee frequeneyy7) The data obeyed the equation v
(MHz) = 34.826 + 1.024(J. The eleetron-releasing substituents have negative (J
values and give rise to smaller e
2
Qq values, beca use the inereased onie eharaeter
in the C-Cl bond makes the ehlorine more negatively eharged.
TABLE 14-1. Values 01 e
2
Qqmol lar Some Diatomic
Halides
Mol ecule" tlQqmol Mol ecule" e
2
Qqmol
FCI -146.0 BrC! 876.8
BrC! -103.6 LiBr 37.2
ICI - 82.5 NaBr 58
TI
-.!
-15.8 DBr 533
KCI 0.04 FBr 1089
RbCl 0.774
DI
- 1827
CsCI 3 Nal -259.87
a Values for e
2
Qq" are 35C1 = -109.74, 79 Br = 769. 76, and
127
1 =
- 2292.84. e
2
Qqmol appli es to the underlined atom.
e
(C
el
tI
~
15
Itl
re
al
W1
co
TI
of
th
El;
A
re,
cal
sa
mi
lat
(di
lo,
inc
ex!
1
2
me
col
[e
[he
ha,
2.1
15.1
ha\
nUl
14-5 Applications 61 7
The general problem of covalency in metal-ligand bonds in a series of
complexes has been investigated by direct measurement of the quadrupole
resonance.(18) By comparing the trends in force constants with the changes in
chlorine quadrupole coupling constants, a consistent interpretation of the data
for a whole series of MCI
6
" - compounds has been offered(1 9) A rigorous
interpretation of the data (especially where small differences are in volved) is again
hampered by the lack of information regarding the four variables in equation
(14-22).
Two transitions are observed in the nqr spectra of 55 Mn (I = 5/
2
), SO both
qzz and r can be obtained, Measurements on a series of organometallic manga-
nese carbonyls ha ve been reported.(20) Substitu tion of methyl groups in the series
(CH
3
)"C
6
H
6
-
II
Mn( Oh + causes only minor changes in the asymmetry param-
eter. A summary of cobalt-59 nqr investigations has appeared.(21) The magni-
tudes of the field gradients are indicative of cis or (rans octahedal geometry. The
e
2
Qq value of [cis-Co(enhCI
2
JCI is 33.71, whereas that for [lrans-Co(enhCI
2
JCI
is 60.63. A rationaliza tion of this difference will be provided in the next chapter,
in the section on partial field gradient parameters.
Thermochemical bond energies have been estimated and compared with the
2 2
results from chlorine-35 nqr for the GeCl/ - , SnC1
6
- and PbC1
6
- ions. The
authors(22) support an earlier conclusion( 23) that these results a re not consistent
with assigning a higher electronega tivity to lead than to germanium or tino
This coverage of quadrupole investigations concerned with elucidating
covalency and other characteristics of chemical bonds is by no means complete.
The presentation is brief because of the ambiguity that exists in the interpretation
of the result s. More information than just the field gradient is needed to sort out
the variables in equation (14-22).
1
e
r Ellecls 01 the Crystal Lattiee on the Magnitude 01 tr Qq
i
A further complication and limitation of the application of nqr spectroscopy
\'
results from the fact that direct measurement of nuclear quadrupole t ransitions
can be obtained only on solids. For very complex molecules, this is the only
'T
source of nuclear quadrupole informa tion because of the complexity of the
microwave spectrum. Measurements on solids introduce the complexities of
lattice effects, For those molecules which have been studied by bot li methods
(direct measurement and microwave), it is found that e
2
Qq is usually 10 to 15%
lower in the solid state. It has been proposed( S) that the decrease is due to
increased ionicity in the solido There are several examples of molecules being
extensively associated in the solid but not in the gas phase or in solution (e.g.,
1
2
and CNCI). In these cases, consi derable care must be exercised in deducing
molecular properties from Qq values, The e
2
Qq values for cobalt in selected
cobalt complexes illustrates(21) the problem, The values for Irans-
[Co(NH3)4Cl2]C1 and Irans- [Co(en}z 1
2
JCl are 59.23 M Hz and 60.63 MHz; Le. ,
there is a difference of J.40 MHz. On the other hand, Irans-[Co(en)2C I2J N03
has an e
2
Qq(Co) value of 62.78 MHz, Changing the anion causes a difference of
2.15 MHz. The e
2
Qq(C I) values of K
2
SnCl
6
and [(CHJ)4N]2SnCI6 are
15.063 MHz and 16.674 MHz. respectively. Potential causes for these differences
have been offered.(22b,22c) Examples in which the crystal lattice affects the
number of lines observed in a sp ctrum will be discussed in the next section.
61 8 Chapter 14 Nuclear Ouadrupole Resonance Spectroscopy, NOR
Slruclural Information from NOR Spectra
Since different field gradients will exist for non-equivalent nuclei in a molecule,
we should expect to obtain a different line (or set of lines, depending on 1) for
each type of nuclear environment. In general , the environment of an atom as
determined by nqr studies is in agreement with results obtained from x-ray
studies. Only one line is found(18) in the halogen nqr spectrum of each of the
following: K
2
SeCI
6
, Cs
2
SeBr
6
, (NH
4
hTeCI
6
, (NH4hSnBr6, and KzPt 16 This
is consistent with 0" structures for these anions.
As mentioned aboye, the following effects can give rise to multiple lines in
the nqr spectrum:
1. Chemically non-equivalent atoms in the molecule.
2. Chemically equivalent atoms in a molecule occupying non-equivalent
positions in the crystal lattice of the solid.
3. Splitting of the degeneracy of quadrupole energy levels by the asym-
metry of the field gradient. Splittings of the quadrupole levels by other magnetic
nuclei in the molecule, similar to spin-spio spli ttings in nmr, are often not detected
io nqr spectra, but are being found with improved instrumentation. Usually these
splittings a re less than, or of the same order of magnitude as, the line widths.
One case in which such splitting has been reported(Z4) is in the spectrum of H10
3
.
The 127) nucleus is split by the proton.
The non-equivalence of lattice positions (2) is illustra ted in the bromine nqr
spectrum of K
z
SeBr
6
, which gives a single line a t room temperature and two
Iines at dry ice temperature. A crystall ine phase change accou nts for the
difference. NQR is one of the most powerful techniques for detecting phase
changes and obtai ning structural information about the phase transi tions.
Although K
2
Ptl
6
, K
z
Sn Br
6
, and K
z
TeBr
6
contai n "octahedal" anions, the
halides are not equivalent in the solid lattice, and the hali de nqr spectra all consist
of three Iines, indicating at leas t three differen t halide environments.
Four resonance lines were found in the chlorine quadr upole spectra of each
of TiC1
4
,(2Sa) SiCI
4
,(25b) a nd SnCI
4
.(25bJ It was concluded that t he crystal struc-
tures of these materials are similar.
The problem of distinguishing non-equivalent positions in the lattice from
chemical non-equivalence in the molecular configuration (which is relatcd to the
structure of the molecule in the gas phase or in a non-coordinating solvent) is
difficult in some cases. In general, the frequency di fference for li nes resulting from
non-equivalent lattice positions is small compared to the differences encountered
for chemically non-equivalent nuclei in a molecule. When only slight separations
between the spectral lines are observed, it is difficult to determine from this
technique alone which of the two effects is op rative. Another difficulty en-
countered in interpretation is illustrated by the chlorine spectrum of M
z
Cl
10
species(Z6J Even though the Nb
2
Cl
1o
molecule has a structure containing both
terminal and bridging chlorines, only a single chlorine resonance assigned(Z6) to
the bridging atom is observed in the spect rum. l n ReZClo and W
2
Cl
1o
, a large
number of resonances were obtained.(Z6) Consequently, arguments based on
assigning the number of d ifferent types of nuclei in the molecular structure to
the number of resonances ob erved can be of doubtful validity.
NQR studies of 14N (1 = 1) are difficult to carry out but produce very
interesti ng results. Since 1 = 1, both eZ Qq and the asymmet ry parameter 11 can be
eva
Th
or
gni
sIl!
the
Th
it i
nit
Br<
h ~
rel1
cor
o f ~
ap
inc
cor
di
exr
resl
etel
the
Al.
10,
Ref
par
A
gra
evaluated from the nqr spectrum. In BrCN, the 14N nqr resonance is a doublet.
T his could result from two non-equivalent nitrogen atoms in the crystal lattice
or from a splitting of the nitrogen resonance because of an asymmetric field
gradient. The former explanation was eliminated by a single crystal x-ray
study(27) The structure of solid BrCN was found to consist of linear chains of
the type:
... Br-C N I" . Br-C- N I' .. Br-e - N I
The nitrogen has axial symmetry here, and only one line is expected. H owever,
it is proposed that interactions between chains reduce the symmetry at the
nitrogen and lead to the two lines. Various resonance forms can be written for
BrCN, and the e
2
Qq values indicate that the bromine has a formal positive
charge. An appreciable increase in e
2
Qq for bromine is observed in the solid
relative to the gaseaus state spectrum of BrCN. This could be due to increased
contributions to the ground state from the structure Br+CN- in the solid because
of stabilization of Br ! by coordination. If the N .... Br-C bond is described as
a pd hybrid, the increased d contribution in the bromine carbon bond wiU also
increase Qq.
The 14N quadrupole transitions in pyridine and various coordination
compounds of pyridine show(28) large changes in the transition energies. As
discussed in conjunction with Fig. 14-6, three transitions v ~ , vo, and v ) are
expected when r #- O, and Qq and r can be determined from the data. T ypical
results are summarized in Table 14-2.
The iodine nqr spectrum of sol id iodine indicates a large asymmetry param-
eter, r(29) Since the iodine atom in an iodine molecule is axially symmetric,
the large asymmetry is taken as indication ofintermolecular bonding in the solido
A large '1 in the iodine nqr spectrum of the molecule ArO) supports the structure
rOz( OH) instead of HI0
3
. The structure HT0
3
has a C
3
axis, so qxx = qyy.
References 1 and 2 contain many additional examples of studi es of this kind.
Information regarding n bondiog can be obtained from the asymmetry
parameter r. Methods for evaluating '1 for various nuc\ei have been discussed.
A single (J bond to a halogen should give rise to an axial1y symmetric fi eld
gradient. Double booding leads to asymmetry, and the extent of n bonding is
TABLE 14-2. 14N Ouadrupole Transitions and Field Gradient
Parameters in Pyridine and Coordinated Pyridine (AII Frequen-
cies in kHz, Temp. = 77 K). (Crystallographic Non-Equivalences,
Where Present, Are Resol ved.)
e2Qq
Compound v+
V
o
h
>J
Pyridine (Py) 3892 2984 908 4584 0.396
Pyridinium nitrate 1000 580 420 1053 0.798
pY2ZnCl2
2387
2332
2078
2038
309
294
2977
2913
0.207
0.202
PY2 Zn(N0
3
)2 2124 1884 240 2672 0.180
2097 1877 220 2649 0.166
PY2
CdCl
2
2850 2298 552 3432 0320
620 Chapler 14 Nuclear Quadrupole Resonance Spectroscopy, NQR
related to 17 . It was concluded that there is appreciable ( ~ 5 ) carbon-halogen
rr bonding in viny! chloride, viny! bromide, and vinyl iodide.(30) Bersohn(31) has
made a complete study of the problem of quantitativel y estimating the extent of
carbon-halogen rr bonding from 17 .
The values of r obtained from the nqr spectra of Si1
4
, Ge1
4
, and SnT
4
were
interpreted to indicate a very small degree (about 1 %) of double bond char-
acter( 32) in the halogen bond to the central atom. This could be due to a
solid state eJfect.
The 77As, 121,
123
Sb, 209 Bi, 35,
37
Cl, and 79,
81
Br nqr spectra ofcompounds
with general formula R
3
MX
2
have been studied(33) for R = CH
3
, CH
2
C
6
H
5
, and
C
6
H
5
, fol' X = F, CI, and Br, and for M = As, Sb, and Bi. Very small asymmetry
parameters were found, indicating a threefold axis in all compounds. The results
suggest that most of the compounds are trigonal bipyramidal. However, the
arsenic compound [(CH3hAsBr " JBr - is not, but probably has a cation with
C
3v
symmetry.
The nqr spectra e
7
CI , 35CI, 121Sb,
12 7
1) of 2ICI' AICl
3
and 2ICI SbCI
5
indicate(34) that these materials should be formulated as ICI
2
+AICI
4
- and
ICI
2
+SbCI
6
-. The nqr spectra of the v-shaped cations ICI
2
+, 13 +, and 1
2
Cl+
have been studied in several diJferent compounds. The 35Cl nqr spectra of the
chloroaluminate group in a wide variety of MAAICI
4
)m compQunds have been
studied.(35) The transition energies can be used to indicate whether the relatively
free ion AICI
4
- exists or whether this anion is strongly coordinated to the cation.
" Ionic" AICI
4
- transitions are found in the 10.6 to 11.3 MHz range. Strong
coordination of AICl
4
- results in an elongation of the AI-Cl bridge bonds ami
an appreciable increase in the range and average frequency of the chlorine
transitions.
In the next chapter, on Mossbauer spectroscopy, we shall discuss an additive,
partial field gradient (pfg), model for correlating field gradients at central atoms.
It is useful for deducing structures of molecules from experimental Mossbauer
data. This model can also be used to infer structures from nqr data. Since most
of the data used to derive and test the pfg model are Mossbauer results, we shall
treat this topic in the next chapter.
14-6 DOUBLE RESONANCE TECHNIQUES
Nuclear double resonance techniques have been reported(3 6- 38) for observing
quadrupolar transitions. These methods greatly increase sensitivity over previous
techniques and also permit one to observe transitions with very low frequencies;
e.g., in 2H spectra, transitions are observed in the 100 to 160 kHz region.(39)
The adiabatic demagnetization double resonance experiment is a novel
technique in this general category. Consider a sample that has a quadrupolar
nucleus in a molecule containing several protons. When this sample is placed in
a magnetic field and we wait long enough for equili brium to be obtained, there
will be an excess of proton nuclear moments aligned with the field that undergo
Larmor precession and give rise to a net magnetization, as discussed in the
chapters on nmr. When the sample is removed from the field , the net magnetiza-
tion is reduced to zero as the sample is removed beca use the individual moments
now become aligned with their local fields. A random orientation of these local
fields in the absence of an external field produces a zero net magnetization. This
1
P
fi
ti
a
w
!TI
m
re
Fi
an
sp
M
o
O
freq
has
bet,
etTe
trar
mel
fiek
infl
the I
and
~ Double Resonance Techniques 621
is illustrated in Fig. 14-8 on the left-hand side, in the region labeled "samp\e
removed."
If TI is longer than the time required to remove the sample, the excess
population of +1/
2
spins wiU remain, but they now precess about a net local
field felt atthenucleusfrom spin-spin interactionwith neighboringprotons.Over
thefull sample,themagnetization is zero; butwhen thissampleis reinserted into
a magnetic field, magnetization is simultaneously induced into the sample
without having to wait the required time for the TI process. This is illustrated
in the region of Fig. 14-8 labeled "sample reinserted." The intensity of the
magnetization can be measured by employing a 90 pulse immediately after
reinserting the sample in the magnetic field and measuring the FI D curve (see
Fig. 14-8).If the time between the removal ofthesamplefrom the magneticfield
and reinserting it is longcompared to TI' the magnetization will decrease as the
spins become randomized.
JL
FIGURE 14-8 Plot of the
magnetization when a
M
sample is removed from a
magnetic field, reinserted,
subjecled to a 90 pulse, and
then allowed lo undergo free
e
induclion decay.
>
O
O
-,
Time I I FID
I
1,
I
I
:r
1 TI I I
Sample Sample 90
. t
Removed Reinserted Pulse
di
Now consider an experiment in which the sample is irradiated with an rf
frequencycorrespondingto thequadrupolarnucleusB transitionafterthesample
has been removed from the field. Furthermore, we shall assume that the time
between removal and reinsertion is small compared to TI for the protons. The
effect of this rf field is to randomize the B nucleus by inducing quadrupolar
transitions in the B spin system. Provided that the appropriate conditions are
met, in terms ofthe amplitude ofthe applied rffield in relationship to the local
field experienced at the protons, the randomization of the B spin system
inftuences thatofthe proton system. Thisoccurs by thefollowing process. When
thesampleis removed from thefield,theenergydifTerence between them = +1/
2
and _1/ 2states (Le., the transition energy ofthe H nucleus) decreases toward
zero.Intheprocess,thereis a timeatwhichtheenergydifferencefor thehydrogen
nuclei matches the energydifference ofthe quadrupolarstates ofthe Bnucleus.
A resonance energy exchange occurs, tending to randomize the proton nuclei.
The process of randomization is often referred to as an increase in the spin
temperature ofthesystem. As a result ofthe randomization ofthe protonsystem
from transitions in B, the magnetization that is recovered when the sample is
returned to the magnetic field is less than it would otherwise be. As a result, the
his
:
1
17
FID measured is less than it would otherwise be. When the frequency used for
the quadrupole transition is not appropriate for resonance, the B nucleus is not
randomized and a large amount of the magnetization is recovered. By sys tem-
atically incrementing the frequency of the B transmitter, the "spectra" of the
quadrupole transitions ofthe B system are mapped out in terms of their effect
on the FID ofthe abundant proton spin system.
By using a spin echo double resonance experiment ,(39- 41
J
much of the
inhomogeneousdipolar broadening(crys tal imperfections,etc.)thatleads to very
broad Iines in the direct nqr experiment can be eJiminated. The nqr ofAI 2Br6
has been determined with this technique.(40
J
Ifone has two quadrupolar nuclei surrounded by nuclei with 1 = O [ e.g.,
as in D-Mn(Co)sJ, the dipolarcouplingofthe manganese and deuterium nuclei
can be observed.(42
J
As discussed in the nmr chapters, the bond distance can be
obtained from the magnitude ofthe dipolarcoupling. A Mn- D bond distance
of1.61 Ais calcuJated from the SSMn nqrspect rum, in excellent agreement with
the neutron diffraction result. (4 3)
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
REFERENCES
CITED
1. C. P.Sl ichter,"PrincipIesofMagnetic Resonance," Harper& Row,New York, 1963,
Seco6.3.
2. R. Bersohn,1. Chem. Phys., 20, 1505 (1952).
3. R. Livingston and H.Zel des, "Tables ofEigenvalues for Pure Quadrupole Spectra,"
Oak Ridge Nat!. Lab. Rept. ORNL- 1913 (1955).
4. a. T. P. Das and E. L. Hahn, "Nuclear Quadrupole Coupling :':pectroscopy,"
Academic Press, ew York, 1958.
b. E.A.C. Lucken,"NuclearQuarupoleCouplingConstants,"Academic Press, New
York, 1969.
5. C. T. O' Konski, " Determination ofOrganic Structures by Ph ys ical Methods," Vo!.
2,ed. F. C. Nachod and W. D. Phillips, Academic Press, New York, 1962.
6. J.A. Popl e, W.G.Schneider,and H.J. Bernstein," High Resolution Nuclear Magnetic
Resonance," McGraw-Hill, New York 1959.
7. C. Dean, Phys. Rey.,86, 607A (1952).
8. F.A. Cottonand C. B.Harris, Proc.Nat!. Acad. Sci. U.S.,56,12(1966); Inorg. Chem. ,
6, 376 (1967).
9. C. H.Townes and B. P. Dailey, J. Chem. Phys. , 17,782 (1949).
JO. M.H.Cohen and F. Reir," Solid StatePhysics," Vo!. 5, ed. F.Seitzand D. Turnbull,
Academic Press New York, 1957.
11. W.J. Oryille-Thomas, Quart. Rev., 11, 162 (1957).
12. B. P. DaiJey, J. Chem. Phys., 33, 1641 (1960).
13. C. T. Q' Knski and T. K. Ha, J. Chem. Phys., 49, 5354 (1968).
]4. a. W. D. White and R. S. Drago,J. Chem. Phys., 52, 4717(1970).
b. R. S. Drago, N. Wong, and D. Ferri s, J. Amer. Chem. Soc., 113, 1970 (1991).
15. R. M. Sternheimer, Phys. Rey. , 130,1423 (1963); bid., 146, 140 (1966) and references
t herei n.
]6. C. H. Townes and B. P. Dailey J. Chem. Phys., 23, 118 (1955); W. Gordy, Disc.
araday Soc., 19, 14 (1955); M.1\. Whitehead and H. H.JafIe, Trans. Faraday Soc. ,
57, 1854 (1961).
32.
33.
34.
35.
36.
37.
38.
39.
40.
41. .
42.
43.:
-
M. I
T. P
E. A.
1. A.
17. H. C. Meal, J. Amer. Chem. Soc., 74, 6121 (1952); P. 1. Bray and R. G. Barnes, J.
Chem. Phys., 27, 551 (1957) and references therein.
18. D. Nakamura, K. Ito,and M. Kubo, Inorg. Chem., 1, 592 (1962); ibid., 2, 61 (1963);
J. Amer. Chem. Soc., 82 5783 (1960) ; ibid., 83, 4526 (1961); ibid., 84, 163 (1962); M.
Kubo and D. Nakamura, Adv. Inorg. Chem. Radiochem., 8, 257 (1966).
19. T. L. Brown,W.G. McDugle,andL. G.Kent,J. Amer.Chem.Soc.,92,3645(1970).
20. T. B. Brill and A. J. Kotlar, Inorg. Chem., 13,470(1974).
21. T. L. Brown, Accts. Chem. Res., 408, (1974) and references therein.
22. a. W. A. Welsh,T. B. Brill, el al., Inorg. Chem, 13, 1797 (1974).
b. T. B. Brill, R. C. Gearhart, and W. A. Welsh, J. Mag. Res. , 13, 27 (1974).
c. T. B. Brill, J. Chem. Phys., 61, 424 (1974).
23. R. S. Drago and N. A. Matwiyoff, J. Organometal. Chem., 3, 62 (1965).
24. R. Livingston and H. Z Ides, J. Chem. Phys., 26, 351 (1957).
25. a. A. H. Reddoch, J. Chem. Phys. ,35,1085 (1961).
b. A. L. Schawlow, J. Chem. Phys., 22, 1211 (1954).
26. P. A. Edwards and R. E. McCarIey, Inorg. Chem., 12, 900 (1973).
27. S. Geller and A. L. Schawlow, J. Chem. Phys., 23, 779 (1955).
28. Y. N. Hsieh, G. R. Rubenacker,C. P.Cheng, and T. L. Brown,J. Amer. Chem. Soc.,
99, 1384(1977).
29. H. G. Dehmelt, Naturwissenschaften, 37, 398 (1950).
30. 1. A. Howe and 1. H. Goldstein, J. Chem. Phys., 26, 7 (1957); 27, 831 (1957) and
references therein.
31. R. Bersohn, J.Chem. Phys., 22, 2078 (1954).
32. H.Robinson,H. G.Dehmelt,andW. Gordy,J. Chem. Phys.,22,511 (1954); S. Kojima
el al., J. Phys. SocoJapan,9, 805 (1954).
33. T. B. Brill and G. G. Long, Inorg, Chem., 13, 1980 (1970).
34. D.1. Merryman and 1. D. Corbett, Inorg. Chem., 13, 1258 (1974)
35. D. J. Merryman, P. A. Edwards, J. D. Corbett, and R. E. McCarIey, lnorg. Chem.,
13, 1471 (1974).
36. SR.Har tmannand E. L. Hahn, P hys. Rev. , 128, 2042 (1962).
37. R. E. Slusher and E. L. Hahn, Phys. Rev., 166, 332 (1968).
38. D.T. Edmondsel al., "Advancesin QuadrupoleResonance," Vol. 1, p. 145, Heyden,
London, 1974; Rev. Pure Appl. Chem., 40, 193 (1974).
39. 1. L. Ragle and K. L. Sherk, J. Chem. Phys., 50, 3553 (1969).
1.
40. M. Emshwiller, E. L. Hahn, and D. Kaplan, Phys. Rev. , 118, 414 (1960).
41. J.L. Ragle el al., 1. Chem. Phys., 61,429,3184(1974).
42. a. P.S.Ireland,L. W.Olson,andT. L. Brown,J. Amer.Chem.Soc.,97,3548(1975).
b. P. S. Ireland and T. L. Brown,J. Mag. Res., 20, 300 (1975).
43. S. J. LaPlacael al., Inorg. Chem. ,8, 1928 (1969).
M. H. Cohen and F. Reif. " Solid State Physics," Vol. 5, ed. F. Seitz and D. Turnbull, ADDITIONAL
Academic Press, New York, 1957.
REFERENCES
T. P. Das and E. L. Hahn, " Nuclear Quadrupole Resonance Spectroscopy," Academic
E. A.C. Lucken,"NuclearQuadrupoleCouplingConstants,"AcademicPress, New York,
1969.
J. A. S. Smith, ed., " Advances in Nuclear Quadrupole Resonance," Heyden and Sons,
London: Vol. 1, 1974; Vol. 2, 1975; Vol. 3,1977.
8
EXERCISES
1. a. Calculatetheenergiesofall thequadrupolarenergy states for a nucleus with ! = 2.
Express the energies as a function ofe
2
Qq.
b. How many transitions are expected, and what IS the relationship between the
energy ofthe transitions and elQq?
2. a. Using the equations presented in tbis chapter for the energies of the Oand
1leve!s ofa nucleus with ! = 1in an asymmetric field, calculate the frequency
in terms ofe
2
Qq and r for the 0--+ +1 and 0--+ - 1 transitions.
b. Express the energy difference between the two transitions in part a in terms of r
and e
2
Qq.
c. Show how r and q can be determined from this information.
3. Describe an nqr experiment that would give information regarding the extent ofn
bondingin the phosphorus-sulfurbondsinPSCl
3
and(C6HshPS.Canyou determine
whether the sulfur is hybridized Sp2 and utilizes a p orbital in bonding or whether
the Px and P
y
orbitals ofsu][ur participateequally in bonding with nqrexperiments ?
(Note: for 33S, ! = 3/2')
4. It has been reported that the
127
1quadrupole resonance in AS!3 is a singlet but has
a very large asymmetry parameter.(281A single crystal x-ray study indicates that the
As is nearly octahedral. Explain the large asymmetry parameter.
5. Indicate the number of resonance lines expected for the following nuclei under the
conditions given:
127
1 a. (1 = 5/2); r =O; Ho =O.
b. 14N (1 = 1); r =O; H o =O.
c. 7sAs (1 = 3/2); r = O; Ho = O.
e. 14N (1 = 1); r = 1; H o= O.
f. 14N (T=l);r=I;H
o
=l=O.
6. The quadrupolar energy ofa nucleus is given by
e
2
Qq[3m
2
- T(l + I)J
E =-----'=c...:..::...____
m 4!(2! _ 1)
S9CO has!=
7
/2 and a natural abundance of100%.
a. How many cobalt nqr transitions wilI be observed for K
3
Co(CN)6? What are the
transition energies in terms ofe
2
Qq?
b. Repeat part a for K3CO(CN)sBr.
9.
10.
11.
Exercises 625
7. Consider the nilrogen nqr ofeach of the fol lowi ng systems. How many lines would
you expect with and wi thout a magnetic field ? (For 14N,1 = 1.)
j
y
1)

;?
as
ne
he
the
c. :NO
8. The S9CO (1 = 7/
2
) frequencies in CI
3
SnCo(CO)4oeeurat 35. 02MHz ( s/2 ..... 7/
2
),
23.37MHz (3/
2
..... s/ 2), and 11.68MHz (1/
2
..... 3/
2
). Calculate r and e
2
Qq.
(Hint: What are the ratios ofthe frequeneies when r = O?)
9. A eompound having the formul a CH
3
InI 2 is k nown. It is believed to be an ionie
compound, (CH3hIn+ InI4-. Provided there are no erystallographically non-equiv-
alent cations or anions, how many resona nce Iines would you expeet for 11 SIn a nd
1271 in thi s eompound ? The cation has r = 0.05. Wh ich strueture of this cation is
suggested by thi s small value?
10. In so.lid pyri dine (C
S
H
5
) at 77 K, 14N Iines are found at 3.90 a nd 2.95 MHz.
What are e
2
Qq/ h a nd '7 for nitrogen in pyridine?
11. The in the speclrum of HgCI
2
lie at 22.05 and 22.25 MHzat 300 K.
I I
22.05 22.25
InHgCI2 .dioxane,a single 3sCllinea t20.50MHzis found at 300 K.Inthedioxanate
/ ,.
eomplex, an Hg <- O"donor-aeceptormteraetlon occurs.
a. What is the probable souree oflhe line splitting in pure HgCI
2
?
b. The eleetrie quadrupole momenls of 3sCI and 3
7
CI are 0,079 x 10- 24 cm
2
and
24
0.062 x 10- cm
2
, res peetively. At what frequency would you expeet to find 37C1
resonanees in HgCl
2
?
c. In terms ofthep orbital populatio ns ofequation ( 14-13), ra tionalize the deerease
in the 35C1 resonanee frequency in the dioxa nate adduct of HgCl
2
compared to
that in pure HgCI
2
.
.
Mossbauer
Spectroscopy
.!) '"

E
:J
e
.:
'" >
ro
Oi
a:
15-1 INTRODUCTION
Mossbauer spectroscopY,( l) abbr viated as MB spectroscopy, involves nuclear
transitions that result from the absorption of y-rays by the sample. This tran ition
is characterized by a change in the nuclear spin quantum n umber, l. The
conditions for absorption depend upon the electro n density about the nucleus,
and the number of peaks obtained is related to the symmetry of the compound.
As a result, structural informat ion can be obtai ned. M any of the concepts and
symbols used in this chapler have beell previously discussed in hapter 14.
To understa nd the principIes of this method, first consi der a gaseous system
consisting of a radioactive so urce of y-rays and the sample, which can a bsorb
y-rays. When a gamma ray is emitted by the source nucleus, it decays to the
ground state. The energies of the emitted y-rays, E
y
, have a range of 10 to 100
keV and are given by equation (15-1):
Ey = Er + D - R (15-1)
where Er is the difference in energy between the excited state and ground state
of the so urce nucleus ; D, the Doppler shift, is due to the trans lat ional motion of
the nucleus, and R is t he recol energy of the nucleus. The recoil energy, similar
to that occurring when a bullet leaves a gun, is generally 10 - 2 to 10 - 3 eV and
is given by the equation:
R = E//2mc
2
(15-2)
where m is the mass of the nucleus and c is the velocity of light. The Doppler
shift accounts for t he fact that the energy of a y-ray emitt d from a nucleus in a
gas molecule moving in the same direction as the emi tted ray is different from
the energy of a y-ray from a nucleus in a gas molecule moving in the Qpposite
direction. The distribution of energies resulting [rom the translational motion of
the source nuclei in many directions is refe rred to as Doppler broadening. The
left-hand curve of Fig. 15- 1 represents the disl ribution of energies of emitted
y-rays, Ey , from Ihis effect. The breadth of the curve resul'ts [rom Doppler
broadening. The dashed line in Fig. 15- 1 is taken as En the energy difference
between the nuclear ground and excited states of the source. The energy difference,
R
re
a
In
to
qu
to
15
rel
As
y-r
sar
101
tra
th(
wh
g ~
Th
a f
the
red
wo
by
nue
soli
rea!
sou
626
-
ear
ion
fhe
eus,
IOd.
and
tem
orb
the
100
5- 1)
tate
,nof
r
and
5-2)
'<-
o
~
Q)
.D
E
:J
e
Q)
>
..,
ro
Q)
a:
FIGURE 15-1 Distribution 01
ener gies 01 emitted and
absorbed l'-rays.
R, between the dotted line and the average energy of the left-hand curve is the
recoil energy transmitted to the source nucleus when a y-ray is emtted.
In MB spectroscopy the energy of the y-ray absorbed for a transi tion in the
sample is given by:
(15-3)
I n this case, R is added beca use lhe exciting y-ray must have energy necessary
to bring about the transi tion and d fcct recoil of the ab orbing nucleus. The
quantity D has the same significance as before, and the value of Er is ass umed
to be the same for the source and the sample. The curve in the ri ght half of Fig.
15-1 shows the distribution of y-ray energies necessary for absorption. The
relationshi p of the sample and source energies can be seen from the entire figure.
As indicated by the shaded region there is only a very slight probability that the
y-ray energy from the source will match that required for absorption by the
sample. Sinee the nuclear energy levels are quant ized, there is accordingly a very
low probability that lhe y-ray from the source wil! be absorbed to give a nuclear
transition in the sample. The main cause for nonmatching of y-ray energies is
the recoil energy, with lhe disl ribution for emission centered about Er - R,
whereas that for absorption is centered about Er +R. The quantit y R for a
gaseous molecule ~ 1 O -
1
eV) is very much larger lhan the typical D oppler energy.
The source would have to move wi th a velocily of 2 x 10
4
cm secO 1 to obt ain
a Doppler effect large enough to make the source and sample peaks overlap, and
these velocities are not readily obtainable. However, if the quantity R could be
reduced, or if condtions for a recoil less transition could be found, the sample
would have a higher proba bi li t y of a bsorbing y-rays from the source. A indicated
by equation (1 5-2), R can be dccreased by increasing m, the mass. By placing the
nucJeus of the sample and source in a solid, t he mass is effectively that of the
solid and the recoil energy will be smaIl as indicated by equat ion (15-2). For this
reason, MB spectra are almost always obtained on so lid samples employing solid
sources.
628 Chapter 15 M6ssbauer Spectroscopy
By placing the source and sample in solid lattices, we have not effected
recoilless transitions for all nuc1ei, but we have increased the probability of a
recoilless transition. The reason for this is that the energy of the y-ray may cause
excitation of lattice vibrational modes. This energy term would function in the
same way as the recoil energy in the gas; i.e., it would decrease the energy of the
emitted partic1e and increase the energy required for absorption. Certain crystal
properties and experimental conditions for emission or absorption will leave the
lattice in its initial vibrational state; i.e., conditions for a recoilless transition will
be satisfied. It should be emphasized that these conditions simply determine the
iotensity ofthe peak s obtained, for it is only the number ofpartic1es with matching
energy that is determined by this effect. We shall not be concerned with the
absolute intensity of a band, so this aspect of MB spectroscopy will not be
discussed. It should be mentioned, however, that for sorne materials (usually
molecular solids), lattice and molecular vibrational modes are excited to such an
extent that very few recoilless transitions occur at room temperature and no
spectrum is obtained. Frequently, the spectrum can be obtained by lowering the
temperature of the sample.
By going to the solid state we have very much reduced the widths of the
resonance lines over that shown in Fig. 15-1. The Doppler broadening is now
negligible, and R becomes 10-
4
eV for a 100 keV gamma ray and an emitting
mass number of 100. The full width of a resooance line at half height is given by
the Heisenberg uncertainty principIe as I1E = hiT = 4.56 x 10-
16
/0.977 x 10-
7
=
4.67 X 10-
9
eV or 0.097 mm sec-
1
(for 57 Fe). The line widths are infinitesimal
compared to the so urce energy of 1.4 x 10
4
eVo The range of excited state lifetimes
for Mossbauer nuc1ei is 10- 5 sec to 10 - 10 sec, and this leads to line widths of
10-
11
eV to 10-
6
eV for most nuc1ei . This subject is treated in references 1 to
5, which contain a more detailed discussion of the entire subject of MB
spectroscopy.
Our main concern will be with the factors affecting the energy required for
y-ray absorption by the sample. There are three main types of interaction of the
nuc1ei with the che mi cal environment that result in small changes in the energy
required for absorption: (1) resonance line shifts from changes in electro n
environment, (2) quadrupole interactions, and (3) magnetic interactions. These
effects give us information of chemical significance and will be our primeconcern.
Before discussing these factors, it is best to describe the procedure for
obtaining spectra and to illustrate a typical MB spectrum. The electron
environment about the nuc1eus infiuences the energy of the y-ray necessary to
cause the nuclear transition from the ground to excited state, i.e., Er in the sample.
The energy of y-rays from the source can be varied over the range of the energy
differences arising from electron environments in different samples by moving
the source relative to the sample. The higher the velocity at which the source is
moved toward the sample, the higher the average energy of the emitted y-ray (by
the Doppler effect) and vice versa. The energy change I1Es of a photon associated
with the source moving relative to the sample is given by:
(15-4)
where El' is the stationary energy of the photon, va is the velocity of the source,
and eis the angle between the velocity of the so urce and the line connecting the
...
'"
e
:::J
O
u
a
a;
.D
E
:::J
Z
a
n
c
\\
ti
1
e'
fr
T
h
be
co
o.e
co
of
are
an
pn
fro
:d
a
se
he
he
lal
he
viII
the
ing
the
be
111y
l an
no
the
the
now
ting
n by
7 =
imal
imes
OSof
1 to
MB
d for
)f the
nergy
(15--4)
source and the sample. When the source is moving directly toward the sample,
cos e= 1. In order to obtain an MB spectrum, the so urce is moved relative to
the sample, and the source velocity at which maximum absorption of y-rays
occurs is determined.
Consider, as a simple example, the MB spectrum of Fe
3
+Fe
lJl
(CN) 6 [where
Fe
JII
Fe
H
and designate weak and strong field iron(IlI), respectively]. This
substance contains ron in two different chemical environments, and y-rays of
two different energies are required to cause transitions in the different nuclei . To
obtain the MB spectrum, the source is moved relative to the fixed sample, and
the absorption of y-rays is plotted as a function of source velocity as shown in
Fig. 15-2. The peaks correspond to source velocities at which maximum y-ray

...
e
:l
o
u
FIGURE 15-2 MB spectrum 01
'+-
o
FeFe(CN)6'
O
.D
E
:l
Z
mm sec-
1
absorption by the sample occurs. Negative relative velocities correspond to
moving the source away from the sample, and positive relative velocities
correspond to moving the so urce toward the sample. The relative velocity at
which the so urce is being moved is plotted along the abscissa of Fig. 15- 2, and
this quantity is related to the energy of the y-rays. For a 57Fe source emitting a
14.4 keV y-ray, the energy is changed by 4.8 x 10- 8 eV or 0.0011 cal mole -1 for
every mm sec - 1 of velocity imposed upon the source. This result can be calculated
from equation (15-4):
I1E
s
1 mm
-
- 3.00 X 10
11
sec-
I
mm sec
1 x 14.4 X 10
3
eV = 4.80 x 10-
8
eV
This energy is equivalent to a frequency of 11.6 MHz (v = E/h, where
h = 4.14 X 10-
15
eV sec). For other nuclei having a y-ray energy of Ey (in keV),
E
1 mm sec - 1 = 11.6 x -y- MHz
14.4
Referring again to the abscissa of Fig. 15-2, one sees that the energy difference
between the nuclear transitions for Fe3+ and Fe
lll
in FeFe(CN)6 is very small,
corresponding to about 2 x 10-
8
eY. The peak in the spectrum in Fig. 15-2 at
Fe
Ill
0.03 mm sec - 1 is assigned(6) to and that at 0.53 tO' the calon Fe
3
+ by
comparison of this spectrum with those for a large number of cyanide complexes
of iron. Different line positions that result from different chemical environments
are indicated by the values for the source velocity in units of cm - 1 or mm sec - 1,
and are referred to as isomer shifts, center shifts, or chemical shifts. We shall now
proceed with a discussion ofthe information contained in the parameters obtained
from the spectrum.
1
i
.
630 Chapter 15 Mssbauer Spectroscopy
15-2 INTERPRETATION OF ISOMER SHIFTS
The two different peaks in Fig. 15-2 arise from the isomer shift differences of the
two different iron atoms in octahedral sites. The isomer shift resu lts from the
electrostatic interaction of the charge distribution in the nucleus with the electron
density that has a finite probability of existing at the nucleus. Only s electrons
have a finite probability of overlapping the nuclear density, so the isomer shift
can be evaluated by considering this interact ion. It should be remembered that
p, d, and other electron densities can inftuence s electron density by screening
the s density from the nuclear charge. Assuming the nucleus to be a uniformly
charged sphere of radius R and the s electron density over the nucleus to be a
constant given by if;/(O), the difference between the electrostatic interacti on of a
spheri cal distribution of electron densit y with a point nucleus and that for a
nucl eus with radius R is given by
bE = K[if; / (O)] R
2
(15-5)
where K is a nuclear constant. Since R will have different values for the ground
state and the excited state, the electron density at the nucleu,s will interact
differentl y with the two states and thus will inftuence the energy of the transi tion;
i. e.,
bE
e
- bEs = K [ if; / (O)J(R / - R/) (15- 6a)
where the subscript e refers to the excited state and g to the ground sta te. The
inftuence of if;/(O) on the e!1ergy of the transition is illustrated in Fig. 15- 3 for
57 Fe, which has l = 1/
2
for the ground state and 1 = %for the excited state. The
energies of these two states are affected di fTerently by if; / (O), and the Iransition
energy is changed.
FIGURE 15-3 Changes in the
ener gy 01 the Mossbauer
E
(e)
<e>
transition lor different values 01
1jJ/(O). This is a graphical
illustration 01 equation (15--16a)
with two different values 01
1jJ / (O) lor an 5
7
Fe nucleus. The
N
E
R
G
Y
r
(g)
dillerences in 1jJ/(O) must result
Irom a cubic or spherical
1 = %
(g)
distribut ion 01 bonded atoms in
order lor this diagram to apply.
.,/cO)
<
.,/cO)
The R values are constant for a given nucleus, but if; / (O) varies from
compound to compound. The center shift in the Mbssbauer spectrum is the
difference between the energy of this transi tion in the sample (or absorber) and
the energy of the same transi ti on in the so urce. This difference is given by the
difference in equati ons of lhe form of (15- 6a) for lhe so urce and sample, or:
(15-6b)
v
s
t
c
s
e
e
1
a
\1
d
d
a
e
\1
t
d
F
a
e
s
11
1
1
a
ti
n
d
l(
l(
e
e
1
e
e
11
~
it
II
g
Y
a
a
a
;)
d
:t
le
lr
le
~
15-3 Quadrupole Interactions 631
where the subscripts a and b refer to absorber and so urce, respecti vel y. Standard
sources are usually employed (e.g., 57CO in Pd for iron Mossbauer spectra, or
BaSn0
3
for tin spectra). The 57 CO decays to 57Fe in an excited state via electron
capture. The excited 57Fe decays to stable 57Fe by ( -ray emission. When standard
sources are emplo):ed [tf ,z(O)]b is replaced by a constant, C. Furthermore, the
change in radi us Re - Rg is very small , leading to the foll owing commonly
employed expression for the center shift:
C.S. = K' (j: [tf / (O) a - CJ (15-6c)
where (jR = Re - Rg ; C is a constant characteristic of the source ; and K' is 2KR
2
Both K' and i3 R/ R are constants for a given nucleus, so the center shift is directly
proportional to the s electro n density at the sample nucleus. The term center shift
is used for the experimentally determined center o[ the peak; the term isomer
shift is now used when the center shift has been corrected [or the small Doppler
contribution from the thermal motion of the Mossbauer atom. The sign of (jR
depends upon the difference between the effective nuclear charge radius, R, of
the excited and ground sta tes (Re2 - R ~ 2). For the 57Fe nucleus, the excited state
is smaller than the ground state, and an increase in s-electro n density produces
a negative shift. In tin , the sign of (jR is positive, so the opposite t rend of shift
with s electron densit y is observed.
As mentioned abo ve, electron density in p or d orbitals can screen the electron
density from the nuclear charge by virtue of the fact that the electron density in
d and p orbitals penet rates the s orbi tal. Hartree- Fock ca1culations show (6,7) t hat
a decrease in the number of d electrons causes a marked increase in the total s
electron density at the iron nucleus. Accordingly, with comparable Iigands and
with negative (jRIR, Fe2+ has an appreciably larger center shift than F 3 I . When
these ions are examined in a series of molecules, the interpretation becornes more
difficult, for the d, s and p el ectron densities are modified by coval ent bonding.
For 57 Fe, for example, an increase in 4s density decreases the center shift , while
an increase in 3d densit y increases Ihe center shift. A series of high spin iron
complexes have been intcrpreted on this basis. (7) [11 the case of 1I 9Sn, the center
shift increases with an increased s electron density and decreases with an increase
in p electron densit y(8)
15-3 QUADRUPOLE INTERACTIONS
The discussion of the center shift in the previous section applies to systerns with
a spherical or cubic di stribution of electron density. As discussed in Chapter 14,
the degeneracy of nuclear energy levels for nuclei wi th 1 > 1/2 is removed by a
non-cubic electron or ligand distribut ion. For non-integral spins, the splitting
does nol rernove the + or - degeneracy of the m levels, but we obtain a differen t
level for each m set. Thus, t he electric field gradient can lead to J + 1/
2
different
levels for half-integer val ues of 1 (e.g., two for 1 = 3/2 corresponding to 1/2 and
%). For integer values of 1 we obtain 21 + 1 levels (e.g., five for 1 = 2
corresponding to 2, 1, O, -1, -2). The influence of this spli tting on the nuclear
energy levels and the spectral appearance is ill ustrated(9) in Fig. 15-4 for 57Fe.
The ground state is not spli t but the exci ted state is spli t, leading to two peaks
l
632 Chapter 15 MssbauerSpectroscopy
m
- ......---( 0.5.
[ ""Ir t%
z
.:1.. __................ "+..!..
2 - 2
O
1-
"-
a:
U)
en
/

O
/
/ Center Quadrupole
1 /
5hift 5plitting
2--
-1 '-VD -4.0 O 4.0
Center5hitt
mmsec-
1
mmsec-
1
(A) (B) (Cl
FIGURE 15--4 The influence of a non-cubic electronic environment on (A) the
nuclearenergy states of 57Fe and (B) the Mbssbauer spectrum. (C) The iron MB
spectrum of Fe(CO)5 at liquid N
2
temperature(9
1
in thespectrum.Thecentershiftis determinedfrom thecenterofthetworesulting
peaks.When both theground and excitedstateshavelargevalues for 1,complex
Mossbauer spectra result.
The Hamiltonian for the quadrupole couplingis the same as that discussed
for nqr.
HQ = e
2
Qq [(31/ - 1(1 + 1) + + 1:.)J
41(21 - 1)
For the 1= %case e
7
Fe and 119Sn), the quadrupole splitting Q.S. is given by
(15-7)
Thesymbols have aJl been defined in the nqrchapter. For 57Fe, q and r cannot
bedeterminedfrom thequadrupolesplitting.Thesignofthequadrupolecoupling
constant is another quantity ofinterest. IfmI = 3/
2
is at high energy, the sign
is positive; the sign is negative if 1/
2
from 1= %is hi ghest. From powder
spectra, the intensities of the transitions to 1/
2
and %are similar, and it
becomes difficult to determine the sign. The sign can be obtained from spectra
oforderedsystemsorfrom measurementofa polycrystaJlinesamplein a magnetic
field (vide infra). For systems in which the 1 values of the ground and excited
states are larger than those for iron, the spectra are more complex and contain
moreinformation.Thesplittingoftheexcited statewiU notoccurin a sphericaJly
symmetricorcubic field but wiJl occur only when there is a field gradient at the
nucleus caused by asymmetric p or d electron distribution in the compound. A
field gradient exists in the trigonal bipyramidal molecule iron pentacarbonyl,so
a splittingofthe nuclearexcited state is expected, giving rise to a doublet in the
spectrum as indicated in Fig. 15-4(C).
set and the e set of orbitals in octahedral transition metal ion Ifthe t
29 g
complexes have equal populations in the component orbitals, the quadrupole
splitting will be zero. Low spin iron(Il ) complexes (t
2
/ ) will not give rise to
j.
s
1
e
n
S
j
....
1
o
a
te
tt
al
w
al
m
15-4 Paramagnetic Mossbauer Spectra 633
g.
n
r
a
e
d
n
y
e

o
le
n
te
:0
quadrupole splitting unless the degeneracy is removed, and these orbitals can
interact differently with the ligand molecular orbitals. On the other hand, high
spin iron(II) (t
2
/e/) has an imbalance in the t
2g
set, and a large quadrupole
splitting is often seen. If the ligand environment about iron(II) were perfectly
octahedral, d ' d ' and d would be degenerate and no splitting would be
xy yz xz
detected. However, this system is subject to Jahn-Teller distortion, which can
lead to a large field gradient. When the energy separaton of the t
2g
orbitals from
Jahn-Teller effects is of the order of magnitude of kT, a very temperature-
dependent quadrupole splitting is observed. The ground state in the distorted
complex can be obtained if the sign of q is known. The sign can be obtained
from oriented systems or from studies in a large magnetic field. Similar
considerations apply to high spin and low spin iron(III) compounds.
The factors contributing to the magnitude ofthe field gradient were discussed
in Chapter 14. It was shown there that these data were of limited utility in
providing further information about bond types.
15-4 PARAMAGNETIC MOSSBAUER SPECTRA
As shown in Fig. 15-4, a non-cubic electronic environment in an iron complex
splits the degenerate 1 = %excited state of 57Fe into mI states 1/
2
and 3/
2
,
The Mossbauer spectrum consists of a doublet corresponding to the two
transitions shown in Fig. 15-4. When an effective magnetic field, H
eff
, acts on
this system, the degeneracies of the 1/
2
ground state as well as the 3/
2
excited states are removed(10) as shown in Fig. 15-5. The ordering of the levels
reflects the fact that the ground-state moment is positive and the excited state
moment is negative. The resulting six-line spectrum is shown in Fig. 15-5(B).
Since the transitions are magnetic dipole in character, the selection rule is L1m = O,
1 as shown in Fig. 15-5(A). The Hamiltonian is
(15-8)
where gN = 0.18 and 1 = 1/
2
for the nuclear ground state and 9 = -0.10 and
1 = % for the excited state. The intensity of the lines changes with 8, the
orientation of the H
eff
relative to the direction of the Mossbauer radiation. For
an ordered sample, the L1m = O transition has zero intensity for a field parallel
to the radiation. When 8 = 90, the L1m = Otransitions are the most intense of
the six.
The effective field of equation (15-8) consists of the internal field and the
applied field:
H eff = H + Hin'
(15-9)
and is given by
(15-10)
where (S) is the expectation val ue of the spin discussed in Chapters 11 and 12
and A the hyperfine coupling tensor. The internal magnetic field controls the
magnetic hyperfine and it depends in a complex way on the zero field splitting
14
634 Chapter 15 Mbssbauer Spectroscopy
6
3 5
2 4
1
FIGURE 15-5
Magnetic and quadrupole splitting
in a ferromagnetic 57Fe compound.
(A) Energy level diagram. (B)
Expected Mssbauer spectrum.
[Copyright 1973 McGraw-Hill
Magnetlc Quadrupole
~
Book Co. (UK) Limited. From G. M.
spl itting splitting
Bancroft, "Mbssbauer
(A)
Spectroscopy." Reproduced by
permission.)
6
-Ve o +Ve
Velocity (mm S-1 )
(B)
parameters D and E, on the electronic 9 tensors and A tensors, and on the
orientation of the molecule relative to the applied field.
Internal fields exist in some systems in the absence of an applied magnetic
field. T he <S) of equation (15-10) is zero for diamagnetic systems and for systems
with integer values of S in the absence of an applied field ( 11 ) These spectra consist
of quadru pole dou blets. For componds wi th hal f-in teger spin (K ramers' do u blets),
two cases need be considered. With fast electron relaxation, the <S ) averaged
over al! thermally accessible states is zera in zero magnetic field, leading to
quadrupo\e doub\ets. \n tne s\ow re\axation \im\t, magnec Moss'oauer spectra
can be obtained, generally at liquid helium temperatures. These spectra generally
are studied at weak applied field to simplify them by decoupling hyperfine
interactions with ligand nucJei.
In applied fields , magnetic Mossbauer splittings can be observed for both
integer and half-integer spin systems. The applied fi Id mixes the state producing
a non-zero expectat ion value of the spin. The resulting spectra are interpreted
using the spin Hamiltonian formalism(l O.1 2) given in equation (15-11).
fI = D[SZ2 - ~ S(S + 1)] + E(Sx
2
- Sy 2) + {3S g. H + S A 7
2
~ . ~ e Qq { ~ 2 ~ 2 ~ 2
- gNf3N
f
H + 412 3L - f(l + 1) + r(lx - f y )}EFG
( 1 - 1)
(1 5- 11)
By
din
Kri
Ha
pro
an I
sta
pw
be
imid
sam
diffi
A fe
disc
Tab
stud
15-'
1
15-U Applications 635
By standing the spectra as a function of temperature, field strength, and field
direction, the various quantities in the spin Hamiltonian can be determined. For
Kramers ' doublets complimentary information can be obtained from the epr.
However for integer S systems, e.g. , high spin iron(II), magnetic Mossbauer
pr vides the sole means of obtaining electronic structural details.(1 3) Reference
14 presents applications of magnetic Mossbauer.
15-5 MOSSBAUER EMISSION SPECTROSCOPY
57CO decays by an electron capture to 57Fe (T
1
/
2
for 57Fe is 0.1 J-lsec), populating
an excited state of the iron nucleus. The emitted y- rays can be absorbed by a
standard single-line absorber to investiga te the energy levels of the 57Fe nuclei
produced when the source decays. The cobalt-57 analogue of the compound to
be studied is prepared and used as the so urce. Information regarding the
short-lived iron complex in the source is obtained' 15) from this experiment. O ne
must be sure that the desired iron complex remains ntact when the high energy
iron atoms are formed in the cobalt decay process. The results obtained from
sorne oxygenated complexes of 57CO protoporphyrin IX dimethyl ester as a
function of the axial base attached are shown in Table 15-1. These are to be
compared with values of I1E
Q
and b for oxygenated hemoglobin, obtained by
absorption measurements, of 2.23 :.1 nd 0.27 respectively.
TABLE 15-1. Mssbauer Emission Studies(l 2)
(Quadrupole splittings and isometric shifts for oxygenated
complexes of 57C O protoporphyrin IX dimethyl es ter. The
ligands coordinated trans to dioxygen are listed in the first
column.)
Ligand oF, (mm/sec)
l-methyl imidazole 2.17 0.29
1,2-dimethyl imidazo1e 2.32 0.30
pyridine 2.28 0.27
piperidine 2.25 OJO
ethylmethyl sulfide 2.27 0.30
Fig. 15-6(A) shows the emission spectrum of the five-coordinate l-methyl
imidazole complex before oxygenati on; Fig. 15-6(B) shows the spectrum of the
same complex after oxygenatio n.
This technique is particularly important when the parent iron compound is
difficult to prepare and iso late.
15-6 APPLlCATIONS
A few chemical applications of Mssbauer spectroscopy have been selected for
di scussion that are illustrative of tbe kind of information tbat can be obtained.
Table 15- 2 summarizes pertinent information about isotopes that have been
studied by this technique.
Facsimiles of spectra obtained on sorne iron complexes are given in Fig.
15-7. As mentioned previously, fo r high spin iron complexes in which all six
636 Chapler 15 Mssbauer Spectroscopy
FIGURE 15-6 Emission
Mssbauer spectra 01 (A) the
1-methyl imidazole adduct 01
cobalt protoporphyrin IX
dimethyl ester and (B) its O
2
adduct.
o -, -2 -3
Absorber velocitv (mm/se<:
ligands are equivalent, a virtually spherical electric field at the nucleus is expected
for Fe
3
+(d
5
) (t
29
3
eg
2) but not for Fe
2
+(d
6
)(t
29
4e
g
2). As a result of the field gradients
at the nucleus, quadrupole splitting should be detected in the spectra of high spin
iron(Il) complexes but not for high spin iron(I1I) complexes. This is borne out
in spectra A and B of the complexes illustrated in Fig. 15-7. For low spin
complexes, iron(lI) has a configuration t
2
/ and iron(llI) has t
2
/ As a result,
quadrupole splitting is now expected for iron(TIJ) but not iron(TI) in the strong
field complexes. This conclusion is confirmed experimentally by the spectra of
ferrocyanide and ferricyanide ions. When the ligand arrangement in a strong field
iron(JJ) complex does not consist of six equivalent ligands, e.g., [Fe(CN)5NH3J3 -,
quadrupole splitting of the strong field iron(JI) will result. The quadrupole splitting
is roughly related to the differences in the d orbital populations (see Chapter 3) by
1
18
19
TABLE 15-2. Mossbauer Isotopes of Chemical Interest"
Gamma
energy Hall life
b
Hall width Q'
<Jo"
Natural
abundance
oR
10' -
Isotope (keV) 01 precursor (mm s e c ~ l Spin (Barns) (10-
19
cm') ("lo)
R
57Fe
14.4 270 d 0.19
3
- --> -
2 2
+0.3 23.5 2.19 -18 4
61Ni
67.4 1.7 h; 3.3 h 0.78
3 5
- --> -
2 2
0.13 7.21 1.19
67Zn
93.3 60 h; 78 h 3.13 X 10-
4
5 3
- --> '--
2 2
+0.17 1.18 4.11
73Ge
67.0 76 d 2. 19
9 7
- --> -
2 2
-0.26 3.54 7.76
83Kr
9.3 83 d, 2.4 h 0.20
9 7
- --> -
2 2
+0.44 18.9 1\.55 +4 2
99Ru
90 16.1 d 0.15
5 3
- --> -
2 2
>0.15 1.42 12.72
107Ag
93.1 6.6 h 6.68 x
10-
11
1 7
_ -->-
2 2
0.54 5135
l19S
n 23.9 245 d 0.62
3
- --> -
2 2
- 0.07 13.8 8.58 + 3.3 1
121Sb.
37.2 76 Y 2.10
5 7
- --> -
2 2
- 0.29 2.04 57.25 -8.5 3
125Te
35.5 58 d 4.94
1 3
- --> -
2 2
0.19 2.72 6.99 +1
129
1 27.8 33 d; 70 m 0.63
7 5
- --> -
2 2
-0.55 3.97 O +3
l29Xe
39.6 1.6 x l0
7
y 6.84
3
- --> -
2 2
-0.41 1.95 26.44 0.3
133CS
81.0 7.2 Y 0.54
7 5
- --> -
2 2
-0.003 1.02 100
l77Hf
[13.0 6.7 d, 56 h 4.66
7 9
- --> -
2 2
+3 1.20 18.50
lB1Ta
6.25 140 d, 45 d
3
6.48 x 10-
7
9
..,. --> -
2 2
+4.2 17.2 99.99
182W
100.1 115d 2.00 O--> 2 -1.87 2.46 26.41 +1.3
l87Re
134.2 23.8 h 203.8
5 7
- --> -
2 2
+2.6 0.54 62.93
l860S
137.2 90 h 2.37 O--> 2 + 1.54 2.89 1.64
193rr
73.1 32 h 0.59
3
- --> -
2 2
+1.5 0.30 62.7 +0.6
195pt
98.7 183 d [7.30
1 3
- --> -
2 2
0.63 33.8
197Au
77.3 65 h, 20 h 1.85
3 1
- --> -
+0.58 0.44 100 3
.ed
lts
)In
lut
,in
lit,
ng
of
:Id
~ g
,y
2 2
Q Copyright 1973 McGraw-Hill, (UK) Li mited. From G. M. Bancroft, "Mossbauer Spectroscopy." Reproduced by permission.
b d = days, h = hours, y = years, m = minutes.
'The ground-stale quadrupo[e moment, where both ground and excited sta tes have 1 > 1/
2
,
d Cross-section for absorption ofa Mossbauer gamma rayo
638 Chapler 15 Mbssbauer Spectroscopy

IIIIV \ I \ .
J
FIGU RE 15-7 M6ssbauer
spectra 01 some iron(ll)
-0..2 o. ... 0..2
and iron(lIl) complexes.
-0.1 o. +0..2
(A) Spin-Iree
(A)
(8)
iron(II)-FeSO. 7H
2
0
(8) Spin-Iree iron(III)-FeeI
3

(e) Spin-paired
iron(II)-K.Fe(eN)6 3Hp.
(D) Spin-paired
iron(III)-K
3
Fe(CN)6' [From P.
R. Brady, P. P. F. Wigley,
and J. F. Duncan, Rev. Pure
Appl. ehem, 12, 181 (1962) .]
-0..2 -0.1 o. ... 0.1 +0..2
(D)
H ere, qvaJence is the contribution to q from valence electrons in the d orbitals. For
, p-electrons we have
qvale nce = K p[ - NI', + (Np, + Np) ]
TASlE 15-3. Ouadrupole Splitting, t1E
o
, and Isomer Shilt, b, lor Some Iron
1
Compounds (b and t1Eo in mm sec- )
-0..2 o. +0..2
(C)
Compound Ea O Compound !l. Ea
/)
High Spln Fe(lI) Low Spi n Fe(lI)
FeS0
4
' 7H
2
O 3.2 1.19 K4[Fe(CN)6J' 3H
2
O -0.13
3.15 1.3 -0.16
FeS0
4
(anhydrous) 2.7 1.2 <0.1 +0.05
Fe(NH
4
lz(S04lz . 6H 20 1.75 1.19 Na
4
[Fe(CN)6J' 10H
2
O <0.2 - 1.01
1.75 1.3 Na
3
[ Fe( N)sNH
3
J 0.6 -0.05
FeCI
2
'4H
2
O 3.00 1.35 K
2
[ Fe(CN)s NO] 1.85 -0.27
Fe 4H40 6 2.6 1.25 1.76 -0.28
FeFz 2.68 Zn[Fe(CN)s NO] 1.90 -0.27
FCC
2
0
4
2H
2
O 1.7 1.25
High Spin Fe(1I1) Low Spln Fe(lII)
K }[Fe(CN)6J -0.12
FeCI}' 6H
2
O 0.2 0.85 -0.17
FeCI} (anhydrous) 0.2 0.5 0.26 -0. 15
Fe 13' 2NH
4
CI' H
2
0 0.3 0045 Na
3
[ Fe(CN)6J 0.60 -0.17
Fe(N0
3
)} 9H 20 004 004
Fe
2
(C
Z
'')3 . 0.5 0045
Fe
2
(C
4
H
4
0
6
h 0.77 0043
FeZO} 0.12 0047
Values measured at room temperature for L1EQ and the isomer shift, (j, for
a number of iron complexes have been collected
11J
and are Iisted in Table 15- 3.
F or iron complexes, isomer shifts in a positive direction correspond to a decrease
in electron density in the region of the nucleus. For high spin complexes, a
correlation exists between isomer shift and s electron density. An increase in (j
of 0.2 mm sec - 1 is equivalent to a decrease in charge density of 8 % at the
nuc!eus(8J The negative values obtained for the low spin ferricyanides compared
to high spin iron(nl ) complexes indicate more electron density at the nucleus in
the ferricyanide ions. This has been explained as being due to extensive n bonding
in the ferricyanides, which removes d electron density from the metal ion, which
in turn decreases the shielding of the s electrons. This effect increases s electron
density at the nucleus and decreases (j. Both strong (J donors and strong n
acceptors decrease (j.
The M B spectrum of the material prepared from iron(I1I) sulfate and
K4Fe(CN)6 is identical to the spectra for the compounds prepared either from
iron(Il) sulfate and K3Fe(CN)6 or by atmospheric oxidation of the compound
from iron(lI) sulfa te and K4Fe(CN)6' The spectra of these materials indicate t hat
the cation is high spin iron( UI), while the anion is low spin iron(lI).
z
The MB spectrum of sodium nitroprusside, Na
2
Fe(CN)s NO, has been
investigated(9J This material has been formlllated earlier as iron(I1) and NO +
because the complex is diamagnetic. The MB spectrum consists of a doublet with
a L1EQ val ue of 1.76 mm sec- and a (j value of -0.165 mm sec- 1 Comparison
of this vallle with reported reslllts
18J
on a series of iron complexes led the authors
to conclude that the iron (j val ue is close to that of iron(rv). The magnetism and
M B spectrum are consistent wi th a structure in which there is extensive n bonding
between the odd electron in the t
2g
set of the orbitals of iron and the odd electron
on nitrogen, as illustrated in F ig. 15-8. The filled n bonding orbital woul d need
a large contribution from the nitrogen atomic orbital, and the empty n antibonding
orbital would have a larger contribution from the iron atomic orbital to produce
iron(IV). More of the n electron density would be locali zed on nitrogen and the
(j value for iron would approacb that of iron(IV) because of decreased shielding
of the s electrons by the d electrons. Since electron density is being placed in
what was previously a n antibonding orbital of nitric oxide, a decrease in the
N-O infrared stretching freqllency is observed. The very large quadrupole
13
splitting is consistent with very extensive n bonding in the Fe-N-O link.
16
Mossbauer spectra are often useful in determining the oxidati on state of
atoms. It has been shown that the spectra originally assigned to some high spin
iron(n) chelates of salicylaldoxime and other chelates were, in effect, those of an
iron{DI) oxidation product. The oxidized materials gave a center shift [relative
to Na
2
Fe(CN) sNO ' 2H
2
0 ] of ~ 0 6 mm sec-
1
and a small quadrupole splitting.
This smaller-than-expected quadrupole splitting for iron(JI) was rationalized in
terms of n-backbonding. The authentic material prepared under conditions that
were rigorously air-free gave normal iron(lJ) center shifts and large quadrupole
splittings, ~ 1.4. Va lues for the cente r shifts of various oxidation states of high
spin iron compounds are shown in Table 15-4.
The effect of pressure on the M ossbauer spectra of a wide variety of iron
compounds is reported.(16) UpOD applicatioD of pressure ("" 165 kba r) to tri sace-
tylacetona to iron(11I), a new species forms that is attributed lO iron(II). The
change is reversed upon removal of the pressure.
T he determination of the oxidation stat s of tin compounds from M B spectra
FIGURE 15-8 Orbital s
involved in the Fe-N n
bonding lo Ihe NO group in
[Fe(CN)s(NO)]2- .
640 Chapter 15 Mbssbauer Spectroscopy
TABLE 15--4. Isomer Shifts for High Spin Iron Compounds [Shifts Relative to
Na2Fe(CN)sNO . 2H
2
0]
Oxidation state + 1 +2 +3 +4 +6
I.S. +2.2 +1.4 +0.7 +0.2 - 0.6
1
is not as clear-cut as in the case of iron. Values of (3 below 2.65 mm sec - are
often due to tin(IV), and those aboye that value to tin(II). Exceptions are known.
The isomer shifts of sorne four- and six-coordinate tin(IV) componds vary
considerably as the attached anion is varied(1 7)
The MB spectra of the iron pentacarbonyls Fe(CO)s' Fe
2
(CO)9' and
Fe
3
(CO)12 have been reported(l 8, 19) The results are as expected froID the known
structures for both Fe(CO)s and Fe
2
(CO)9' The structure of Fe
3
(COL2 deduced
from its MB spectrum was at odds with infrared results and a preliminary x-ray
study. The MB indicated more than one type of iron, as shown in Fig. 15-9(A).
The outer two lines are assigned to one type of iron and the inner two to a
second type. In general, the areas are roughly proportional to the number of a
particular type of iron present. A definitive crystal structure study has supported
the structure shown in Fig. 15-9(B), which was predicted from the Mssbauer
results. The spectra of Fe(II)X
2
(CO)2 P2 (where X = CI, Br, and 1, and
P = phosphines and phosphites) have been interpreted in terms of the five different
isomers that exist.
e
o
.:;
D.

.o

/ \

(S)
FIGURE 15-9 The Mbssbauer spectrum (A) and structure (B) of Fe
3
(CO)12'
Several systems involving spin equilibrium between high spin and low spin
iron(II) complexes have been studied by Mossbauer spectroscopy. A typical
resu!t(20) involves the hexadentate ligand {4-[(6-R)-2-pyridyl]-3-azabutenyl} 3
ami ne. The spectra obtained when two or three of the R groups are methyl are
characteristic of low spin iron(Il) eA 1) at 77 K, while at 294 K the large isomer
shift and quadrupole splitting found are characteristic of high spin iron(Il) eT
2
)
At intermediate temperatures, both forms are observed in the spectrum. This
establishes that it is a tme equilibrium e T
2
::: 1A1) and that these sta tes are
Velocity (mm/sec)
(A)
Appli cat ions 641
long-lived on the Mossbauer time scale; Le., the lifetime must be 10 -
9
sec or
greater.
There are several interesting biological applications of Mossbauer spectros-
copy(S,12,21 .22) Horseradish peroxidase is an iron(III) heme protein. It can be
oxidized in two one-electron steps, producing red and green compounds. The
Mossbauer spectrum changes(23) upon oxidation to either form and in both cases
is interpreted in terms of iron(IV). The remo val of the second electro n leading
to the green form is believed to come from the protein or porphyrin.
Mossbauer studies have been of considerable utility in the study of the redox
centers that exist in several classes of iron-sulfur proteins. A crystal structure
investigation of the ferredoxin HP,ed photosynthetic (high potential) protein from
Chromatium has been carried out, and it has been shown to contain an
Fe
4
S
4
(SCYS)4 (SCys refers to cystein) core with the cubane-like structure shown
in Fig. 15-10. Similar units are present in other proteins. The compound H P'Od
is readily oxidized to form HPox' The crystal structure does not provide
information about the oxidation states of the iron or the charge on the cluster.
The Mossbauer spectra of several proteins containing this unit consist of a
quadrupole split doublet.( 24) By comparing the isomer shift in HP,ed with those
of other iron systems, it was concluded(24) that the core consists of an average
of two Fe3+ and two Fe
2
+ ions. The irons are antiferromagnetically coupled,
le.ading to a diamagnetic material, and the metal electrons in the system are
delocalized so that only one kind of iron atom exists. The sensitivity of isomer
shift to oxidation state is indicated in Ta ble 15- 5.
TABLE 15-5. Center Shifts for Various
Iron-Sulfur Compounds
Species
Fe
3
+ (rubredoxin) 0.25
3Fe3+ + lFe
2
+ (Chromatium HP
ox
) 0.32
2Fe
3
+ + 2Fe2+ (Chromatium HP
rcd
0.42
and ox. ferredoxin)
l Fe3+ + 3Fe2+ (red. fe rredoxin) 0.57
Fe
2
+ (rubredoxin) 0.65
SR-
S ---Fe/"
1'" 1\
-RS- Fe---t-S

s - --Fe
""SR-
FIGURE Cubane-like
structure 01 the Fe. S.(S- R-).
core 01 sorne lerredoxins.
DAn entry such as 3Fe
H
+ IFe2+ is meant to imply an
average oxidat ion state for the iron atoms corresponding
to the given combinat on.
The model compound [(C2Hs)4N]2[Fe4S4(SCH2C6Hs)4] has been pre-
pared.(2S) The charge on this anion is known to be minus two , so it must be a
2Fe
2
+ + 2Fe
3
+ case. The Mossbauer spectrum(26) shown in Fig. 15- 11 and the
crystal structure are similar to those of HP,ed or oxidized ferredoxin with
equivalent iron atoms and an isomer shift of 0.36 mm sec-
1
. This supports the
assignment(24) of the corresponding ferredoxins as 2Fe2+ + 2Fe3+ systems.
The Mossbauer spectrum of (Et4N) 2[Fe4S4(SCH2C.,Hs)4] shown in Fig.
15-11(A) is a quadrupole split doublet arising from the low symmetry about the
iron center. The lines are further split by a magnetic field, as shown in (B). The
solid hne in (A) is a least squares fit of the data, employing Lorentzian hne shapes.
The solid line in (B) is a computer-generated spectrum employing H = 80
kilogauss, r = O, and I!!.E
Q
= 1.26 mm sec-
1
. The sign of the principal component
of the field gradient is found to be positive from the spectral fit.
642 Chapler 15 Mbssbauer Spectroscopy
FIGURE 15-11 Mossbauer
spectrum 01
(Et4Nh[Fe4S4(SCH2C6H4)4] (A)
at 1.5 K and Ho = O, and (8)
at 4.7 K and Ho = 80
kOersteds. [Reprinted with
permission Irom R. H. Holm,
et al., J. Amer . Chem. Soc.,
96, 2644 (1974). Copyright by
the American Chemical
Society.]
o
- .",e
.-
: -If"""-"'.
.- '
(8)
VElOCITY (mm/sed
As we have mentioned several times, it is difficult to interpret field gradients.
However, it has been found possible to parametrize ions and groups attached to
a cent ral metal ion and to use these parameters, called additive partial quadrupole
splittings, to predict the quadrupole coupling. T he basic model is one of a point
charge. Tn a diagonal electric field gradient coordinate system, the contributions
to V
xx
, Vy,Y ' and V
z z
from a charge Z are given by
V = Z er-
3
(3 sin
2
ecos
2
q; - 1)
xx
v;, y= Zer-
3
(3 sin
2
esin
2
q; - 1)
v;, z= Zer -
3
(3 cos
2
e- 1)
where eand q; have their usual definitions in the polar coordinate system. For
a tetragonal complex (Fig. 15-12), for example, we must take each ligand (a point
charge) and sum the individual contributions to Vxx' v;,y , and V
zz
. Table 15-6
contains a summary of this calculation for the Gis and trans complexes in Fig.
15- 12.
Summing the contributions in Ti bIe 15-6, we obtain for the trans complex
V
u
= VVy = (- 2[A] + 2[ B])e
v;, z= (4[A] - 4[ B] )e
where [A] and [B] are unspecified contributions from ligands A and B,
respectively. For the cis complex we obtain
V
u
= VVY = ([ A] - [BJ)e
v;,z = (- 2[A] + 2[B])e
15-6 Applicati ons 643
? z
,
, '
A, 8,
FIGURE 15-12 Geometries
and coord'inates tor (A) trans
and (B) cis MB.A2 '
8 - A" ",,)(
I
B
2
(B)
B
4
-B,..,.,
I 'X
A
2
(A)
TABLE 15--6. Individual Point Charge Contributions to the EFG Tensor in
trans- and cis-MA
2
B
4
." The Quantity [A] Equals ZAe/r
A
3
Irans-MAaB.
Ligand
(Fig. 15-12) 9 Ijl sin O cos 9 sin Ijl cos <p V" /e Vyyle Vale
Al
A
2
O
180
O
O
O
O
1
-1
O
O
1
1
- [AJ
-[AJ
- [AJ
- [AJ
+2[A]
+2[AJ
DI 90 O 1 O O 1 +2[8J -[BJ - [ BJ
Bl 90 90 O 1 O - [8 J +2[8J - [ BJ
B3 90 180 O O -1 +2[BJ - [8J -[8J
B.. 90 270 O -1 O - [ BJ +2[8J -[8 J
cis-MA. B.
Lfgand 9 Ijl sin O cos O sin Ijl COS Ijl V .. , /e Vyyle Vzz /e
Al
90 O 1 O O 1 +2[AJ - [AJ -[AJ
Al 90 90 1 O 1 O - [A] +2 AJ - [AJ
BI O O O 1 O 1 - [BJ - [8J +2[8 J
Bl
180 O O -1 O 1 - [BJ -[BJ +2[8J
B3 90 180 1 O O -1 +2[ BJ - LBJ - [ H]
B4 90 270 1 O - 1 O - [ BJ +2[BJ - [BJ
aCo pyri ght 1973 McGraw-Hill (UK) Limit ed. From G. M. Bancrort, "Mossbauer Spectroscopy."
Reprod uced by permi ssion.
The ratio of the trans to cis quadrupole splittings is
(4[A] - 4[B])e
= -2
(- 2[ AJ + 2[B])e
If both isomers are available, Mossbauer spectra provide a ready means of
distinguishing them, with t his ratio. l n the partial quadrupole coupling approach,
magnitudes are empi ricall y assi gned to [ A] and [ BJ, and the field gradients are
644 Chapler 15 Mossbauer Spectroscopy
predicted.Acis ortrans geometryis readilydeterminedwiththeaboyeequations.
Forothergeometries,theappropriateequationsmust bederived.Thecompound
Fe(CO)2(PMe3)212canexistasfive differentisomerswhoseca1culatedquadrupole
spiittings differ considerably. Two isomers can be prepared with observed
quadrupolesplittingsof-0.90and +1.31 mmsec-
1
Theseare readilyidentified
as the (trans P, cis 1, cis COl and all trans isomers, respectively. (27) Partial
quadrupole splitting parameters( 27) for various ligands bonded to iron(I1) are
listed in Tab!e 15-7.
When the values for the ligands in Table 15-7 are used with appropriate
equations for the complexes in Table 15-8, the values listed under the column
labeled "predicted" result (27)
TABLE 15-7. Ligand Partial Ouadrupole Splitting (POS)
Parameters(27) for Iron(ll)"
Ligand POS value Ligand POS value
NO+
b
x-
+0.01
-0.30
P(OPh)}
CO
-0.55
-0.55
\
N
z
N} -
CH}CN
SnCl }-
H
2
0
b
SnPh}
NCS-
AsPh}
NH/
NCO-
PPh}
-0.37
- 0.38
-0.43
-0.43
-0.45
-0.50
-0.51
-0.51
-0.52
-0.52
-0.53
PPhzEt
PPhzMe
depbj 2
P(OEt)}
depej 2
P(OMeh
PMe
3
dmpej 2
ArNC
CN-
b
H-
-0.58
-0.58
-0.59
-0.63
-0.65
-0.65
-0.66
-0. 70
-0.70
-0. 84
-1.04
"Copyright 1973 McGraw-Hill (UK) Limited. From G. M. Bancroft ,
"Mossbauer Spectroscopy. " Reproduced by permission.
b PQS values derived from room temperature data.
TABLE 15-8. Predicted and Observed(27.28) OS (mm sec-
1
) at 295 Ka
Observed Predicled
trans-FeCl
z
(ArNC)4
cis-FeCI
2
(ArNC)4
[FeCl(ArNC)sJCI0
4
trans-Fe(SnCI
3
)2(ArNC)4
cis-Fe(SnCl
3
)2(ArNC)4
cis-FeCISnCI
3
(ArNC)4
trans-FeH
2
(depb)2
trans-FeHCI(depe)2
trans- Fe(EtNC)4(CN)2
cis- Fe(EtNC)4(CN)2
trans-[FeH(ArNC)(depe)2JBPh
4
trans- [FeH (CO)( depe)2J8Ph
4
+1.55
-0.78
0.73
+1.05
0.50
0.61
-1.84
<0.12
-0.60
0. 29
-1.14
1.00
-0.78
+0.78
-0.52
- 0.69 (11 = 0.60)
- 0.20
+0.30
- 0.98
-0.46
r
a Copyright (j:) 1973 McGraw-Hill(UK) Limited. FromG. M.Bancroft,"Moss bauerSpectroscopy." lJ
Reproduced by permission.
e
Other parameters have been reported for use with tin compounds. (27) The
approach has been applied to a large number ofsystems with a high degree of
success. (27 .28) Thereclearlyaresorneshortcomingsin thepointchargemodel ,(29)
but more work is required to enable one to predict when it will break down in
empirical type applications.
The sign and magnitude of the field gradient can be used to provide
informationabout the electronicground stateofa transition metal ion complex.
The approximate value of the field gradient for different ground states can be
estimated by adding the d orbital contributions of the populated orbitals,
employing Table 15- 9.
TABLE 15-9. Magnitude of q and '7 for
Various Atomic Orbitals
Orbital q
11
pz

O
5
2
+ - <,- 3) - 3
Px
5
2
+_<,- 3)
+3 Py
5
d,, _ y'
+_
4
<,- 3)
O
7
4 3
dz'
- - <t- ) O
7
4
+_<,- 3)
d
xy
O
7
2
_ - <,- 3)
dxz +3
7
2
_ - <,- 3)
-3 d
yZ
7
The quantity ( r-
3
) is the expectation value of 1/,.3 for the appropriate
orbital function. Thi s table is constructed by using the various orbital functions
to evaluate the matrix elements :
qtt =q= _(t/J1 3 cos:
3
e-
1
1t/J )
2
= ( t/J 1 sin cos 2cp 1t/J )
0.60)
3
In a typical application, the a/(dzz), e
2
/ (d
xy
, d
X
2_ y2) ground state for ferrocene
is predicted to have a qzz value of2(-4/7(r-
3
) + 4(4/
7
(r-)) = %(r -
3
) . Alarge
positive field gradient is observed. In forming theferricenium cation,a decrease
in the quadrupole splitting is observed, which is consistent with the loss ofan
e
2g
electron.(30)
646 Chepler 15 Mi:issbauer Spectroscopy
REFERENCES
CITED
1. P.G. Debrunnerand H. Frauenfelder,in "Introductionto MbssbauerSpectroscopy,"
ed. L. May, Plenurn Press, New York, 1971.
2. G.M. Bancraft,"MbssbauerSpectrascopy-AnIntroductionfor InorganicChernists
and Geochernists,' McGraw-Hill (UK), 1973.
3. M. Weissbluth, Structure and Bonding, 2, 1(1967).
4. A. 1. Bearden and W. R. Dunharn, Structure and Bonding,8, 1(1970).
5. T. C. GibbandN. N.Greenwood,"MbssbauerSpectroscopy,"Chaprnan& Hall, 1971.
6. 1. F. Duncan and P.W. R. Wigley, 1. Chern. Soc., 1963, 1120.
7. R. E. Watson and A. 1. Freernan, Phys. Rey., 120, 1125 (1960).
8. L. R. Walker, G. K. Wertheirn, and V. Jaccarino, Phys. Rey. Lett., 6, 98 (1961).
9. L. M. Epstein, 1. Chern. Phys., 36, 2731 (1962).
10. a. E. Mnck and B. H. Huynh in "ESR and NMR of Pararnagnetic Species in
BioJogical and Related Systerns," eds. 1. Bertini and R. S. Drago, D. Reidel,
Dordrecht, 1980.
b. E. Mnck, Methods Enzyrnol., 54, 346 (1978).
11. A. Abragamand B. Bleaney,"EJectran Pararnagnetic Resonance ofTransition lons,"
Chapter 15, Oxford Uniyersit y Press, New York, 1970.
12. il. R. L. ollins and 1. C. Trayis, Mbssbauer Effec! Methodol., 3, 123 (1967).
b. G. Lang, Quart. Rey. Biophys., 3, 1(1970).
13. a. E. Mnck and P. M. Charnpion,1. Physique, Suppl. 12/ 35, C6-33 (1974).
b. "Mbssbauer Spectrascopy," Topics in Applied Physics, Volurne5,ed. U.Gonser,
Springer VerIag, New York, 1975.
14. a. R. L. Collins, 1. Chern. Phys., 42, 1072 (1965).
b. E. Mnck, in "The Porphyrins," ed. D. 1-1 .Dolphin, Acadernic Press, New York,
1975.
c. W. T. Oosterhuis, Structure and Bonding, 20, 59 (1974).
d. G. Lang, Quart. Rey. Biophys., 3, 1(1970).
15. L. Marchant, M. Sharrock, B. M. Hoffrnan, and E. Mnck, Proc. Nat!. Acad., Sci.
USA, 69, 2396 (1972).
J6. A. R. Charnpion, R. W. Vaughan, and H. G. Drickamer, J. Chern. Phys., 47, 2583
(1967) and references therein.
17. R. V. Parish, Prog. Inorg. Chern., 15, 101 (1972).
18. R. H. Herber, W. R. Kingston, and G. K. Wertheirn, Inorg. Chern., 2, 153 (1963).
19. R. H. Herber. R. B. Kingston, and G. K. Wertheirn, Inorg. Chern., 3, 101 (1964).
20. M.A.Hoselton, L. 1. Wilson,and R.S. rago, 1. Arner. Chern. Soc., 97, 1722 (1975).
21. W. Marshall and G. Lang, Proc. Phys. Soco (London), 87,3 (1966).
22. T. H. Moss, A. Ehrenberg, and A. 1. Bearden, Biochernistry, 8, 4159 (1969).
23. P. Debrunner, in "SpectroscopicApproaches to Biornolecular Conforrnation,"ed. D.
W. Urry, American Medical Association P ress, Chicago, 1969.
24. C. L. Thornpson el al. , 1. Biochern. 139, 97 (1974) and references therein.
25. R. H. Holrn, Endeayour, 1975,38 and references therein.
26, R.H. Holm el al., 1. Arner. Chern. Soc., 96, 2644 (1974) and references therein.
27. G. M. Bancroft, Coord. Chern. Rey., 11, 247 (1973) and references therein.
28. G. M. Bancraft and K. D. Butler, Inorg. Chim. Acta, 15, 57 (1975).
29. A.P. Marks,R.S.Drago,R.H.Herber,andM.J. Potasek,Inorg,Chern., 15,259(1976).
30. W. H. Morrison,lr. , and D. N. Hendrickson, Inorg. Chern., !J, 2279 (1974).
SERIES " Mbssbauer Effect Methodology," Volurnes 1to 9, Plenurn Press, Ncw York, 1965.
10
Exercises 647
,"
,
1. Whateffectdoesincreasingelectrondensityatthe nucleus haveontherelativeenergies EXERCISES
ts
ofthe ground andexcited statesofs7Feand 1l9Sn? Explain theexpected isomershift
from thi s change in terms ofeffective nuclear charge radii ofthese states.
,1.
2. Suppose you read an art icle in which the authorclaimed that the two peaks in a MB
spectrum ofa low spin iron(lIl) complex were the result ofJ ahn-Teller distortion.
Criticize this conclusion
3. Draw the structurefor SnF4 and explain why quadrupolesplittingis observed in this
compound but not in SnCI
4
.
d,
4. Suppose you wereinterested in determiningwhetherSn-OorSn-Sn bondingwere
present, and which was greater, in the compounds (C6HshSnOCH) and
(C
6
HshSnSCH). Describe experiments involving MB spectroscopy that might shed
light on this problem.
S. Would you expect the !lE
Q
value to
Explain.
be greatest in SnCI
2
Br2' SnCI)Br, or SnF)I?
6. The productobtained from the reaction offerrous sulfate and potassium ferricyanide
gives rise to the spectrum below. Interpret this spectrum.
1.
K3
-1.0
mmsec-
1
7. Usinga pointchargeexpression,indicatethe threediagonalcomponentsoftheelectric
field gradient ror the two isomers of MAJ B3' P redict the sign of the quadrupole
sphtting in the two isomers.
8. ( H))2SnCI 2is a chloro-bridged polymerwithoctahedralcoordinationabouttino The
methyl groups are transo With the CH
3
-Snbond as the z field gradient axis, predict
the signs ofq a nd Qq.
9. Which componds would have the largest quadrupolesplittings for thestarred atom:
a. cis 01' lrans *Fe(CO)4Cl 2?
b. (CH)h*SnCl (C
Jv
) or polymeric, chloro-bridged ( H)h*SpCl (D
3h
about tin)?
c. high spin cis 01' lrans *Fe(NH )4CI2?
10. The Mossbauerspectrumfor Fe(CO)s atliquid nitrogen tempera ture is shown below.
648 Chapter 15 M6ssbauer Spectroscopy
-4.0 o 4.0
mm sec-
1
a. Why are the unusual units on the x-axis equivalent to energy?
b. Whatgives risetothedoubletobserved?Show(andlabel)theenergylevelsinvolved.
ll. The enzyme putidaredoxin has sites with two iron atoms. The oxidized form gives
rise to the spectrum shown below:
0.011
0.016
5 0.022
~ 0.027
0.033
0.038
0.044
0.049
10.055
.,.
fi.

-0.1 o +0.1
Velocity (cm/sec)
The g-tensors are anisotropic. Does the enzyme consist ofa single type ofiron site
or two different iron sites?
12. Oneofthe Mossbauerspectra below is K3Fe(CN)6' Theotheris K
4
Fe(CN)6' Which
is which? Why?
70
60
130
50
0.2 -0.1 o 0.1 0.2
(B)
Exercises 649
13. An article[lAmer.Chem.Soc., 97,6714(1975)]dealtwitliaseriesof square-pyramidal
iron(I1I) complexes having an N
4
S (the sulfur donor is axial) set of donor atoms.
Thesecomplexesvaried considerably inelectronicstructure,dependingupontheexact
nature of the N
4
macrocyclic ligand and the axial ligand, as shown by various
spectroscopic measurements.
a. Using one-electron energy level diagrams, indicate which spin states might
reasonably be expected for square-pyramidal iron(IlI). Remember that the relative
energies ofthe d orbitals may vary slightly as a function ofthe donor se\.
b. Usingspectrafrom thefigurebelow,assign probable,spinstates tocomplexes A, B,
and C. Explain what features ofthe Mssbauerspectra influenced yourdecision,
and why.
(A)
ved.
ves
(B)
~
~
e
l!i
e
(e)
o
Velocity (mm/ sec) ,
,
,
l
Mass
Spectrometry
650
lonization Methods:
Mass Spectrometry,
IonCyclotronResonance,
PhotoeIectron
Spectroscopy
16-1 INSTRUMENTOPERATIONANOPRESENTATIONOF
SPECTRA
There are many different type of mas spectrometers available, and the details
of the conslruction and relati ve m rit s of the various types of inslrumenls have
been describedY- 6} Most of the basic pri ncipIes of mass spectromctry can be
ill ustrated with the aid of Fig. 16-1. The sampl , contai ned in a reservoir, is
added through the port, enters the ion so urce (a), and passes through the e[ectron
beam at (c). (The beam is indicated by a dott d line.) Interaction of the sarnple
with an energetic electron produces a positive ion, whi ch moves toward the
acce[erating plates (d) and (e) because of a small-potential difference between the
back wall (i nlet) and the front wall of thi s compartment. The back wall, wruch
.{
\
\
- 1-9
Detector
and
amplifier
Inlet system
FIGURE ~ A schemati c of a 180
0
deflecti on mass spectrometer.
is
10:
lal
th
th
tr<
of
[i .,
101
rel
Wi
501
of
sar
ten
[ov
del
a r
Sp
c h ~
IOn
eral
be
all
Th
[sel
rad
the
In
cO n
(16-
tior
16-
p r e ~
by
ene
In t
He
~ Instrument Operation and Presentation 01 Spectra 651
is positively charged relative to the front, attracts and discharges the negative
ions. The positive ions pass through (d) and (e), are acc lerated by virtue ofa
large potential difference (a few thousand volts) between these pIates, and leave
the ion source through (b). Charged ions move in a circular path under
the influence of a magnetic field. The semicircle indicated by (1) is the path
traced by an accelerated ion movingin a magneticfield ofstrength H. The radius
ofthesemicircle, r, depends upon the following: (1) the accelerating potential, V
[i.e., the potential di ffe rence between plates (d) and (e)J; (2) the mass, m, ofthe
ion; (3) the charge, e, of the ion; and (4) the magnetic field sl rength, H. The
relationship between these quantities is given* by equation (1 6-1):
(16-1)
e 2V
When the ions pass through slit (g) into lhe detector, a signal is recorded. The
source and t he path through which the ions pass must be kept under 10-
7
mm
ofmercury pressure in order to provide a I ng mean free palh for the ion. The
sample vapor pressure in the inlet should be at least 10-
2
mm Hg at the
temperature of the inlet system, although special techniques permit use of
lowerpressures.Ingeneral,onlyon 01" twomicromolesofsamplea rerequired.
Si nce H,V, and r can be controlled experimentaJl y, the ratio m/e ca n be
determined. Note that a dipositive ion ofmass S4 gives rise to the same m/eas
a monoposit ive ion of mass 27. Under usual condi ti ons for running a mas
spectrometer, most oflhe ions are produced as si ngly charged species. Doubly
chargedionsaremuch lessfrequentlyencountered,whereas morehighlycharged
ions are not present in significant concentrations.
Obtaining t he mass spect rum consists in determining the m/e ratio for aH
fragment s produced when a moleculc is bomba rded by a high int ensity electron
beam.Todothis, thedetectorslitcould be movedand thevalueofrmeasured ror
aJl particles continuouslyproduced by electron bombardment in the ion source.
Thisis notfeasibleexperimenlally.It is muchsimplertovaryHor Vcontinuously
[seeequation(16-1)J so thatal\ particleseventually travelin a semicircle offixed
radius.Thesignalintensity,whichis directly relatedtothenumberofionsstriking
the detector, can be plotted as a function ofH or V, whichever is bei ng varied.
In practice it is easiest to measure a varying potential, so the field is often held
.constant. If H and r are constant, V is inversely related to mle [by equation
(1 1)] and m/eca n be plotted versus the signal intensit y to producea conven-
tionalmass spectrum.Anarrow region ofa typical spectr um is iHustrated in Fig.
16-2.
On instruments in which the potential is varied, the results are readily
presented in tennsofm/e values.Tbe accuracy varies withmass,ascan beseen
by comparing the potential difference corresponding to mle values of 400
This equation issimply derived: The potentialenergy of(he ion,eV, isconverted to kinetic
energy ('/ 2)mu
2
(where m is the mass and uthe velocity). At full acceleration,
(16-2)
In the magnetic field the centrifugal force mu'/r is balanced by centripetal force Hev. Solving
Heu=mu'/, forryieldsr=mu/eH.Us ingthiseguation toeliminateufrom(16-2)produces(16- 1).
:
652 Chapter 16 lonization Methods
-
FIGURE 16--2 Mass spectrum 01
Iragments with m/e in the range Irom
-
40 to 48. The peaks have been
automatically attenuated, and the
number 01 horizontal lines aboye
each peak indicates the attenuation
lactor.
40 41 42 43 44 45 46 47
m/e
and 401 with the difference for m/e values of 20 and 21 [caIculated by using
equation (16--1)]. With modern low-resolulion instruments, one can count on
0.4 to 1 m/e accuracy up to 1000 mass units. For high-resolution work,
accuracy to 2 or 3 ppm can be obtained up to very high masses (> 3000) if
reference compounds are available that have accurately known peaks within
10 to 12% of the unknown mass peaks. Perftuorokerosine is a common
reference compound, with many peaks that are accurately known up to about
900 mass units.
The mass spectrum obtained from the instrument may be a long and
cumbersome record. As a result, the data are often centroided and summarized
by a bar graph that plots intensity (relative abundance of each fragment) on
the ordinate and the m/e ratio on the abscissa. The relative a bundance is given
as the percent intensity of a given peak reJative to the most in tense peak in
the spectrum. Often it is informative to express the intensity in tenns of total
ionization units, S. This is an expression of the percentage that each peak
contri bu tes to the total ionization, and is obtained by dividing the intensity of
a given peak by the sum of (he intensities of aH the peaks. W hen the spectrum
has not been obtained over the range from 1 lO the molecular weight of the
material, the lower limit is indicated on the ordinate as a subscript to L (e.g.,
L
12
means that the spectrum was recorded from 12 to the molecular weight).
A typical graph is iHustrated in Fig. 16--3. For the comparison of the intensity
of various peaks in the same spectrum, the relative abundance is adequate. For
comparison of the intensity of peaks in different spectra, total ionization units
should be employed. In general, a peak with an intensity equal to 0.5% of L
is easil y detected.
Must modern spectrometers contain computers to store and process the
large amount of info rmation from molecular fragmentation and to control the
experimental variables involved in running the instrument. Accurate masses can
be obtained with computer interfacing by introducing standards with the
sample. The computer recognizes the standard peaks and employs them to
determine the mass of the unknown peaks. Computer libraries(7) are available
to match the sample spectra with that of known compounds in 70-eV electron
impact ionization.
u
E
thl
to
n
pe
be
of
th.
10
po
th(
y ~
inl
ior
COI
ou
y ~
In
dir
ph
1m
Fif
pn
aTE
Fr
m<
ma
bal
or
16-1 Instrument Operation and Presentation of Spectra 653
100,---- ---.----- ,38.2
i
30

.;

e
20 ::
50 e
e Q)
u
>
Q)
Q;
CL

10
u
e
10 20 30
.1111.
40 50
m/e
FIGURE 16-3
Representation of the mass spectrum
of ethanol.
Our next concern is with the method of indicating the resolving power of
ing
the instrument. For many inorganic and organic applications, it is necessary
rt on
to know the m/e ratio to an accuracy of one unit (i. e., whether it is 249 or 250).
ork,
The resolution of the instrument is sometimes expressed as m/'m, where two
10) if
peaks m and m + 'm are separateJy resolved and the minimum intensity
between the two peaks is only 10% of the total of m. For example, a resolution
of 250 means that two peaks with m/e values of 251 and 250 are separated and
that at the minimum between them the pen returns to the base line to within
10% of the total ion current (plotted as intensity in Fig. 16-2). I nstruments with
poor resolution will not do this with high mass peaks, and the magnitude of
the m/e value for which peaks are resolved is the criterion for resolution.
Modern mass spectrometers provide a wide range of options in inlet
systems, ion sources, mass analyzers, detectors, and signal processors. Batch
inlet systems volatilize a sample externally and allow it to lea k into the
ionization region. The sample must have an appreciable vapor pressure beJow
500
Q
C. The direct probe inlet introduces non-volatile and thermally unstable
compounds with a sample probe that is inserted through a vacuum lock. The
output from a chromatographic colurnn can also be used as the inlet in GC- MS
systems.
Most commercial mass spectrometers are equipped with accessories that
allow use of several ion sources interchangeably. So me common ones are listed
in Table 16-1. The desorption types use a sample probe from which energy
directly transfers ion s or molecules in the condensed phase to ions in the gas
phase. Non-volatiJe and thermally fragite molecules can be studied. Electron
impact, El, uses a beam of energetic electrons to ionize the gaseous molecule.
Field ionization and field desorption employ large voltages (10 -
20
kV) to
produce large electric fields (10
8
V/cm) to ionize molecules. Gaseous samples
are used in the former and non-volatile samples on a probe in the latter.
Fragmentation of the molecule is minimized with the latter technique and the
molecular ion, M + , and one with a mass one unit larger, (M + 1t, are the
major peaks in the spectrum. In chemicaJ ionization, CI, the sample is bom-
barded by positive ions produced by electron bombardment of a gaseous atom
or molecule (often CH
4
) present with the sample and in 1000- to 1O,000-fold
l
l
'
I
TABlE 16-1. Some Common Ion Sources
Name Abbrevlatlon Type lonlzing Agenl
electron ionization El gas phase energetic electrons
field ionization FI gas phase high-potential electrode
chemical ionization CI gas phase reagent positive ions or
electron capture
fast atom bombardment FAB desorption
a
energetic atoms
fi eld desorption FO desorption
b
high-potentiaI electrode
Iaser desorption LO desportion
b
laser beam
plasma desorption PO desorption
b
high-energy fissi'on
fragments from 252Cf
secondary ion mass SIMS desorption
b
1 to 20 keV ions
spectrometry
thermal desorption TIMS desorption
b
heat
repl e
cont
lons
verSl
techl
tech
secti
a Samples as solids or solutions
b Samples as solids, gases, or solutions.
excess. We can illustrat e the reactions in chernical ioruza tion that lead to
product ions with CH
4
as an exarnple. The CH
4
+ ion forrned by ionization
reacts with another methane molecule forrning CH
s
+ The CH
s
+ or CH
4
+ can
react with substrate SH forrn ing SH
2
+ and CH
4
or CH
3
forrni ng the substrate
(M + 1)+ ion. With sorne substrates, CH
s
+ or CH
4
+ can a bstract hydride
forming H
2
and S+ , where S + is the (M - 1) + ion. In both instances, reactions
of the ion with the sample lead to sample ions. Cl ust er ions can al o form in
CJ, e.g , reactions occur to form (M + C
2
H
s
)+ and (M + C
3
H
s
)+ peaks in
rnethane Cl. Less fragmentati on results with Cl than wit h EL In fast atorn
bombardrnent (FAB), the sample in a condensed state (often a glycerol malrix)
is ionized by bornbardrnent with energetic Xe or Ar atoms. M olecular ions are
often forrned even for large molecular-weight sarnples.
Analyzers are cornmonly radio-frequency filters or electromagnets in
cornbination with electrostatic fiel ds. The radial rnagneti c field shown in Fig.
16- 1 ernploys single-focusing magnetic sector analysis. D ouble focusing analy-
zers first pass the beam througb a radial electrostatic field and then the radial
rnagnetic field. The el ectrostat ic field rocuses part icIes with the same kinetic
energy on a second slit which int roduces the beam into the magnetic fi eld.
Much bett er resolution is achi eved. The quadrupole analyzer consists of fou r,
short, parallel metal rods a rranged syrnrnetrically around the bearn. One pair
of opposite rods is attached to the posit ive terminal of a variable dc source and
the other pair to the negat iv ter minaL O n top of this, variable radio-frequency
ac potentials, that are 180
u
out of phase are applied to each pai r of rods. The
cornbined fields ca use t he charged pa rt icles in the bea m to oscillate about a
central ax.is describing their direction of trave!. O nly fields with a certai n rnass
to charge ratio pass through t he rods. The ot hers collide wit h one of the rods.
The m/e ratio is scanned by varying the frequency of the ac source or by varying
the potential of the two sources keeping their rati o a nd frequency constan!.
The ion trap uses a fi Id generated by a sandwich geometry wi th a r ing electrode
in the mi ddIe and caps on each end to trap and store ions of a selected
rnass-to-charge ratio. The mass spcct rurn is produced by varying the elect ric
field to sequentialI y eject ions of diffcrent m/e ralios for detection.
16-:
1t is
only
wit h
thes
plat
mod
tion
The
Imp
elec
15 e
10m
mol
ene!
ind\
the
glve
to
acc
initl
Ion.
mol
can
elec
16-2 Processes !ha! can Occur When a Molecule and a High Energy Elec!ron Combine 655
In a time-of-ftight instrument, the semicircular path and magnet are
replaced by a straight path (no magnetic field). The ions are not produced
rode
JI or
continuously but in spurts and are allowed to diffuse toward the detector. Heavy
ions will move more sJowly than light ions. The spectrum is a plot of intensity
versus the time of ftight of the partic1e. The application of the Fourier transfoJm
technique to mass spectrometry has many of the advantages of applying this
technique to other spectroscopies. This method will be discussed in the next
section on ion cyc1otron resonance.
16-2 PROCESSES THAT CAN OCCUR WHEN A
MOLECULE ANO A HIGH ENERGY ELECTRON
COMBINE
It is important to emphasize the rather obvious point that a detector analyzes
only those species impinging on it. We must, therefore, be concerned not only
with the species produced in the ionization process but also with the reactions
these species may undergo in the 10-
5
sec required to travel from the accelerating
plates to the detector. When a molecule, A, is bombarded with electrons of
moderate energy, the initial processes that can occur are summarized by equa-
tions (16-3) to (16- 5):
(16-3)
(16-4)
(1 5)
The process represented by reaction (16-3) is the most common and the most
important in mass spectrometry. It will occur if the energy of the bombarding
electron is equal to OI higher than the ionization energy of the molecule (7 to
15 eV). When the energy of the bombarding electro n beam is just equal to the
ionization potential, all of the electron's energy must be transferred to the
molecule to remo ve an electron. The probability of this happening is low. As the
energy of the bombarding electro n increases, the probability that a collision will
induce ionization increases, and a higher intensity peak results. As the energy of
the bombarding electron is increased further, much of this excess energy can be
given to the molecular ion that is formed. This excess energy can be high enough
to break bonds in the ion, and fragmentation of the partic1e results. The
acceleration potential of the bombardi ng electron that is just great enough to
initiate fragmentation is referred to as the appearance potential of the fragment
ion. When the electron energy is large enough, more than one bond in the
molecule can be broken. The following sequen ce summarizes the processes that
can occur when a hypothetical molecule B- C- D- E is bombarded with an
electron:
(a) Ionization process
(1 6-6)
l
l
(b) Fragmentation of the positive ion
(16--7)
BCDE I -+ BC I + DE (16-8)
BC+ -+ ~ + C (16-9)
or BC+ -+ B +C+ (16--10)
(16--11)
(1 S (2)
(16-13)
etc. (16--14)
BCDE+ -+ CD+ + BE etc. (16--15)
(c) Pair production
(16-16)
(d) Resonance capture
(16-17)
Ol her modes of cIeavage are possible, but only positiveJy charged species will
travel to the detector and give rise to peak s in the mass spectrum. or lhe scheme
above, peaks corresponding lo B+, BC+, C+, DE+ D , E l. , BE-I and CD+
will occur in the spectrum if B, C, D, and E have different masses. More energy
will have to be imparted to tbe BCDE + ion to get cIeavage into B+, C-, and
DE [equation (1 6--9)] than for cIeavage into BC+ + DE- [ equation (16--8)].
In equation (1 6--14), the ion has rearranged in the di ssociation process,
leading to fragments that contai n bonds that are not originally prcsent in the
molecule BCDE. These rearrangement processes complicate the interpretation
of a mass spectrum, and experience is necessary to be able to predict when
rearrangements will occur e.g., alkenes commonly rearrange. In general, re-
arrangements are invoked to explain the occurrence of peaks of unexpected mass
or unexpected intensi ty.
Ion-molecule reactions can give rise to mass peaks in the spectrum that are
greater than the molecular weight of the sample. This process is r presented by
equation (16--18):
RCDE + + CDE- -+ BCDEC+ + DE (16--18)
The reaction involves a coJl ision of the molecular ion with a neutral molecule
and as such is a second-order rate process, the rate of which is proportionaJ to
the product of the conc ntrat ions of the reactants. The intensity of peaks resulting
fro
ane
in
pre
tiol
ele(
exc
IS r
car
ofl
m;
the
fo n
fral
di sl
fra!
of I
~ I
tim
Thf
inte
Ace
mo
con
Fra
on
IS \\
the
16-
Tht
bea
acc
ind
ti or
slm
are
are
vail
inte
to I
me
ane
rel;;
insl
16-3 Fingerprint Application 657
from this process will depend upon the product of the partial pressures of BCDE +
and CDE. Examination of the spectrum at di ffe rent pressures causes variation
in the relative intensities of these peaks, and as a result, the occurrence of this
process can be easily detected.
The reactions discussed aboye are all unimolecular decay reactions. Produc-
tion of ions by electron bombardment often in volves loss of the least tightly held
electron, and ions are often formed in vibrationally excited states that have an
excess of internal energy. In sorne molecules of the sample, a low energy electron
is removed, leaving an ion in an excited electronic Slale. The excited state ion
can undergo internal conversion of energy, producng the electronc ground state
of the ion having an excess of vibrational energy. The molecule could dissociate
in any of the excited states involved in the internal conversions associated with
the radiationless transfer of cnergy. In other molecules of the sample, ions are
formed with energy in excess of the dissociation energy. In this case, the ion wiH
fr agment as soon a it starts to vi brate. Thus, in a giveo sample, ions wi th a wide
distribution of energies a"re produced and many mechanisms are available for
fragmen tat on processes. It is informative to compare the time scales for sorne
of the processes we have been discussing. The time for a bond vibration is
1O-
l 3
sec, the maximum hfetime of an excited state ion is 10-
8
sec, and lhe
time an ion spends in the mass spectrometer ion chamber is LO -s to 10-
6
seco
There is ample time for t he excess el cctronic energy in an ion to be converted
into an excess of vibrational energy in a lower electronically excited state.
Accordingly, we view the processes in the ionizalion chamber as producing
molecular ions in different energy states, whi ch undergo rapid internal energy
conversion to produce individual ons with varying amounts of excess energy.
Fragmentation lakes place via a first order process at different rates, dependi ng
on the electronic state and excess vibrational energy of the individual ion. This
is why all of the different pro ces ses represented aboye for the fragmentati on of
the ion BCDE + can occur and be refl ected in the mass spectrum.
16-3 FINGERPRINT APPLlCATION
The fingerprint application is immedi ately obvious. For this purpose an electron
beam of 70 eV is usually employed to yield reproducible spectra, for this
accelerating potental is aboye the appearance potent al of most fragments. As
ndicated by equatons (16-6) to (16-16), a large number of different fragmenta-
tion processes can occur, resulting in a large number of peaks n the spectra of
simple molecules. Figure 16-3 contains the peaks with appr ci able intensi ty that
are found in the mass spectrum of ethanol. Counting the ver y weak peaks, wruch
are not ill ustrated, a total of about 30 peaks are found. These weak peaks are
valuable for a fingerprint application but gene rally are not accounted for in the
interpretaton of the spectrum (i. e. , assigning the fragmentaton processes leading
to the peak s).
For a fingerprint application, the more peaks the better. Accordingly, El
methods are preferred. Spectral libraries for El at 70 eV are available in text( 8)
and computer form(7) for matching an unknown spectrum to a known one. The
relative intensities are of less hel p in unknown identification for they vary wi th
instrument and wi th experimental conditions. It is best to make a direct
l
FIGURE 16-4 Mass spectra
of thr ee isomers of
ethylpyridine. [Copyright
1960 McGraw-Hill Book
Company. From K. Biemann.
"Mass Spectrometry."
Reproduced by permission.)
comparison of the spectrum ofthe unknown compound with that of a known
sampleon thesameinstrumentifadecisionis tobe basedonrelativeintensities.
An interesting fingerprint application is illustrated in Fig. 16- 4, where the
mass spectra of the three isomers of ethylpyridine are indicated. Pronounced
differences occur in the spectra of these similar compounds that are ofvalue in
the fingerprint application. On the other hand, similarities in the spectra of
hydrocarbons makes the fingerprint application of limited utility for this c1ass
of compounds. Optical isomers and racemates give rise to identical spectra.
Impurities create a problem in fingerprint applications because the major
fragments of these impurities give rise to several low intensity peaks in the
100
(A)
50
100
>-
'" e
Q)
e
Q)
50
:>
.2
~
u
e
100
50
(B)
o
llN
A
cHz- CH
3
Mol. ..,!. 107
UCHZ-
~
N

CH3
s
t
r
(C)
40 60 80 100
m /e
1&-4 Interpretation 01 Mass Spectra 659
,wn
spectrum. If the same material is prepared in two different solvents, the spectra
lo may appearto bequitedfferent fall solvent has not been removed. Contamina-
t he tion from hydrocarbon grease also gves rise to many lines.
ced
in
l of 16-4 INTERPRETATION OF MASS SPECTRA
lass
:tra. Theinterpretationofamassspectruminvolvesassigningeachofthemajorpeaks
ljor in a spectrum to a particular fragment. An intense peak corresponds to a high
the probability for the formation of this ion in the fragmentation process. In the
absence ofrearrangement [equaton (16- 14)J, the arrangement ofatoms in the
molecule can often be deduced from the masses of the fragments lhat are
produced. For example, a strong peak at m/e = 30 for the compound methyl
hydroxylamine would favor the structure CH
3
NHOH over HzNOCH3because
an m/e = 30 peak could result from c1eavage ofthe O- N bond in the former
case but cannot result by any simple cleavage mechanism from the alter
compound. The higher mass fragm nts are usuaJly more important than the
smaller ones for structure determination.
It is often hel pful in assigning the peaks in a spectrum to be able to predict
probable fragmentation products for various molecular str uctures. The energy
required to produce a fragment from the molecular ion depends upon the
activation energy for bond cleavage, which is often rel ated to thestrengt h oft he
bond to be broken. The dist ribution ofions detected depends not only on this
but also on the stability of the resulting posi tive ion. In most cases it is fo und
that the stability ofthe positi ve ion is ofgreatest importance. This st,l bil ity is
related to the effecti veness wit h whi ch the resulting fragment can delocali ze the
positive charge. Fragmentation of HOCH
2
CH
2
NH
2
+ can occur to produce
'CH
2
0H and CH
2
NH
2
+ (m/e = 30) or ' CH
2
NH
2
and CH
2
0H+(m/e = 31).
Since ni trogen is not as electronegative as oxygen, the resonance form CH
2
=
NH
2
+ contributes more to the stability ofthis ion t han a similar form CH
2
=
OH+, does to its ion. As a result, charge is more effectivel y delocalized in the
species CH
2
NH
2
1- than in CH
2
0H+ and t he m/e = 30 peak is abour ten times
more intense than lhe m/e = 31 peak. Charge is not slabilized as effectively by
sulfur as it is by oxygen because carbon-sulfur n bonding is not as effective as
carbon-oxygen n bonding. Thus, the m/e = 3 L peak for CH
2
0H-'- [rom
HSCH
2
CH
2
0H has about twice t he intensity ofthe m/e = 47 peak that arises
from CH
2
SH l .
Rearrangem nts ofthe posi tive ion will occur wh n a more stable species
res ults. For example, lhe ion ~ rea rranges to 0+ and
1
~ C H 2
the benzyl cation rearranges to the tropylium ion, C7H7+. An intense m/e = 93
peak from this fragmen t is seen in alkyl benzenes.
The production of many different fragments is often.belpful in putti ng
together the structure oft he molecule. However, onemust employ caution even
in this applicalion. Th ion produced in the ion chamber und rgoes many
vibrations, during which rearrangement could occur to produce bonds thal did
not exist in the parent compound [see, e.g. , equalion (16-14)]. Thc production
ofall these di fferent ions makes it difficult to determine the chemical processes
thatleadto the variouspeaks.Thisin turo makcsitdifficult to inferthe infl uence
660 Chapler16 lonization Methods
that bond strength or other properties of the molecule have on the relative
abundances of the ion fragments formed. A quantitative treatment of mass
spectrometric fragmentation has been attempted and is referred to as the
quasi-equilibrium theory.(10) The internal energy is distributed over all the
available oscillators and rotators in the molecule, and the rates of decomposition
via different paths are calculated. A weighting factor or frequency factor (i.e. , an
entropic term) is given to each vibration leve/. The fu/l analysis is complex for
a molecule of reasonable size. Approximations have been introduced, leading to
a highly parametrized approach.(IO,ll)
The mass spectrometric shift rule(ll) has been of considerable utility in
elucidation of the structure of alkaloids and i/lustrates a basic idea of general
utility. H there are low energy pathways for the breakdown of a complex molecule
and t his breakdown is not influenced by the addition of a substituent , the location
of the substituent can often be determined. This is accomplished by finding an
increase in the molecular weight of the fragment to which the substituent is
bonded that corresponds to the weight of the substituent or a characteristic
fragment of the substituent.
Mass spect romet ry is used for routine sequencing of small peptides. The
interested reader is referred to the review described in reference 12.
The low volatility of many substances hampers their analysis by mass
spectroscopy. The volatility can often be increased by making derivatives of the
polar groups in the molecule ; e.g., carboxyl groups can be con verted to methyl
esters or trimethylsilylesters. Field ionization techni ques (vide infra) are also
advantageous for t his problem.
The combination of mass spectroscopy with GLC provides an excellent
method for analysi of mixtures. Very small amounts of material are nceded. The
mass spectrometer may be used as the G LC detector, and numerous mass spectra
can be accumulated as each component emerges from the column. A partially

resolved GLC peak is readily detected by the change in mass spectra of the peak
e
with time.
Many more examples anda thorough discussion of factors leading to stable
11
II
ions produced from organic compounds are contained in the textbook references
at the end of the chapter and reference 9. Generalizations for predicting when
rearrangements are expected are also discussed. If,starting with a given structure,
one can account for the principal fragments and assign the peaks in the mass
spectrum by invoking a reasonable fragmentation pattern, this assignment
1
amounts to considerable support for that structure.
r
16-5 EFFECTOF ISOTOPES ON THE APPEARANCE OF A
MASS SPECTRUM
When the spect rurn of a compound containing an elernent that has more than
one stable, abundant isotope is examined, more t han one peak will be found for
each fragmen t cont aining this elernent. In the spectrum of CHj Br two peaks of
nearl y equal intensity wi ll occur at m/ e values of 94 and 96, corresponding mainly e
to ( H/9Br)+ and (CH
3
81
Br)+. The abundances of 79Br and 8lBr are almost F
the same (50.54 versus 49.46%), so two peaks of nearly equal intensity, separated
by two rnass units, will occur for all brornine-containing fragments. In a fragment
contai ning two eqivalent bromine atoms, a triplet with ratios 1:2: 1 would result e
16-5 EHect 01 Isotopes on the Appearance ot,a Mass Spectrum 661
ve
from different combinations ofisotopes, In addition to these peaks, there will be
ISS
small peaks resulti ng from the small natural abundances ofD and 13C,
sponding to all combinations ofmasses of!lC, l3e,D, H, 79Br, and 81Be The
he
resulting cluster ofpeaks for a given fragmcnt is important in establishing the
he
on
assignmentofthepeaks toa fragment Their relativeintensities will depend upon
the relativeabundances ofthe various naturally occurring isotopes ofthe al oms
an
in the fragment; e,g., CO+ can consist of mass fragments at 28, 29, 30, and 3I.
ror
The relative abundances of these fragments can be calculated from simple
lo
probability theory.<13,14) Computer programs have been reported to carry out
thesecalculationsY5,16) Thesecharacteristicpatternsarequiteuseful in assigning
in
spectra ofmolecules thatcontain anatomwi th more than oneabundantisotope,
ral
Molecules containing transition metals often give such isotope patterns. Use of
ule
the l3C peaks enablcs one to determine the number of carbon atoms in a
Ion
fragment
an
The advantages ofhigh resolution mass speclrometry can be illustrated(17)
is
by the incorrect assignment of a peak at 56 in the low resolution spectrum of
tic
Fe[(e 2Hs)2NeS2J 3 to iron, At high resolut ion, a peak is expected at 55,9500,
but none is found. Instead, one is obtained at 56,0350, which is assigned to the
rhe
fragment 3H6N,
ss
Another importantapplication ofthe mass spectrometerinvolving isot opes
is thestudyofexchangereactionsinvolvingnonradioactiveisotopes,Theproduct
the
of the exchange from labeled starting material is examined fo r isot ope content
yl
as a function of time to obtain the rate of exchange. The product or starting
lIso
material can be degraded to a gaseous material containi ng the label, and the
isotopic ratio is obtained from the mass spectrum, These materials may also be
examioed directly, and the location and amount of la bel incorporated can be
deduced from an analysis of the change in spectrum of various fr agments. By
determiningwhichpeaksin thespectrumchangeonincorporatioIloft he isotope,
one can determine which parts ofa molecule have undergone exchange, [n the
reaction of methanol with benzoic acid, it has been shown by a lracer study
involvingmassspectralanalysis thattheesteroxygen in the product comes from
methanol:
In another interesting application it was shown that the following exchange
reactions occurred:
BF3+BX
3
-> BX
2
F +BFzX
3RBX
z
+2BF3-> 3RBFz+2BX
3
(also BFnXm)
3RzBX+BF3->3R
2
BF+BX
3
(also BF"X
m
)
where R is alkyl or vinyl and X is CI or Br. Fragments corresponding to
the products were obtained, although only starting were re-
covered on attempted separation(18) A four-center intermediate of the type
R", ;=1" /F
/B",/B", was proposed for the exchange, In order to determine
el F F
662 Chapter16 lonization Methods
whether or not alkyl groups were exchanged in the reaction:
the boron trifluoride was enriched in lOB o The absence ofenrichment of 10B in
fragments in the mass spectrum containing alkyl or vinyl groups enabled the
authors to conclude that neither alkyl nor vinyl groups were exchanged under
conditiOns where RBX
2
species were stable.
It should be pointed out that in all of the aboye applications it is not
necessary to label the compound completely. A slight enrichment will suffice.
16-6 MOLECULAR WEIGHT DETERMINATIONS;
FIELOIONIZATION TECHNIQUES
Determination ofthe molecular weight requires methods that will produce the
parentionpeak.Thedramaticdi fference in EIand FImet hods is illustrated with
the mass spectrain Fig. 16-5.The M +1peak occurs from addition ofa proton
in the presence ofthe reagent ion. rn sornecases, proton abstraction Jeads toan
M - 1peak.
Jn ig. 16-6,the spectra ofglutamic acid(19
a
)
HOOCCH(NH
2
)CH
2
CH
2
COOH
100
73
i80
- 60
*-
..;
e 40
Qi M = 150
FIGURE ~ 5 (A) Formula
HOH2CUOH
H H
H OH
oc
20
29 43 re!' int. = 0.2%
01 D-ribose. (B) Electron
bombardment mass
OH OH
O
20 40 60 80 100 120 140 160
spectrum. (e) Field ionization
spectrum.
MW = 150
(A)
m/e-
(B)
100
151
i80
19 M
- 60
~
..;
e 40
Qj
29
OC
20
o
20 40 60 80 100 120 140 160
m/e--
(C)
16-7 Evalualion 01 Heals 01 Sublimation and Species in the Vapor Over High Melling Solids 663
100
Q)
u
80 e
u
in e
ro
::J 60
D
ro
Q)
40
>
.;:
~
Q) 20
a:
O
(M - H20 + H) +
(M + H) +
130
84
O 40 80 120
m/e
(A)
148
100
Q)
u
e 80
ro
u
e
::J 60
D
ro
Q)
(M + H)+
40
>
148
~
Qi 20
a:
O
' 160
O 40 80 120 160
m/e
(B)
FIGURE16-6 Mass spectra lor glutamic acid: (A) lield ionization; (B) lield desorption.
obtained by field ionization and field desorption methods are compared. Very
an
Iittle fragmentation occurs with field desorption. Either method is adequate
for molecular weight determination. FAB is lhe most frequently used met hod
for molecular weight determination ofnon-volatile materials giving dominant
(M + H) + and(M - H) + ionsfor organicmaterials. With organicmaterials and
organometallic compounds, significant fragment ion information is obtained
providingstructuralinformation.Acomparison ofthe resultsonorganometallic
compounds from various ionization techniqucs is reported(19b)
16- 7 EVALUATION OF HEATS OF SUBLIMATION
ANOSPECIES IN THE VAPOR OVER HIGH
MEL TING SOLIOS
Evaluation of the heat ofsublimation is based upon the fact that the intensity
ofthe peaks in a spectrum is directly propo.Lional to the press ure ofthe sample
in the ion source. The sample is placed in a reservoir eontaining a very small
pinhole (a Knudsen cell), which is connected to the ion souree so t hat the only
way that the samplecan enter thesource is by diffusion through the holeo If the
eell is thermo tated and enough sample is placed in the eell so that the solid
phase is always present, the heat ofsublimation ofthe solid can be Obtained by
sl udying the change in peak intensity (whi ch is related to vapor pressure) as a
function ofsample tcmperature. The small amount ofsample di ffusing into the
ion beam does not radically affect the equilibrium in the eeH. Sorne interesting
results concerning the nat ure ofthe species present in the vapor over sorne high
melting solids have been obtained from this type ofstudy. Monomers, dimers,
and trimerswerefound over lithium chloride, while monomers and dimers were
found in the vapor over sodi um, potassium, and cesium chl oride.(20)
The species e r, e rO, er0
2
, 0, and 0 z were found over solid e rZ03'
Appearance potentials nd bond dissociation energies of these species are
reported(ZI) The vapors over Mo0
3
were found lo consist of trimer, tet ramer,
and pentamer. Vapor pressures,freeenergy ehanges, and enlhalpies ofsublima-
ti on were evaluated(22)
160
664 Chapter16 lonizat ion Methods
16-8 APPEARANCE POTENTIALSANO IONIZATION
POTENTIALS
As mentioned earlier, the molecular ion is produced whenever colJi sion occurs
with an electron with energy equal to or greater than the ionization energy of
the molecule. A typical curve relating electron energy to the number of ion
fragment s of a particular type produced (Le., relative intensity of a given peak)
is illustrated in Fig. 16--6. This is referred to as an ionization efficiency curve. At
electron energies well below the ionization energy, no ions are produced. When
the energy of tne electron beam equals the ionization energy, a very low intensity
peak results, for in the col!ision al! of the energy of the electron wil! have to be
imparted to the molecule, and this is not too probable. As the electron energy
is increased, the probabiJity that the electron will impart enough energy to the
molecule to cause ionization is increased, and a more intense peak results unti l
a plateau fi nally occurs in the curve. Tbe tail of this curve at low energies results
because of the variation in the energies of the electron in (he bombarding beam.
Therefore, the cur ve has to be extrapolated (dotted line in Fig. 16--7) to produce
the ionization energy. Various procedures for extrapolation and the error
introduced by these procedures have been discussed in det ail. (2 1) When the peak
observed is that of the molecular ion, e- + RX -+ RX t- + 2e-, the ionization
energy of the molecule can be obtained by extrapolation of the ionization
efficiency curve. When the peak is that of a fragment, extrapolation of the
ioni zation efficiency curve produces the appearance potential of that fragment.
For example if the peak being investigated is that of the fragm nt R + from the
molecule R - X, the appearance potenti al, A
R
+, is obtained by extrapolation of
the ion efficiency curve for this peak. The appearance potential is related to the
following quantities :
(1 6--19)
where D
R
_ x is the gas phase dissociation energy of the bond R - X; IR is the
ionization potential of R; Ek is the kinetic energy of the particles produced; and
Ee is the excitation energy of the fr agments (Le., the electronic, vibrational and
t
~
' ;;
e
~
FIGURE 16-7 An ionization
e
efficiency curve"
~
'"
ro
ti
e
lne. eleetron energy --
16-9 The Fourier Transform Ion Cyclotron Resonance Technique 665
rotational energy if the fragments are produced in excted states). Generally, Eh
and Eeare small and equation (16--19) s adequately approximated by:
(16-20)
If D
R
-
X
is known, IR can be calculated from appearance potenti al data. Often,
IR is known, and D
R
-
X
can be calculated. The value for IR must be less than Ix
for equaton (16--20) to apply ; otherwise, X+ is dissociated or electronically
excited. Experiments of ths sort provide one of the best methods for evaluating
bond dissociation energies but give less exact ionization energy data than can
be obtained by other means.
An article on the mass spectrometric study of phosphine and diphosphine
contains a nice summary of sorne of the information that can be obtained from
these studies. Ionization energies and appearance potentials of the principal
positive ions formed are reported. The energetics of the fragmentation processes
are discussed and a mechanism is proposed.(22)
16-9 THE FOURIER TRANSFORM ION CYCLOTRON
RESONANCE TECHNIQUE
In FTICRj MS, an ion is generated with mass, m, and charge, e, as previousl y
discussed for mass spectroscopy. In a uniform magnetic field , the magnetic force
acting on a particle with initial velocity causes the ion to follow a helical path
along the axis of the magnetic field. The frequency of the circular motion 10
Hertz, i. e., the cyclotron frequency is given by
Ve = eHj2nm (16--21)
and The cyclotron frequency is independent of the velocity of the ion, v.The velocity
and distribution will give rise to a distribution of helical circular radii , r, for ions
with the same cyclotron frequency according to
For magnetic fields of 1 T, the cyclotron frequency falls in the r.f. range (0.01 to
7.00 MHz).
In an ICR trapping cell, two trapping plates perpendicular to the magnetic
field are used to prevent the ions from travelling along the field direction. The
plates are maintained al a potential of about + 1 V for positive ions and -1 V
for negative ions. The magnetic field and trapping potential constrain the ions
to a region of space in the center of the trap. Two parallel receiving plates and
two parallel transmitter plates Iying along the axis of the field and in between
the trapping pIates form a box shaped cell of six plates. The cel! is mounted in
a high vacuum in a strong magnetic field (typically 21 tesla).
Application of an externa) oscillating field with a frequency corresponding
to the cyclotron frequency of an ion, Ve' across the transmitter plates causes ions
of that mass [equation (16--21)] to move into resonance with the applied field
FTICR/MS
666 Chapler 16 lonization Methods
and spiral out to orbits of larger radii. The kinetic energy of the particle is
increased and its radius also increases according to
(16-22)
As the resonance condition is fulfilled, the random distribution of phases for the
ions is changed to a " packet" of ions that all move simultaneously with the
applied field. If the appl i d field is turned off or its frequency changed so it moves
out of resonance with Ve' the ion packet persists long enough to induce an image
current in the detector pi ate. The signal decays with time as collisions of the ion
with neutral molecules restore the original random distributi on of phases. The
signal in the time domajn contains infor mation a bout the frequency of the ion
and the ion concentrati on. (23)
A mass spectrum of the total ion population in thc cell is detected by
applying a field to the transmitter plates whose radio frequency changes rapidly
over the range corresponding to the masses of interest [recall equation (16-21)].
As each ion undergoes resonance, a superpo ilion of image currents is observed
in the detector circuit and stored in a computer. The transmit-detect cycle is
repeated many times and signal averaged. A ourier transform of this data
produces a plot of ampl itude versus frequency or mass [equa t ion (16-21)J of al l
the ions present, Le. , the mass spectrum. The mass limit of detection depends on
the magnetic field. At 3 T, good mass resol ution up to 3000 amu results.
After the ions are formed in the cell and b fore detection, any one ion can
be excited or, if they absorb sufficient energy, be caused to spir' 1 to such large
orbits that they are ej ected from the cell. The excited ions collide with neutral
molecules and fragment, a phenomenon called chemically induced dissoci a t ion
(CID). This techni que is advantageous for str ucture det erminarion or for provi -
ding endothermicities of bond dissociative pat hways. If the cj ected ion is reformed
with time by a chemical reaction, the rate of the reaction can be studied. By
monitoring changes that occur in ion concentrations when a reactive species is
introduced into the tra pped ion eeH, reaction rates and equilibria for gas phase
reactions can be measured(23,24)
Adiabatic elect ron affinities for a metal complex, M - , can be studied by
measuring the equilibrium constant for the reaction:
and knowing that the EA ofS0
2
is 1.097 eVo Ifthe reaction does not occur other
reference compounds besides S02 can be employed. lf the reaction goes to
completion wi lh a compound X a nd does not occur with S02, the electron affinity
of M- is bracketed bet ween X and S02 ' Aboul 100 organie compound, have
been bracketed between known sy tems over a range of 3 eV by this technique. (2S)
Adi abatic ionizat ion energies for a substance M are obtained in an analogous
fashion by st udying the reaction
where the lE of X is known.
16-11 Photoelectron Spectroscopy 667
is
Ligand exchange reactions have also been studied enabling one to obtain
ligand basicity orders toward various cations.(26a)
22)
ML+ + L ~ M L + + L
In sorne instances the equilibrium constant can be measured, and in other
he
instances the relative basicities are estimated by laddering. Several excellent
the
reviews providedetailsconcerningthe aboyeapplications(26)Analytical applica-
"'es
tions oflCR have also been reviewed.( 27)
ge
on
me
16-10 INTRODUCTION
In this section we inelude techniques that, when applied to solids, provide
information primarily about the surface of the material. Sorne of the methods
can also be used to study gaseous and liquid samples. UPS is included in this
section even lhough it is used primarily on gaseous samples because of its
similarity to XPS. There is an immense literature background in this area. A
brief introduction to selected methods will be presented that discusses the
principies of operation and provides an ill ust ration of the kind of information
obtained. Most ofthe methods use an ion,electron,orx-raysourceand monitor
the energy or spatial resolution of the scattered (or rcs ulting) ion, el ectron, or
photon beamproducedafter thesourceimpingesOn the samplc.Since t hesource
can be very high in energy, induced reactions uruortunately can lead to (he
detection of materials that are not characteristic of the sample. One must also
be concerned with the homogeneity ofthe surface when methods that pr oduce
information abouta small areaareemployed. Methodology that permits exami-
nationofthesurfacelateraland transverseplanesaddressesthisconcern.FinalJy,
onemust becareful not to infer propertiesabout the bulk sample from a surface
measurement unless it is known that the surface actually represents the bulk
property.
by
16-11 PHOTOELECTRON SPECTROSCOPV
Photoelectron spectroscopy has its basis in the photoelectric effect. There is a
her
threshold frequency, v" required in order for radiation impinging on a solid to
be able to eject an electron from the solid into a vacuum. The work function cjJ
is defined as the correspondingminimum energy required,
(16-23)
where e is the charge of the eJectron and h is Planck's constant. At higher
frequencies of incident radiation, the emitted electrons have a ki netic energy
corresponding to this excess frequency, Le.,
E
kin
= hv - ecjJ (1 24)
Surface
Science
Techniques
The emitted electrons with maximum kinetic energy come from the conduc-
tion bando Electrons in orbitals below the conduction band are bound and emerge
with less energy than those in the conduction bando
(16-25)
where Es is the binding energy. Using photons whose energies are greater
than the work function and measuring the kinetic energy of the ionized electrons
produces the photoelectron spectrum. The spectrum is a plot of the number of
electrons emitted versus the ki netic energy of the electron, (see Fig. 16- 8). The
peaks in the spect rum provide Es for various electron states of the surface species.
If a sample contains the same element in different chemical environments
(e.g., the nitrogen in N-N-O), different values fOT Es will result. Only a single
electro n is ionized from a given molecule so the different signals arise fr om
different molecules. The difference in energy for the different E
B
values corre-
sponding to different environments is called the chemical shifi.
The so urce photon is monochromatic. Depending upon whether x-ray or
ultraviolet radiation is employed, two different experiments result. The x-ray
source(28a) experiment is caBed either x-ray photoelectron spectroscopy (XPS) or
electron spectroscopy for chemical analysis (ESCA). The ultrayiolet source(28b)
is called ultraviolet photoelectron spectroscopy (UPS or PES). XPS is concerned
with both valence a,nd non-valence shell (core) electrons and UPS with valence
shell electrons. We shall discuss the applications of these two spectroscopic
methods separately.
XPS
Solids (inc1uding frozen solutions), gases, liquids, and solutions have been studied
~ by XPS. Binding energies, E
B
, of both core and valence electrons can be measured
as seen in equation (16-25). In the XPS experiment, the binding energies are
expressed reJative to a reference leve!. Since the solid sample is in electrical contact
with the spectrometer, the Fermi level, e<f;, of the sample and spectrometer are
the same. As a result, only the spectrometer work function is needed to calculate
Es, referred to the Fermi level, [rom a measured kinetic energy. With an
insulating sample a buildup of positive charge can occur near the surface resulting
in a dipole layer and perturbation of the binding energies. An external standard
with a known core energy, (e.g., Au) can be deposited on the surface and binding
energies measured relative to the standard. The energies can also be measured
relative to the edge of the valence band.(29)
The binding energies of atoms vary with oxidation state and partiaJ charges
on the atoms. Compilations exist(30) that enable one to use binding energies to
determine these quantities by a fingerprint type of application. Generally, the
binding energies of cations increase with increasing oxidation state. O pposite
behavior is observed for PbO in comparison to Pb0
2
and this is attributed to
differences in the Madelung potential in the twostructures. Very small differences
in binding energy are found for Ag
2
0 compared to Ag and for Cu
2
0 compared
to Cu. On the other band, the Es (1s) for C u and CuO differ by 4.4 eY.
It is interesting to note that linear correlations have been found between
core-electron binding energies and Mossbauer isomer shifts for compounds of
or
ay
or
Bb)
ed
.ce
,ic
.ed
tu
Ir
lct
are
lte
an
lng
lrd
ing
red
ges
to
the
lite
to
.ces
red
een
i of
tin andiron.(31a) Also, acorrelationofchlorinecorebindingenergieswithnuclear
quadrupole resonance frequenci es has been found( 31b)
Attempts have been made to correlate the binding energies to orbital
energies from molecular orbital calculations. The basis for this approach is
Koopmans ' theorem,whichstatesthatthe vertical ionizationenergyfor removal
of an electron from a molecul ar orbital corresponds to the negative of the
eigenval ue obtai ned from the molecul ar orbital calculation. It is thus assumed
tha! the molecula r orbitals for the pareot molecule and the ionized molecule are
the same. Any electronic relaxati on or change in correlation energies causes
Koopmans' theorem to break down leading to li mited quantitative success for
this approach.(32)
The photoemission process comprises the following events:
1. Absorptioo ofthe photon by the boundelectron, thereby iocreasing the
kinetic energy ofthe electron.
2. EjectionoftheeJectronfrom theatom usingsorneofits kineticenergyto
overcome the Coulomb att raction ofthe nucJeus.
3. Simultaneous wit h 2, the electrons in the outero rbitals readj ust(intra-
atomicrelaxat ion)to a lower-energy final state, transferri ng this energy
to the outgoing elect ron.
Relaxation does not necessarily result in the formation ofthe ground state
of the ion. Simultaneous with the photoioni zation ofan electron, there can be
excitation ofone ofthe remaioing electrons to an initially unoccupied orbital.
Thisphenomenoniscalleda"shakeup"process.Thehigherenergy,lowintensity
structureonXPScore-electronpeakscanthenbeusedtostudyvariouselectronic
transitions occurring simultaneo usly with t he photoionization. These satellite
features arefound in the rangefrom zero to 50eVtoward higher bindi ngenergy
than the main peak. Obviously, an electronic a bsor ption at 50 V ( = 404,000
cm- 1= 25 nm) is a very high energy absorption in the vacuum ultravi olet.
Photoemission from states belonging to a shell with an emply or partially filled
subsheJl will exciteall states accessible by redistributingtheelectrons within that
shell that have the same symmetry as the state produced by t he one electron
transition.
An example of such satellite XPS features appears in Fig. 16--8. Broad
features are seen toward higher binding energy than the two 1. peaks for
02'Thefealures markedA,B, andC are "shakeup"peaksappearingassateUites
on t he valence-electron peaks.
I n ions with a partially filled outer shell, the coupli ng ofthe outer shell to
the core hole (all pin and angular momenta) wi Uresult in a sel of final states
with distinct energies. Thespectrum will exhibit fine structure(vide infra).
The "mixed-valent" species that was described in Chapter 10 [(NH
3
)sRu-
(pyrazi ne)Ru(NH
3
h]5+,hasalsobeenst udiedbyXPS.(33)TheXPSspectrumhas
been reported to contain ionization peaks from two non-equivalent transition
metal ions. The carbon 15peaks occur in the same spectrai region as the metal
ionization peaks, and tbeconclusion rests 0 0 the ability to subtract these peaks
from the spectrum.The XPS technique hasa very short timescale,on the order
of 10-
17
seco However, when a core el ctron is removed fr om a mixed-valenl
compound, only discrele valences are obtained a nd ftuctuati ons cannOl persist
in the fi nal state. Depending on t he spin of the core electron removed, two
differenl spin states can result from lbe final ion. Thus, t wo "discrete peaks " in
e/200s
e/200s
OXYGEN
o o
01s
2s 2s
Ou2s
5000 500
1 I
('I)('I)
w
1- OgOuls
<l:
1s --- -%-15 a::
o
z
:::
4000 400
z
W :::J
1- o
<l: u
a:
o
z
:::
z
63000 300
u
Og2s
('L)('I) Og2p
('1)('1)
1
2000
200
I
e B A nu2p
('n)('n)
1 1 1
ng2p
1I 1
100
1000
O
\o

BINDING ENERGY
FIGURE 16-8 XPS speetrum 01 eore and valenee eleetrons in O
2
exeited by Mg Ka
X-radiation. Two peaks are obtained lor eaeh lully oeeupied orbital , inelud ing the
oxygen 1 s eore orbital. (27) The peaks A, B, and C, and the peaks toward higher
binding energy Irom the 0'5 peak, are satellite peaks (vide infra). (From K.
Siegbahn, et al., " ESCA Applied to Free Moleeules, " North Holland/Ameriean
Elsevier, New York, 1969.)
16--11 Photoelectron Spectroscopy 671
the XPS do not distinguish mixed valence from delocalized systems. The reader
is referred to reference 34 for a critical discussion of the application of physical
methods to mixed-valent systems.
UPS
In the U PS experiment, vacuum ultraviolet radiation is used as the ionizing
radiation ; usually this is provided by a hel ium [si ngly ionized, indicated as He(I)]
resonance lamp with an energy of 21.21 eVo O ther discharge lamps have been
used. The energy of these lamps limits UPS to studies of valence electrons and,
in general, measurements have been mostly confined to gaseous samples. There
have been sorne reports of work on solutions(3S) and solids(36)
The PS spectrum of a gaseous sample of N
2
is shown in Fig. 16--9. With
the He(l) so urce determi ning an ioni zing limit of 21.21 eV, three vibrationally
structured photoionizations are seen ~ 1 5 . 6 , ~ 17.0, and ~ 18.8 eV). These can
be assigned to ionizations from the three highest-energy filled molecular o rbitals
for N
z
, t he 2IJ,,, n", and 3IJ
g
orbitals. Tbe peak s have been assigned on t he basis
of the observed vibrational struct ure. As an aside, it should be noted that an
XPS spectrum has the same three peaks (vibrational struct ure not seen beca use
of lower resolution) in addi tion to a peak at 37.3 eV for ioniza tion from the 2IJ
g
level as well as a single peak at 409. 9 eV for bOlh the 1IJ
g
and llJ" levels(28a)
In Chapter 3 the symmetry and constructi on of lhe molecular orbitals of
NH
3
were worked out. There it was fo und that tbe seven atomic orbitals in C
3v
symmetry form a representation that is reduced to gi ve three a and two e
irreducible species. The eight valence electrons of NH) fill two of the a and one
of the e molecular orbitals to give a ground state configuration of
The only other filled orbital, the 1a
l
orbital, is essentially the nitrogen ls atomic
or bital. The He(I) (21.21 eV) spectrum is shown in Fig. 16--10, where vertical
ionizations are seen at 10.88 eV for t he 3a level and at 16.0 eV (fi r t maximum)
ror the 1 e level. These assignments were made with the use of res ults from various
m.O. calculations. The more energetic He(II (42.42 eV) source has been used to
observe the 2a vertical photoionization at 27.0 eV(38) In passing, it is of interest
to note the doubled or spli t cha racter of the le peak al ~ 16 eVo This spiitting
has been assigned to Jahn-Teller splitting in the ion resulting from a
(2a ?(le)3(3a)Z configurat ion. The spli tting is 0.78 eY. Other examples of Jahn-
Teller splitting have been reported(28b)
The vibra tional structu re on a UP S band tells something about t. he bonding
cha racteristics of tbe electron t hat is ionized. The ionization of a non-bondi ng
electron will result in an ion wit h the same internuclear distance as t he parent
molecule. In this case the lowest energy (v = 0, v' = O) vibrational peak will
dominate the spect rum (see F ig. 16-11). Referri ng to the Ni spectrum in Fig.
16--9, we see t bat ionization of electrons from ei thcr Ihe 3IJ
g
level at 15.6 eV or
the 2IJ" level at 18. 8 eV in each case gives essentially only one strong peak. These
levels are weakly antibonding and weakly bondi ng, respectively.
Photoionization of either a slrongly bonding electron or a strongly anti-
bonding electron will result in cha ng S in equiJi brium bond distances, as ill us-
trated in F ig. 16- 11. I n these cases, the most intense peak (i. e. , vertical ionization)
3,000
I
U
:ll

e
:J
O
U
18,75(9)
I / 16,69(1)
"....".1557(9)
eV
(A)
"+----+ +----+',
(8)
FIGURE 16-9 PES spectrum tor a gaseous nitrogen sample, [From D, W, Turner
and D, p,May,J,Chem. Phys., 45, 471 (1966), ]
will be at hgher energy than the p ak corresponding to adiabatic ionization.
This is exempli fi ed by the JIu peak for N
2
. In fact, the relative intensities (caBed
Franck-Condon factors) of the respective vibrational peaks can be theoreticalIy
calculated with reasonabl e succ SS.(3 7) The vibrational frequencies ob rved for
the ionized molecular state are al so of further assistance in characterizing lhe
molecular orbital fr m which the electron is ionned. The ground state stretching
1&-11 Photoelectron Spectroscopy 673
1
U

e
::J
O
U
M+
lonized
Molecule
M
frequency for N 2 is 2345 cm -1. Table 16-2 li ts the stretching freq uencies seen
for various N
2
+ ionized states. A comparison of each of these values with
the 2345 cm - 1 N 2 frequency leads to the implied m.o. characters of the lost
electron given in Table 16-2.
In addition to vibrational structure, other fine structure is seen in UPS
spectra. The first (i.e ., lowest binding energy) peak in the spectra of CH
3
CI,
CH
3
Br, and CH
3
1 is, obviously, from the highest occupied molecular orbital,
and this is largely localized on the halogen atom (with sorne X - H anti-bonding
eV
(A) (8)
FIGURE 16-10 PES
spectrum of a gaseous
sample of ammonia. (From
D. W. Turner , et al.,
" Molecular photoelectron
Spectroscopy, "
Wiley-Interscience, New
York, 1970.)
FIGURE 16-11 Vibrational
states for the parent
molecule M and the ionized
molecule M+. (A) In this case
the electron ionized comes
from a non-bonding orbital
and the two electronic
potential wells lie one aboye
the other . The most intense
transition (indicated with an
arrow) is the V' = O<- V = O
transition. (B) The wells are
displaced (molecule
dimensions change) when
the electron ionized comes
from either a bonding or an
antibondl ng orbital. In this
case the V' = 2 <- V = O
transition is the most intense
band seen.
TABLE 16-2. Vibrational Structure in the
N
2
UPS Spectrum
Implied
Peak v(N-N) M.O. Characler
(Jg(2p)
2150 cm-
weakly bonding
1'C
u
(2p)
1810cm-
strongly bonding
(J,,(2s) 2390 cm -
weakly antibonding
and C- H bonding character(38) Spin-orbit splitting is secn in this peak, where
the separation varies in the series: CHJl t- , 0.62eV; CH
3
Br +, 0.3 1eV; and
CH
3
Cl ", ~ eV(28b) These spin-orbit intcractions agree with Mulliken's predica-
tions of 0.625, 0.32, and 0.08 eV, respectively.(39) Many other such observations
of spin-orbit interact ions ha ve been noted. In fact, recent work at lhe high
resol ution of 10 meV has detected spin-orbit splittings in NO of 0.012 to
0.016 eV.(40)
A considerable number of smaJl gaseous molecules have now been studied
with UPS and, for that matter, XPS. Sorne radical and excited state spe ies have
also been tudied. The three expected states (2P, 4S, and 2D) of 0
1
have been
detected(41) An electrodeless microwave discharge was uscd 'to produce the
excited state species 0 2e Ll
g
), and the photoelectron spect rum of t his species
shows a vibrationall y structured peak owing to formation of O
2
+eO,,). Compar-
ison with the peak corresponding to ionization of ground state 0 2eLg - ) to the
same onic sta te gives a val ue of 11.09 0.005 eV for the adiaba tic ionization
potential Of02e Llg).(42) Several other such species (e.g. , SO and NF
2
) ha ve been
sl udied.
In comparison with di amagnetic compounds, paramagneti c species , how
additional complexity in the UPS (and XPS) spectra. The oxygen molecule has
two unpaired 7r
g
electrons. The UPS spectrum of O
2
is given in Fig. 1 12. The
photoionization of an electron from the partl y filled, antibonding 7r
g
(2p)
molecular orbi tal appears as the first peak in the UPS spectrum. Only one ionic
state is realized. On the other hand, photoioni zation of an electron from one of
the olher fi Iled molecul ar orbitals leads, in each casc, to t\Vo clectronic states of
the ion O
2
+. Thus, if an electron i ionized from th fi ll ed bonding 7r" level, the
unpaired electron remaining in the 7r
u
orbital can be aligned eit her with or against
the two unpair d el ctrons in the ant ibonding 7r
g
leve!. When the elect roo is
aligned with lhe two 7r
g
electrons, there are three unpaired electrons, the total
spin S = 3/
2
, and lhe electronic state of the O
2
+ molecule is 4 n u. The other
alignment gives a 20" electronic state for the O
2
+ molecule. The 4IT" and l IT"
sta tes of O
2
+ are at different energies, and thus there is a splitting of t he 7r
u
orbital ionization peak. In Table 16- 3, the observed features fo r the O
2
molecule
from bot h UPS and XJ.JS spectra are listed.
The XPS spectrum of gaseous O
2
is shown in Fig. 16-8. Thc oxygen l s peak
is also split, in t his case by 1.1 eVo This splitting is not the difference bet ween the
O
2
molecular orbi tals IsO'" and lsO'g, which is calclllated to be smal!. Recall that
no such spli tting is seeo in the case of N
2
. Even further , the intensity ratio of
the two O l s feal ures is 2:1 and not the l:1 ratio expected if the lsO'u/1sO'g
explanation applied. Again, as occurred in the valcnce orbi tals, there is an
interaction between the lI npaired electron in the O l. leve! and the two unpaired
+ 4
O;, ?4E 0;)41';
021 nu
o;,2ng"'- 02.X J rg
V
,
IP FeF. v IP.
v IP.
v' I.P.
O 16.12
O 20. 29 0 18 O 18 .17 O 12.08
1 16.26
1 20.42 0.24 1 18'. 33
2 16.37
1 12.32
2 20.55 022 2 18.45 3 16.49
2 1254
3 2067 0.16 3 18 . 58 4 16.60 3 12.73
4 20.78 0.12 4 18.71 5 16 72
5 20.88 0.04 6 16.83
6 2096 0.03 7
8 1704
9 17.' 14
10 1723 FIGURE 16-12 Oxygen PES
11 17. 33
spectrum. (From H. A. O. Hill
12 17.43
and P. Day, "Physical
Methods in Advanced

Inorganic Chemistry,"
o
u .
Interscience, New York, p.
88, 1968. )
1000
0L-________ ____
2 :3 4 5 6 7 8 9 10
Eleclrone<lergy (ev)
TABLE 16-3. Vertical O
2
lonization Data"
OneElectron lonlcElectronlc
MolecularOrbital State XPS, eV PES,eV
ng2p 13.1 12.10
16.26
{:::
17.0
n,,2p
?
f
2
n
"
g
18.8 18.18
!J
g
2p
2g 21.1 20.31
25.3 24.5 [ viaHe(ll)]
!J,,2s
f"
27. 9
2"
39.6
fg
!J
g
2s
2g
41.6
543.1
f
2 Oxygen 1s
544.2
See reference 27.
electrons in lhe O
2
+ng ant ibonding molecular orbital. Ioni zation ofeven these
oxygen eoreeleetronsl ads lo two Oz+ states, 2and 4, th-at differappreeiably
in energy.
The observation ofsueh splittings is vcry interesting. One-eenlcr exehange
integrals dominate theenergydifference bet ween the quartet and doublet,tates.
Thus, intereleet ron repulsions (e z/rj, where rj is lhe distance between the ith
and jth eleetrons and e is the eharge on the eleelron)ofthe exchange type are
appreciable even between valence unpaired el ctrons and lhe oxygen eore
FIGURE 16-13 (A)
Photoelectron spectrum 01
NO using the He 304- line;
three small peaks marked
"a" are due to the He 320
line; recording time was 75
h. (B) Photoelectron
spectrum 01 the B' 'L+ state
01 NO using the He 304
line; the peak at "a" is
again due to the 320 line.
(e) Photoelectron spectrum
01 NO using the 584 line.
Resolution 10 meV.
Deconvolution 01 the peaks is
indicated by the dot!ed lines.
[From O. Edqvist, L. sbrink,
and E. Lindholm, Z.
Naturlorsch., 26a, 1407
(1971).]
electron. Such intereJectron spin polarizations are found to be of importance in
explaining the shifts in nmr peaks for paramagnetic molecules (see Chapter 12).
Electron exchange splitting is also seen for core electrons of paramagnetic
transition metal complexes, as is described in a later section.
It is clear fr om the aboye discussion that the UPS spectra of relatively large
molecules are quite rich with information about ionization potentials, vibrational
quanta for the ionized molecule, spin-orbit in teractions, ] ahn-Teller spli ttings,
and electron exchange interactions. U nfortunately, there is frequently an over-
lapping of features, and broad peaks appear with no resolved vibrational
structure. As an example of a small molecule with many photoionization peaks,
Fig. 16- L3 illustrates sorne of the spectral detail obtained(40) fo r gaseous NO at
a resolution of 10 meV for a He(I) source and at 25 meV for a He(JT) source. For
A' n
__ w \,.
3
(A)
24 22 20 18 16
eV
(B)
I I I I
24.0 23.5 23.0 22.5
eV
')
\
\
\
\
I
f
I \ ' \ ~
IJA\ ~
'0 '1:- '\" '1;-
'0
'\,.
(e) I I I I
18.8 18.7 18.6 18.5
eV
31;-
in
2).
tic
ge
lal
~ S
:r-
lal
(S,
at
or
r-
16-12 SIMS (Secondary Ion Mass Spectrometry) 677
the fine points of assignment (he reader is referred to reference 40. fi gure 16-13
shows that both exchange and spin-orbit splittings ha ve been resolved.
16-12 SIMS (SECONDARV ION MASS SPECTROMETRV)
Secondary ion mass spectrometry(43.44) employs an energetic (> 4 keV) beam of
primary ions (e.g., 4Ar+, 202Hg+, 11' 0 - ) to collide with surface species and
dislodge them as secondary ions. Upon collision with the surface, the primary
ion is implanted in the solid and its kinetic energy is transferred to atoms in the
condensed phase. This energy causes desorption (sputtering) of a surface species
producing gas phase ions. The mass spectra of these secondary ions are then
detected. Both positive ion and negative ion spectra are detected. Figure 16-14
shows both types of spectra that result from Ar+ bombardment of an aluminium
surface.
0-C
2
0- AIO-
AI- ~ I - / AIO;
,
o 20 40 60 80 100 120 O 20 40 60 80
Mass number/charge (mle) ~ - (A) Mass number/charge (mle) ~
sec (B)
(A)
FIGURE 16-14 SIMS spectrum. Secondary ion intensity versus mass number/ion
charge 01 an aluminum target under Ar bombardment. (A) Positive secondary ion
spectrum. (B) Negative secondary ion spectrum.
The escape depth for sputtered partic1es ranges from the surface to greater
than 20 , depending on the target material and energy of the primary ion. The
predominant secondary ion species observed in SIMS are singly charged atomic
and molecular ions. As in mass spectroscopy, the isotopic composition aids in
identification of the fragments, which in tum leads to information about the
chemical composition of atomic layers at or near the surface. This is referred to
as static SI MS. By using ion etching (high primary ion current densities),
underlying layers can be exposed and the SIMS determined as a funct on of
depth. This is referred to as dynamic SIMS. I n the dynamic SlMS mode, the
chemical composition of the material in the deeper layers is changed by the
prebombardment of the surface. I n addition to chemical reactions, the more
volatile components can be " boiled" otT. Static SIMS minimizes this problem
with negligible surface perturbati on by the bombardment but provides informa-
tion only about processes occurring on the surface. Even in static SIMS
perturbation of the emission region befo re the secondary ion part ic1e is emitted
cannot be exc1uded. (44) SIMS instruments are available that provide lateral or
xy information about the surface. Ion microprobes provide this information
through probe imaging. Other inst rumenls provi de a direct image of the surface.
Since the dete lion limits are very low (1 ppb for many el ements), surface
contamination by hyelrocarbons, Cu, CO
2
H
2
, 0z, and H
2
0 is common. N
z
The surfaces close to the sample can also be contaminated by sputtered material.
An additional complication is decomposition of the surface material by the high
energy primary ion so urce, thereby producing materials that are not actually on
the surface. The reader is referred to references 43 and 44 for a discussion of
experimental problems.
SIMS is used to identify surface species and also to study the dynamics of
surface processes (e.g., diffusion and corrosion). The catalytic decomposition and
synthesis of ammonia on iron metal has been studied.(45) The surface species
present on the commercial silver catalyst used to convert ethylene to ethylene
oxide have also been investigated.(46) The reader is referred to references 47, 48,
and 49 for reviews of SIMS applications.
In molecular Sl MS, the primary beam expels molecular secondary ions from
samples of organic molecules supported on the surface. The molecular ions can
dissociate to give fragments that contribute to the SIMS spectrum. The region
just aboye the surface, called the selvedge, has a relatively high pressure where
ion-neutral molecule association reactions can occur. For example, the SIMS
spectrum of a sil ver fi lm studied in the presence of benzene vapor produces
(AgC
6
H
6
t in SIMS. In the vacuum chamber, unimolecular dissociation reac-
tions occur in the course of traveling to the analyzer.
Molecular species are converted into secondary ions via three distinct
processes listed in order of efficiency: direcl sputtering, cationization (or anioniza-
tion), and electro n loss or gain. In sputtering, m0111cntum transfer from the
primary ion di slodges organic cations and anions from l he solid to the gas phase.
Organic dications in solids have been vaporized as gaseous doubly charg d ions.
The limited degree of di ssociation seen in SIMS spectra i!lust rates tile low internal
energy of the ions formed(49) Cationization, in molecular SJMS, results fr0111 the
ion-molecule reaction during or fo!lowing the formation of suppor t metal ions
and the thermally induced evaporation of a supported orga nic molecule from
the surface. One of the complications in the interpretation of SIMS involves
distinguishing weak aggregates in a solid from aggregates formed in the selvedge
under ion bombardment. The ion-molecule complex fo rmed in the selvedge can
fragment in the course of travelling to the analyzer much in the same way as the
unimolecular dissociations mentioned previously. The final process to be dis-
cussed involves electron transfer from or to the surface molecule generating M +
and M . These ions can undergo unimolecular decomposition leading to
fragment ions. Examples of compounds that produce secondary ion s by these
mechanisms have been reported(49)
lnvestigation of the chemistry that can occur when reactive primary ion
beams are employed represents a recent growth area for SIMS. Studies show
that N
z
I is a reactive primary beam(50)
16- 13 LEED, AES, AND HREELS SPECTROSCOPY
LEED
Ln low energy electron diffraction (LEED), a monoenergetic beam of electrons
(l O to 500 eV) is incidcnt on one face of a si ngle crystal. About half of the electrons
are back scattered and the elastically scattered fraction hits a ft uorescent screen.
A we!l-ordered surface resul ts in a diffraction pattern. Surface crysta!lography is
al.
h
on
of
es
c-
lct
za-
.he
.se.
ns.
lal
.he
lOS
)m
ves
Igc
:an
Ihe
lis-
fi-
to
ese
on
ow
)ns
lOS
en.
is
carried out(51) by finding the surface structure that optimizes the fit of an
estimated calculated pattern and theexperimental one over a significantly large
range of diffraction conditions (electron energy, beam angles and number of
diffracted beams). In order to obtain information normal to the surface, the
variation in the intensity ofa given spot in the difraction pattern is studied as
a function ofthe incident beam energy. The theory involved in the calculation
oftheexperimentalobservablesis complex. (51)Studieshaveenabled thecompar-
ison of the surface structure with bulk structure and have shown the preseuce
ofa terrace geometry involving stepped surfaces(51) (often one atom in height).
Oxidationorcarbidizationofthesurface has been studiedandthecorresponding
change in surface structure determined. Reactivity of the stepped surfaces are
found to be different from those that are not stepped and different for various
types ofsteps.(52)
A very interesting application of LEED involves determination of the
structure of ordered adsorbate-substrate structures. Adsorbate-substrate dis-
tances accurate to 0.1 Aare claimed. A large number ofsurface structures for
gases (e.g., O
2
, HzS, C
2
H
4
, C
6
H
6
, CO, CH
4
, C
5
H
s
N) adsorbed on substrates
have been compiled.(51)
AES (AUGER ELECTRON SPECTROSCOPY)
In Augerspectroscopy(AES), the incident electron beam ionizes an atomic core
level electron. The energy reJeased when a higher-energy electron falls back to
fill the core level is transferred to a valence electron, which is ejected into the
gasphasewhereitis detected asanAUGERelectron with anelectronspectrom-
eter.( S3) The AUGER electrons appear as small peaks on a large background
of backscattered electrons including the elastically scattered primary electrons,
of LEED. The LEED optics can tberefore be used to obtain the AUGER
spectrum and the two met hods areoften used in combination. The energy ofthe
AUGER electron varies with the surface element and ,ts oxidation state. The
AUGER electron escape depth varies from to 25 A depending on the
material,so this is clearly onlya surface method.(53) Diffusion,corrosion,surface
aggregation,andsegregationcanbemonitored.ThereactionofsulfurwithO
2
on
a Ni(111) surfacewasstudied(54) byAES in conjunction with massspectrometry.
The rate of growth of the oxygen peak and decrease in the sulfur peak was
monitoredasa function ofOz pressure.Themechanisminvolved O
2
adsorption,
reaction of adsorbed Oz with adsorbed slllfur to produce adsorbed SOz, and
desorption of S02 ' The reaction to form adsorbed S02 is rate controlling.
Adhesion, friction, and wear have been investigated showing changes in surface
segregation of various componentsY1) Changes in the surface composition of
heterogeneolls catalysts have also been studied and correlated with catalyst
poisoning.(55,56)
HREELS
High resol uti on electron energy loss spectroscopy(HREELS) is anotherform of
electron beam spectroscopy. Vibra tional excitation of surface atoms is induced
by inelastic refiections oflo energy elect rons.The st ructure ofthesurface and
adsorbed species is determined. The HREELS spectrum of CO coadsorbed
wit h K on the Ru(111) slI rface is hown in Fig. 16-1 5.Thest retchingfrequencies
16-13 LEED, AES, and HREELS Spectroscopy 679
-
e
:::J
e

2
e
' ij
e
Q)
2065
e
o 1000 2000
(cm-
1
)
FIGURE 16-15 HREELS
spectra 01 cacoadsorbed
with K on a Rh(1 11) surlace.
680 Chapler16 lonization Methods
FIGURE16-16 An STM
image 01 carbon atoms in a
highly oriented pyrolytic
graphite sample. The image
is a series 01 line scans,
each displaced in the y
direction Irom the previous
one, displaying the path 01
the tip over the surlace.
for two different types of bound ca are seen at 1855 and 2065 em - l . HREELS,
in combinati on wit h the foregoi ng teehniq\jes, has provided considerable insight
into heterogeneous catalysis. Studies of the hydrogenation of ethylene on
platinum, the hydrodesulfurization of thiophene on sulfided molybdenum, the
reforming of hexane, and the hydrogenation of carbon monoxide have been
summarized(57)
16-14 STM (SCANNINGTUNNELlNG MICROSCOPY) ANO
AFM (ATOMIC FORCE MICROSCOPY)
The resolution of mieroseopic techniques is determi ned by the size of the
measuring probe. Wit h conventional mi croscopies, using light or electron beams,
10
11
the area resolved encompasses more than atomic si tes, produeing an
averaged macroscopic pict ure of the surface. I n 1982, th Nobel Prize in physics
was awarded to G. Binning and H. Rohrer(58) for developing the scanning
tunneling mieroscope- a method that provides the topography of surfaces with
atomie resolu tion. (5 8)
In STM(59.60) a sharp conducting metal tip is brought to withi n 5 to 10
of the sample. The tip traces the contours of the surface with resolution
so it must be very sharp, ideally termi nating in a si ngle atom. Al 5 to 10 , t he
wave funetions of the sample and the tip overlap. lf a bias is applied to the
sample, an eleetron tunnel ing eurrent flOWS(6 J) between the tip and the surface.
The electron fiow ean be in ei ther direetion depending on lhe sign of the bias
imposed. The tip can be moved in the x, y, and z directi ons using lhree
orthogonal x, y, and z piezoeleetrie translators. The t ip moves in steps of
1 nm atoms) per vol t applied to the translat or. Moving the x and
y translators maps t be surfaee while the z transl ator varies lhe tip-surfaee
distanee. The tunneling eurrent is very sensiti ve to the tip-surfacc distanee,
typically changing by a faetor of 2 for a 0.1 nm ehange. Di ffi rences of l / lOO of
an atomic diameter ean be delermined in the z direction. As one performs the
sean, the voltage into the z translator is ehanged to change the tip-surfaee
distanee in order to maintain a constant current, typieally 1 nA. Alternatively
the tip-surface distance can be kept fixed and the tunneling current mcasured.
With a ti p the size of an atom, atomie resol ut ion is aehieved. Figure 16-16 is all
STM image showing carbon atoms in a sample of highJy oriented pyrolytie
graphite. The dashed lines in the figure correspond to a scan in the x direction.
The voltage along z required to vary the distanee and keep the eurrent eonstant
is measured as a function of the voltage applied to move X. The image is made
by multiple seans changing the y direction for each.
The STM has been used in teehnologieal applieations to guide the man-
ufacture of a spectral grating master(62) and in improving magnetie recording
heads(63) By removing and depositing atoms, images with atomic dimensions
have been made. By exciting individual atoms, nanoscale surface chemistry can
be induced.(64) The surface chemistry of silicon has been explored and ehanges
that occur when ehemical reactions take place monit ored.(60) Referenee 60 is
highly recommended reading.
The application of STM is limited to eondueting samples. Sorne suecess
has been aehieved by studying eondueting images of non-metaIl ic substanees,(65)
by direet ejeetion of electrons into the eonduction band,(66) and by using
nonlinear alternating current STM.(6 7) The atomic force microscope,' AFM, can
image non-conducting surfaces.(68) A sharp tip, e.g., a sma)] fractured diamond
fragment, attached to a spring in t he form of a cantilever, traces over the sample
and sen ses the repuJsive forces between the tip and the sample. Repulsive forces
usualJy in the range 10- 6 to 10- 9 N are recorded by measuring minute deflec-
tions of the ca ntilever. The spring defl ection is measured by electron tunneling
with an interferometer by defl ection of a Jaser beam off a mirror on the spring
or with a fiber- optic interferometer. Boron nitride has been imaged in this
way.(69)
16- 15 INTRODUCTION
Every element shows discontin uous j umps or " edges" in its X-ray absorpti on
coefficient correspondi ng to the ex itation of a core e1ectron (F ig. 16-17(A)). The
energy of the edge depends on the elernent and the e re elect ro n excited. The K
edge (ls state) is observed for elements between sulfur and cadmium and the L
n
edge (2s and 2p states) ror elements of higher atomic numbers. Extended X-ray
e
absorption fine structure (EXAFS) employs high intensi t y X-ray beams (energies
e
to 40 keV; wavelength to 0.25 ) from a synchnotron source. The brightness is
as much as 10 orders of magnitude larger than t bat from conv ntional X-ray
s
tubes. A typi eal plot of t he absorption coefficient as a function of the synehnotron
e
photon energy, E, is shown in F ig. 16-17(B). X-ray a bsorption spectroscopy(7 0)
,f
refers to the study of the struetured absorption which is superimposed on the
d
edge.
.
e
The EXAFS regio n is 50 to 1000 eV above the edge, wh reas t he X-ray
-,
absorption near-edge struct ure (XANES) regio n refers to absorption within 50 eV
)r
of bot h sides of the edge. The same principies govern absorpti on in both EXAFS
e
and XANES, b ut different information can be obtained.
e
The incident photon energy in EXAFS is much larger than the core-binding
y
energy leading to an excited photoelectron with significant kinetic energy. The
i.
emitted photoeJectron can be pictured as a wave propagating from the excited
o
atom. Upon reaching a neighboring liga nd, the wave front is scattered back
le
toward the abso rber. As the energy of the X-ray is increased, constructive and
l.
destructive interference of the outgoing and backsca ttered wave occurs near the
It
origin giving r ise to the sinusoidal vari aton of the amplitude versus E, (F ig.
le
16-17(B)), .e., EXAFS fi ne struct ure. The amplit ude and frequency of this
sinusoidal modul ation depends 00 Ihe type and bonding of the neighboring
,-
atoms and their distances away from the absorbing atom. Tbe scatteri ng is similar
g
for atoms in the sarue row of the periodic table. Thus, e, N, and o a re not
s
distinguished but N and S are. After considerable mathematical manipulaton,
n
EXAFS provides t he sarne eompositional information as can be obtained from
s
X-ray crystallography with the advantage of being applicable to oon-crystal line
s
systems. However, t he mean free pat h damping factor limits information to A
from the absorbing atom and does oot provide information regarding the angular
s
arrangement of t he surroundi og atom . It should be emphasized that EXAFS
;)
measures a bulk property a nd is not a surface technique. If the sample is not
pure, a meaningle average EXAFS spectrum will result o
16-15 Inlroduclion 681
EXAFS and XANES
2s
2pl s
iiJlllI Ti I
Absorption L2
edge L3 L1 k
{SI
EXAFS
Energy
(Al
FIGURE 16-17 (A)
Schematic representation 01
absorpti on edges i n X-ray
absorption spectroscopy. (B)
Fine structure on a
absorption edge.
682 Chapter 16 lonizalion Melhods
16-16 APPLlCATIONS
Many ofthe aboye limitations turn out to be an advantage in the elucidation
of the coordination environment of metals and metal clusters in biological
systems. The molybdenum si te in a nitrogenase enzyme was shown(71) to be
predominantly coordinated by su lfur ligands with another metal (inferred t o be
iron) 2.7 A from a molybdenum center. Several model compounds were
synthesized with structures consistent with the EXAFS result s. These models
contai n oxygen and nitrogen ligands that could not be seen in the EXAFS of
the models in the presence ofthe sulfur ligands and thus are not expected to be
seen in the EXAFS of the enzyme. EXAFS was also used(72) to how sulfur
coordinationtotheiron hemeofcytochrom PA50, whichis retained throughout
the catalytic oxidation cycle. EXAFS provides very accurate bond distances. It
improved( 73) considerably on the iron-sulfur distances from an x-ray crystal
structure ofthe iron-sulfurprotein, rubredoxin. The initial x-ray st udy reported
non-equivalent metal-sulfur distances. EXAFS showed them to be the same to
within 0.04 A. Other applications illustrating the advantages and limitations of
the technique have been summarized(74)
REFERENCES 1. R. A. W. Johnstone, "Mass Spectrometry for Organic Chemists," Cambridge
University Press, London, 1972.
CITED
2. M. R. Litzow and T. R. Spalding, '"Mass Spectrometry of Inorganic and Organo-
metallic Compounds," Elsevier, ew York, 1973; J. Lewis and B. F. G. Johnson,
Acc. Chem. Res., 1, 245 (1968) ; M. 1. Bruce, Adv. Organomet. Chcm., 6, 273 (1968).
3. M. E. Rose and R. A. W. Johnst one, "Mass Spectromet ry for Chemists and Bio-
chcmists, " Cambridge University Press Cambridge, MA; 1982.
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Exercises 685
1. Iftheaccelerating potential in a mass spectrometerisdecreased in runninga spectrum, EXERCISES
will the large or small mje ratios be recorded first?
2. Sulfur-carbon n bonding is not as effective as nitrogen-carbon n bonding. In the mass
spectrumofHSCHzCHzN 2, wouldthemje =30ormje =47 peakbe moreintense?
3. Refer to Fig. 16-4 and recall the discussion on the relation ofcharge delocali zation
and stabilit y of the positive ion. Explain why the mass 92 peak corresponding to
&
CH +
LYJ z is less intense for the isomer of ethyl pyridine with the et hyl
N
group in the 3 position.
4. a. What mje peak in the mass spectrum of CH
4
would you examine as a function of
accelerating potential in order to determine the ionization potential ofthe methyl
radical?
b. Writean equation for the appearance potentialofthe fragment in part(a) in terms
ofionizati on potential and dissociation energy.
c. In evaluating the dissociation energy ofpart (b) from thermochemical data, what
is wrongwithusingone-fourthvaluefor theheatofformation(fromgaseouscarbon
and hydrogen) ofCH
4
?
5. PS spectra for even relatively small molecules Iike butadiene are complicated (see
figures). Using Hckel calculations on butadiene, assign the peaks in the butadiene
spectr um (t he peaks at 8.6 and 10.95 eV are impurity peaks.) Three vibrational
progressions (1520, 1180, and 500cm-
l
) have been tentatively identified in the first
band at 9.08 eVo Discuss the vibrational structure on this band (both sha pe and
magnitude) with respect to your ass ignment. (Bands are seen in the infrared spectrum
ofground state butadiene at 1643, 1205, and 513 cm- l.)
9.08
1000
I
u
~
~
e
::J
O
U
8.6
I
eV
300
\
e:
(J
...
e
:J
O
U
.-----.-------19.08
eV
6. The effects ofcoordinationofsmall moleculesto transition metalscan be studied with
photoelectron spectroscopy. Spectra are given below for CO and W(CO)6. Qualitat-
ively explain what observations bearing on the bonding in this complex are possible.
Take into account symmetry and energy considerations ifapplicable.
1000
ca
14.01(81
19.68(81
16.53(61
e:
(J
...
e
:J
O
U

20 19 18 17 16 15 14 13
eV
11 9
Exercses 687
I
u
~
~
e
::J
O
U
8
eV
7. Given below are the UV photoelectron spectrum and m.o. diagram for ammonia.
Bonding (b), non-bondi ng (n), and antibonding (*) levels are indicated.
/, '
/,
~ a ~
\
/.J---e*\
2p---' I \ \
t- \
~ \ \\
\\ '>--*- a ~ _~
,\< }---lS
25-_1; \' //
\ '4HV
eb
j
\\ /
\ ~
a
b
1
100.

u
~
~
e
::J
O
U
eV
a. What phenomenagive rise to the two bands centered at 11 and 16eVo
b. What gives rise to the fine structure observed for each band? (Explain in one or
two sentences.)
C. Is the fine structure what you would predict, assumi ng the m.o. diagram given?
Why or why not ? How might you justify any anomalies ? Hint: consider the
shapes ofthe "before" and "after" species.
8. Describe which ofthe techniques described in this chapter you would use to:
a. determine the molecular weight ofa non-volatile solid.
b. measure the C-O stretching frequency ofCO adsorbed on a surface.
C. determine the oxidation state of a metal surface species after a metal film was
exposed to C1
2
.
d. determine if the entire film in (C) had reacted with C1
2
.
e. determine the atoms in the coordination sphere ofa metal ion in a metallo-protein.
9. Describe the differences and features in common for LEED, AUGER, and HREELs.
X-Ray Crystallography
7
JOSEPH W. ZILLER ANO ARNOLO L. RHEINGOLO*
17- 1 INTROOUCTION
X-ray crystallography is the most powerful and unambiguous method for the
structure elucidation of solids avai lable to modern scientists. X-ray diffraction
has grown steadily since Max von Laue discovered in 1912 that a copper sulfate
crystal could act as a three-dimensional diffraction grating upon irridation with
X-rays. Early diffraction experiments were recorded on photograpruc pi ates or
film. The labor invol ved in determini ng a three-dimensional structure from these
early experiments could easily lead to one's thesis being based solely on one or
two structural determinations. The advent of modern high speed computers,
automated diffractometers, and powerful structure solution programs has allowed
X-ray diffraction to become widely accepted as a necessary standard technique.
Progress in X-ray diffraction is probably best traced by the number and
complexity of structures being reported each year. Information compiled in the
Cambridge Crystallographic Database(ll illustrates how rapidly structural in-
formation is growing (Table 17-1). It is clear that researchers are increasingly
relying on crystallography.
TABLE 17- 1. Growth in the Cambridge Crystallographic Database
Vear Structures Added Avg. Number 01 Atoms/Mol ecul e Tolal Slructures
1960 224 15.1 583
1970 1260 27.9 5577
1980 4324 38.6 30475
1988 7162 51.7 71619
1989 8005 53.1 82130
This chapter was written by Joseph W. Ziller, University of California - rvine and Aroold
L. Rheingold, University of Delaware. 689
690 Chapler 17 X-Ray Crystallography
The basic requirement to conduct an X-ray diffraction experiment is a single
crystal that can withstand exposure to X-rays of a given frequency for many
hours or days. Depending on the experimental conditions and the information
desired from the diffraction experiment (e.g., does one need to establish atom
connectivity or the absolute configuration of a resolved chiral molecule?), an
X-ray diffraction experiment may be carried out in as little as a few hours(2) or
take several days.
It is the intent of this chapter to familiarize the novice with general X-ray
diffraction principIes, illustrate useful techniques for growingjhandlingjmounting
crystals, explain briefty the diffraction experiment, and illustrate how to interpret
and evaluate the results of a single-crystal X-ray diffraction study.
Principies 17-2 DIFFRACTION OF X-RAYS
In order to understand how the interaction of X-rays with single crystals yields
a diffraction pattern and ultimately (in most cases) a three-dimensional crystal
structure, it is necessary to know basic diffraction physics. A convenient and
conceptual!y easy way to describe diffraction of X-rays from crystals is to consider
that diffracted beams are" reftected" from planes in the crystal lattice analogous
to the reftection of an object from a mirror. The mathematical expression used
to describe how X-rays interact with crystals to produce a diffraction pattern is
given by Bragg's law:
n), = 2d sin (J (17-1)
where n is an integer, Ais the wavelength of the radiation, d is the perpendicular
spacing between adjacent planes in the crystal lattice, and 8 is the angle of
Incidence and "refiection" ofthe X-ray beam. Figure 17-1 shows how X-rays are
"refiected" from planes in the crystallattice. Electromagnetic wa ves 1 and 2 strike
planes PI and P2, respectively, at points A and B making the angle 8. For
diffraction to occur, it is necessary for the waves generated (1' and 2') to be
"in-phase" when "reftected" from P I and P2. Constructive interference (in-phase)
of the waves emanating from points A and B occurs only when the path lengths
travelled are an integral multiple of the wavelength, n),. From Fig. 17-1 it is seen
that the path-length difference is 2d sin 8. When this equal s n)" the Bragg equation
is satisfied and the resulting constructive interference produces a diffraction
maximum or " reftection."
Since the foregoing discussion considers diffraction of X-rays from lattice
planes in a un t cel!, these planes must be designated in a consistent manner.
This is done by assigning Miller indices to the lattice planes. Miller indices are
represented by (hk0 values, which are universally used to represent indices. Miller
indices are also used to designate lattice points hkl that correspond to the (hk0
family of planes. Each "reftection" of an X-ray from a crystal is assigned a unique
hkl value. (Note: when Miller indices are written in parentheses (hk0, they
designate lattice planes or crystal faces and when simply written as hkl, they refer
to a lattice point or "refiection"). Miller indices representing lattice planes and
lattice points are shown in Figs. 17-2(A) and 17-2(B), respectively.
17-3 Reflection and Reciprocal Space 691
e
'Diffractionvector '
direction
y
n
Angle of
1'
incidence:
n
FIGURE 17-1 "Reflection"
2 90 - 9 : 90 - 9 2'
..... -""t-
n /
\
I
01 X-rays Irom crystal lattice
I
)r
I
planes.
Pl
29
(Deviation Irom
P2
ly
directbeam)
Ig P3
-;
et
Path differences
each dsin9
17-3 REFLECTI ON ANO RECIPROCAL SPACE
Itis now necessary to relate diffraction from crystal planes to Bragg's law and
the direction ofthe diffracted beams. Rewriting Bragg's law in the form sin () =
nJcj 2(1 Id) , it is c\ear that sin e is inversely proportional to the d-spacing in the
crystallattice. As a result ,structures having larged-spacings exhibit compressed
diffractionpatternsandstructureswithsmalld-spacingsshowexpandedpatterns.
er
Itwould be more convenient to express a direct relationship between sin f) and
US
d. This is accomplished by construction of a reciprocal lattice in which l i d is
ed
directly proportional to sin e. A reciprocal lattice can be constructed from a
is
direct lattice as shown in Figs. 17- 2(A) and 17- 2(B).
From the origin O, lnes P, Q, and R aredrawn normal to the direct lattice
planes(hk0. Points along the normals are marked offat distances l l d
hkl
from O
whered
hkl
is the d-spacing between lattice planes. Theresulting reciprocallattice
for a primitive (P) monoc\inic ceH is shown in Fig. 17-2(b). The mathematical
relationships between direct and reciprocallattices can be found in reference 3a.
The relationship of the direct and reciprocal lattices is shown below for a
monoc\inic cel!.
The reciprocal lattice parameters (a* , b*, c*, [3*, and V*) are determined
from the direct lattice parameters according to Table 17-2. Figure 17-3 shows

Ix axis
z axis
101
002 003
102
103
200
201
202
203
300
301
302
(A)
303
1x" axis
(B)
004
z"axis
104 ----
204
304
FIGURE 17- 2 (A) Direct and (B) reciprocal lattices. (Reproduced with permission
lrom M. F. C. Ladd and R. A. Palmer, "Structure Determination by X-Ray
Crystallography. " 2nd ed. Plenum Press, New York.)
692 Chaple r 17 X-Ray Crystall ography
TABLE 17-2. Relationships between Direct and Reciprocal Lattices for the
Monoclinic Cel l
e
a
~
)(
FIGURE 17-3 Direct (so lid)
and reciprocal (dashed)
monoclinic cells.
(Reproduced with permission
from G. H. Stout and L. H.
Jensen, "X-Ray Structure
Determination. A Practical
Guide." 2nd ed. John Wiley
& Sons, New York, 1989.)
a* = I/(a sin fl) a= If(a* sin fl*) a = y= a* = y* = 90
b* = l /b b= I/b* fl*=180 o - fl
c* = l/(e sin fl) e = 1/(e*sin b*) V* = l /V = a*b*c* sin fl*
V = I/V* = abe sin fl
the reciprocallattice outlined with dashes and the direct cell with solid lines. The
reciprocallattice may be used to illustrate how Bragg's law is satisfied.
Figure 17-4 shows the a*c*section of a reciprocallattice of a crystal bathed
in X-rays with wavelength X The X-ray beam (line XO) passes through the
reciprocal lattice origin O. The circle with radius l / Ais centered at point e such
that the origin o is located on its circumference. Point P is a reciprocal lattice
point at any convenient point on the circle and angle OPBis a right angle because
itlies within the semicircle. The foIlowing equations are derived from Fig. 17-4(a):
. . OP OP
SIn OBP = SIn e= - = - (17-2)
OB 2J..
sin e= (OP/ 2)2 (17-3)
Because P is a reciprocal lattice point, l /d
hkl
is the Jength of OP.Substitution
and rearrangement yields sin e= U/2d
l
'kl or Bragg' s law with n = 1, i.e. , lA = 2d
sin e. Since Bragg's law is satisfied, reflection occurs. Figure 17- 4(B) shows that
the reflecting plane is perpendicular to OP and therefore parallel to BP because
OPB is a right angle. The angles ethat the incident and diffr.acted beams make
with the reflecting plane must be equal for constructive interference and thus the
diffracted beam OD is at the necessary 2e angle to the incident beam. When Fig.
17- 4(a) is constructed in three dimensions, a*c*, a*b*, and b*c*, the resulting
sphere is called the " sphere of reflection." Whenever a point on this sphere satisfies
the foregoing arguments, the Bragg condition for reflection is satisfied and a
diffraction maximum can be measured.
(B)
(A)
FIGURE 17-4 (A) Reciprocal lattice ; (B) direct plane. (Reproduced with permission
from G. H. Stout and L. H. Jensen, "X-Ray Structure Determination. A Practical
Guide." 2nd ed. John Wiley & Sons, New York, 1989.)
17-5 X-Ray Scattering by Atoms and Structures 693
17-4 THE OIFFRACTION PATTERN
The diffraction maximum or X-ray data collected from a single cryst al yields an
intensity, Miller indices, and the diffraction angle 2e for each "reflection." The
intensity of the reflection depends on the nature and arrangement of atoms in
the unit cell and 2e is dependent only on the dimensions of the crystal lattice.
As previously stated, for reflection to occur, Bragg's law must be satisfied, but
it must be recognized that atoms are not usually arranged in a unit cell such
that all atoms lie directly on lattice planes. The "reflections" observed are
e
composed of the sum of waves scattered from different atoms at different positions
in the unit cel!. Actually, all atoms (in fact , all electrons) contribute to the intensities
d
of aJl reflections.
le
Superposition of waves is the method of combining different waves to
h
generate the resultant wave observed as the "reflection " or hkl. This principie
:e
states that the resultant wave amplitude in a gi ven direction is obtained by
se
summing the individual waves scattered in that direction. A vector representation
l):
of thi s superposition is shown in Fig. 17- 5. The magnitude IF I and phase ang1e
ex may be calculated for the resultant F. The formul as may be found in reference 3a.
2)
3)
17-5 X-RAY SCATTERING BY ATOMS ANO STRUCTURES
on
2d The scattering of X-rays by the electrons in the crystal produces the diffraction
!lat pattern. The scattering power of a given atom is a function of the atom type, i.e.,
Llse number of electrons and (sin e)/Je. The sca ttering amplitude of an atom is
lke designated as the "atomic scattering fact or " or " atom form factor" (fa). At 2e = O
lhe (sin e/ J,. = O) the scattering factor is equal to the total number of electrons in the
i g. atom. As (sin e)/J,. increases, the scattering of X-rays from different e1ectrons in
ng the atom will become more out of phase. Figure 17- 6 illustrates the decrease in
Iies the scattering factor for several atoms at increasing (sin e)/J,. values.
d a Since the frequency of X-radiation is high, the diffraction time scale is very
short and all motion is frozen. However, since the structure determined will
s to 10
2 0
represent the frozen atomic positions a veraged over 10
1
unit cells, the
structure wiU show the effects of thermal activity, and any differences in atomic
arrangement within the unit cell will be revealed as disorder.
The scattering power of a real atom is also affected by thermal motion or
vibration of the atom. Thermal motion causes the electron cloud to be more
diffuse. This phenomenon is usually associated with such factors as temperature,
how tightly bound atoms are in a molecule, or how rigid the molecules are packed
together in the crystal lattice. The correct expression of the structure factor for
a spherical or isotropic atom is:
2
f = f e-
B
(sin 0)/J'
(1 7-4)
o
where B is a temperature parameter related to the mean-square amplitude of
vibration (/12) by B = 81(2/12
Since we are interested in the scattering from a group of atoms that constitutes
the structure being investigated, we must define a nother quantity, the "structure
~
(A)
(B)
FIGURE 17-5 (A) Vector
rerresentation 01 the
superposition 01 waves '1,
'2, and '3. (B) Resultant
wave il F with phase angle el..
Irom G. H. Stout and L. H.
Jensen, " X-Ray Structure
Guide." 2nd ed . John Wiley
694 Chapter 17 X-Ray Crystallography
FIGURE Scattering
lactor curves lor atoms as a
lunction 01 (sin (JI }.. ).
Irom J. P. Glusker and K. N.
Trueblood, "Crystal
Structure Analysis. A
Primer." Oxlord University
Press, Oxlord, U.K. , 1985.)
40
35
30
25
20
15
10
5

sin9(),.-
factor " IFlor IFhkll. The structure factor is proportional to the observed intensity
taken according to equation (17-5). (See reference 4).
(17-5)
K is an initially unknown scale factor, Lp is the Lorentz and polarization correction
factor and (Abs) is absorption. The observed intensities or "refiections" are
con verted into lFobs I(F observed). These quantities are used to ca\culate electron
density maps from which atomic positions and uJtimately the three-dimensional
structure are determined.
The electron density at any point in the unit cell is given by the Fourier
series in equation (17-6).
p(x, y, z) = Fhkl e-
2ni
(h, + k,+I,l
(17-6)
--V- -- k I
Satisfying this equation results in a three-dimensional mapping of the electro n

density of the un! cen. An atom would be located at each value of p(x, y, z) in
the map with atomic coordinates x, y, z. Unfortunately, the foregoing equation
cannot be solved straightforwardly because only the magnitudes and not the
phases of the Fhkl values are contained in the X-ray data. The uncertainty of
knowing the phases of the measured F-values is known as the phase problem in
crystallography. Fortunately for the modern crystallographer (and especially for
the amateur crystallographer), there exist excellent computer programs that have
been very successful in cracking the phase problem (see reference 3a, p. 245 for
a review of the phase problem and reference 4, p. 248 for a list of computer
programs). Once the phase problem is solved, subsequent least -squares analyses
and difference-Fourier syntheses are used to refine atomic positions and locate
any missing atoms. (As a testamen! to the importance of the work that resulted
17--6 Crystal Growth 695
in direct calculation of phases, in 1985 the Nobel Prizein chemistry was awarded
to Jerome Karle and Herbert Hauptman.)
-1
1,3
sity
7-5)
lion
are
tron
)nal
Irier
7-6)
17-6 CRYSTAL GROWTH
The growing of high quality single crystals is often referred to as an "art." There
are many different methodologies and schemes used to grow crystals. The answer
to the question, ., What is the best method for growing good cry tals of this
compound?" is " The best method is the one that works!" Sorne of the standard
crystallization techniques are discussed here.
Most crystallization attempts begin with a saturated solution, It is usually
best to begin with as much solute as possible since working wi th only a few
milligrams of compound often results in v ry small or poor quality crystals.
Slow evaporation of the solvent is probably the most often used and simplest
crystallization technique, During evaporation it is best to minimize agitation or
vibration ofthe sample because this may cause crystal to "crash out 'loo quickly
or cause developing crystals to go back into solution. A small vial or ftask fitted
with a septum into which a small needle is inserted makes an excellent and cheap
crystalli zation device, If the solution requires heat to dissolve the solid, it is often
best to allow the solution to cool slowly rather [hat immersing it in an ice bath
or putting it in a freezer. This can be done by simply placing t he crystalli zation
vessel on a bench top, For very slow cooling, lhe vessel may be placed in a warm
oil bath and both the bath and sample allowed to reach ambient temperature
on their own, Alternatively, the temperature may be electronically decreased over
a period of time,
Vapor diffusion is another method for obtaining high quality crystals.'gure
17-7 shows an "H-tube" apparatus, A solute/ solvent solution (Si) is placed into
side A and a second solvent (S2) is placed into side B. S2 should be a solvent in
which the solute is less soluble. Upon mixing of the solvents by diffusion, crystals
should form since they should be less soluble in the mixed solvent system than
in the solvent (SI), An H-tube is quite versatile since it may be easily heatcd or
cooled or used under an inert atmos phere such as nitrogen or argon for
air-sensitive compounds.
Liquid di ffusion prod uces crystals at the zone where two solvents mix. In
another approach, a sol ute/ solvent solution (SI) is placed into the vesseJ and a
solvent of different density is " Iayered" on top of the mixture; Fig. 17-8 as the
two solvents diffuse, crystals should appear at the interface and grow as mixing
proceeds.
A rather elaborate method for growi ng crystals of low mclli ng compounds
directl y on an X-f ay diffractometer has been developed. (5) Focused heat radi ation
and simultaneous cooli ng in a capillary affords crystals that may be examined
on the same machine on which they wcre grown,
A method for obtaining good quali ly cry' lals for low-yield compounds or
for those that crystallize poorly is to complex the target molecllle with something
such as triphenylphosphi ne oxide (TIPO), which itself forms hi gh qualit y
crystals,(6) Basically, the approach involves either cOllpling or cocrystall izing a
compound that forms hi gh quali ty crystals with one that does not. TTPO is a
good proton acceptor, and when it couples with the desired crystal, it often
imparts its crystallizing characteristics to the product.
Crystals
A B
FIGURE 17-7 H-tube
apparatus for growing
crystals by vapor diffusion.
~ S l
FIGURE 7 ~
Liquid-diffusion vessel,
Compressed
alr
FIGURE 11-9 Air-driven
crystal grinder. (Reproduced
with permission from G. H.
Stout and L. H. Jensen,
"X-Ray Structu re
Guide." Macmillan, New
York, 1968.)
17-7 SELECTION OF CRYSTALS
A crystal suitable for a single-crystal X-ray diffraction study must possess internal
order and be of the proper size and shape. Internal order means that a crystal
should be "pure" on the atomic leve!. A "twinned" crystal is one that has more
than one orientation of a crystal in the lattice, but is often confused with a
"multiple" or "grown-together" crysta!. Twinned crystals may sometimes be
detected from the diffraction pattern. Observations to note are multiple spots
(reftections) lying close together on a rotation photograph or "split" reftection
profiles. It is often difficult to determine the unit cell of a twinned crystal and if
it is decided that a crystal is twinned, the best and least frustrating way to deal
with it is to throw it away and try another crysta!. However, in some cases it is
a property of all specimens.
Crystals should not contain cracks or have satellite crystals stuck to them
and should be as equidimensional as possible; however, this is not a strict
requirement. Many X-ray structures have been correctly determined and properly
refined using plates, needles, or even "potato-shaped" crystals. If the nature of
the crystal permits, it may be ground to a sphere using a device such as that
depicted in Fig. 17-9. M r (or N
2
, etc.) causes the crystal to tumble around in the
abrasive cavity producing a spherical or nearly spherical shape. If grinding is not
desired or successful (more likely), crystals can usually be cut and sized with a
razor blade.
A polarizing microscope may be used to determine whether a crystal is single
or made up of several fragments. Under polarized Iight, a good crystal should
appear uniformly Iight and dark with every 90 rotation. Finally, the diffraction
pattern of a good crystal should show sharp single spots with no "tails" or severe
powder rings.
The next concern we have is the size of the crysta!. Several factors need to
be considered. First, the crystal must be small enough to remain wit hin the
uniform intensity of the primary X-ray beam since the entire crystal should be
irradiated by the same intensity radiation. This uniformity is usually about
0.50 mm x 0.50 mm. Crystals larger than 0.50 mm in any direction should be
avoided or cut smaller. The optimum size depending on the diffracting power of
the crystal and its absorption coefficient is about 0.10 to 0.40 mm on an edge.
As stated previously, absorption of X-rays by crystals must be considered
when deciding how large a crystal to use or which radiation to use. The resultant
intensity 1 of the X-ray beam after passing through an absorbing crystal of
thickness (t) is given by the equation 1 = l oe-PI, where lo is the incident beam
intensity and (11) is the linear absorption coefficient of the compound. Unfortu-
nately, since the linear absorption coefficient is a function of wavelength of the
radiation used and atomic number, it cannot be calculated until the makeup of
the structure is known. This does not pose many difficulties since it is not usual
for one to begin an X-ray study assuming a "light-atom-structure" and later
determine that the crystal was a heavy-atom complex. The li near absorption
coefficient for the complex is calculated by summing the mass absorption
coefficients (11/ p) for the individual atoms present according to equation (17-7).
11 = (density) L (mass %)(I1/p) (17-7)
Mass absorption coefficients for elements for several different types of radiation
are listed in the International Tables, Vo!. m, pp. 161- 165(7a)
17-8 Mounting Crystals 697
Si nce the X-ray beam is only uniform to just over 0.50 mm, this should be
used as an upper three-dimensionallimit. For " Iight-atom," organic-type crystals
with no heavy atoms, such as Br, 1, or higher (in atomic number), crystals
approaching the upper limit may be used. It is usually necessary to use large
crystals for " Iight-atom" structures d ue to their low scattering power. With
organometallic or inorganic compounds that contain higher percentages of
transition-metals, lanthanides, actinides, or other elements that absorb X-rays,
crystals should be as uniform as possible and not exceed about 0.20 to 0.40 mm
on an edge.
17- 8 MOUNTING CRYSTALS
Depending on the nature of the crystal and the apparatus to be used, there are
many different methods of crystal mounting that may be utilized. O nce good
quality crystals are obtained and the sizejshape requirements are met, the crystaJ
must be mounted on the diffractometer. Unlike traditional film methods, modern
diffractometers do not require that a crystal be oriented in any special direction
f
t
.e
relative to the X-ray beam. Itis therefore not necessary to be concerned about
,t
the orientation of the crystal on the mounting device (goniometer head) but it is
a
preferable to mount crystals so that their most nearly cylindrical axis is aligned
wit h the z-axis of the goniometer head. A typical xyz style head is shown in
Fig. 17-10. The goniometer head allows the crystal to be moved in three directions
le
in order to center it in the X-ray beam. Typically, a crystat is secured to a glass
Id
m
fiber or wedged in a capillary tube that is inserted into a brass or aluminum pin,
which in turn is inserted into the goniometer head. The assembly is then screwed
re
onto the instrument.
The method used to mount a crystal depends on the nature of the crystal
lo
be
and on the experimental conditions. The most often-used method to mount
airj moisture-stable crystals is to glue them to a glass fiber. Five-minute epoxy is
be
lut
an excellent adhesive in most cases. A very small bead of epoxy will usually
suffice and, in fact, large globs of glue should be avoided since some of the crystal
be
may be obstructed making optical alignment of the crystal difficult and beam
intensity wi]] be diminished by random scatter. For crystals that are air sensitive,
of
e.
moisture sensitive, or lose solvent, a capillary tube may be used. Crystals should
'ed
nt
be placed into the capillary tube under an inert atmosphere either in a glove box
or glove bago The capillary is then fiame seaJed to prevent decomposition.
of
Capillaries are suited for either room or low temperature data collection ; however,
aro
they are somewhat awkward when using a low temperature device that utilizes
t u-
a cold air or nitrogen stream to cool the crystal. A routine method of "oil
the
mounting" crystals for low temperature studies has been developed.(8) The crystal
of
is immersed in a thick hydrocarbon oil and attached to a gJass fiber, which is
~ l
mounted on the end of an elongated brass or copper pi no The oil acts as an
on
adhesive and also as an insulator, keeping the crystal from .decomposing until it
on
is quick-frozen in the cold stream. This method is very usefu] for mounting crystals
7).
that decompose when separated from their mot her liquor or solvent. Sin ce
mounting crystals in a glove bag or glove box can be an exercise in fu tili ty, this
7-7)
method aIJows one to even shape (with a razor blade) the desired crystal under
a microscope on the benchtop. Although "oil mounting" may not be applicable
ter
'00
for every crystalline sample, experience has shown that if one works quickly, even
Z-axis loek
X-axis X-axis loek Y-axis
adJustment adjustment
FIGURE 17- 10 Goniometer
head. (Reproduced with
permission from
Nieolet/Siemens, User's
Guide. Siemens Analytical
X-Ray Instruments, Ine.,
Madison, Wis.)
698 Chapter 17 X-Ray Grystallography
the most delicate and sensitive crystals stand a very good chance of surviving
this procedure.(Note:attheUniversityofCalifornia- Irvine, nearly all structural
determinations, approximately 100/year, are done using this method).
Methodology 17- 9 DIFFRACTION EQUIPMENT
The principal instrument used in modern X-ray laboratories is the four-circle
diffractometer. Although more traditional film methodsarestill employed, these
are becoming less standard practice. Modern diffractometers do not require
alignment ofcrystals in anyt hing but a random fashion. The orientation ofthe
crystal relative to the diffractometer geometry is determined automatically by a
computer.
The main advantagesofthe automated diffractometerare that the accuracy
of results is far greatct than that available from film, the instrument runs
automaticallyviacomputercontrol,andlhe rateatwhichreflectionsaremeasured
allowsresearchersto employX-raydiffract ionasa"routine,"albeit,unparalleled,
analytical tool.
There are four basic components ofa four-circle diffractometer:
1. The X-raysource,which ineludes a high voltage generator and a sealed
X-ray tube or a high intensity rotating anode
2. The goniometer or " crystalorientor "
3. The detector, which is usually a scintillation counter
4. The computer, which is used for di ffractometer control and data
manipulation.
17-10 DIFFRACTOMETER DATA COLLECTION
Theheartofthediffractomet eris lhegoniometer.The mostwidely used geometry
is that ofthe four-cirele or Eul rian cradle.The Eulerian cradle consists offour
cirelesthattogetheractlo rientthecrystalsuch thatallpossiblereftcctingplanes
maybe examined automatical1y. The ecireles are designated 2-thet a, omega,phi,
andchi. Only three ofthe cireles operate independently si nce 2-theta and omega
are usuall y coupled. Figure 17- 11shows that 2-theta and omega are mounted
about the same axis.
A struct ural determination is usually begun by mounting a crystal on lhe
instrument and taking a photograph, known as a rotat ion photograph, using
PoJaroid film. Thecryst al is rotated on the spindle axis phifor several complete
revolutions taking about 10 minutes; the diffraclion pattern is recorded on the
film.Filmmeasurementsareinputtolhecomputerwhichpositionst hegoniometer
to locate and center (determine the angular settings of2-theta, omega, phi, and
chi) on 10 to 15 reflections. An alternate method is to allow the computer to
randomly search for reftections on which to center. This melhod works well for
strongly diffracti ng crystals but does not allow one to visually i n s p e ~ the
diffra tion pattern of the crystal. Visual inspection is advised since problem
crystals may be discovered and dealtwith by mounting a new crystai.
17-10 Diffractometer Data Collection 699
cD
I
X-ray tube
FIGURE 17- 11 The Eulerian cradle
showing the tour circles.
Once several reftections have been centered, aulomatic computer routines
areusedwit hcareful attentionbythecrystallographerlodetermineanorientation
matrix that relates the crystal's geometry to that of the diffractometer and the
crystal's unit-cell parameters (a, b, e, IX, (J, '/, andcell volume). Photographs along
the cell axes should be taken to determine the presenceorabsence ofsymmet ry.
In most laboratories, t his is also done on the diffract ometer rather than by
traditional film techniques.
Datacollectionshould beginonlyafteraccuratecell paramet rsareobtained
andafterasmuch informationaboutthecrystalaspossibleis known.Oneshould
always try to determine the crystal' ' pace group, possibly from a fas t limited
dataset, prior to final data collcction. The number ofunique dat a points to be
collected dependsont he typeofradi ation used,theLauesymmetryofthecrystal,
and the quality ofthe crystal.
The total number of accessible reflections for a crystal is known as the
" limi ting phere " and depends only on the wavelength and is given without
furt her explanat on as N = 33,5 (vol. direct celJjA. 3). The volume of a molecule
contaninga typical mix ofli ght and heavy a toms may be approximated by the
remarkably consistant observation that t he average atom occupies 9- 11 A3;
when domi nated by heavier at ms, often usi ng 18 A
3
for j ust t he non-hydrogen
atoms will prove morereliable. Fora cell wit h volume=3000A3, t hemaximum
theoreticalnumberofreflect ionsfor Moradiation(A. = 0.71073)isapproximalely
280,000, whereas ror eu (J. = 1.54l 8) the number is approximately 27,000.
Fortunately, it is not nece ary lOcollect a1l of Ih se relleclioDs. According lO
Friedel's law, hkl == hkl, therefore the maxi mum number ofreflections necessary
wi ll be one-hal foft he preceding number , Forh.igher-syrnmet ry crystal systems,
the number of unique data is reduced evcn further. For inst ance, if the crys tal
sys tem is ortho rhombic, the symmetry is mmm (three mutually perpendicula r
mi rror planes) and only one oclet ofdala needs to b collected since
hkl =hkl =H/= hk7 = hKI = hk7 = hkl = hkT
Typical hkl ranges for triclinic, monoelinic, and orthorhombic crystal systems are:
Sorne Future
Developrnents
Okl -4 hkl, triclinic
001 -4 hkl, monoclinic
000 -4 hkl, orthorhombic
Another fact or that determines how much data should be collected is the ract
t hat the intensity of reflections deereases wit h inereasing (sin 8)jX D ata are
collected between a ruin and max 2-theta (or theta) limit. Typical values of
20(max) for Mo radiation are 45 t o 55 (or 0.54 to 0.65 (sin 8)jA.) and the total
number of observable refl ections is gi ven by N o = N, x si n
3
8. (For the foregoing,
N o = 280,000 x si n
3
(25) = 21,135 for 28-max = 50.) Cryst al quali ty, possibl y
due t thermal motion, may dietate that there will be no usable data beyond the
50 li mi t.
A method used to improve data qual ity that is quickly beeoming routine in
many laboratories is low temperature data collection. As already discussed, low
temperature data coJlection allows for easier handling and mounting of crystals.
Reflection profiles are sharpened and backgrounds are usually reduced. Improving
the signal-to-noise rat io aids in resolution of weaker r fl ections and those at
higher (sin ell A. values. Tbermal motion is also reduced, although not eliminated.
Decomposition can be reduced or may be completely eliminated for crystals that
are prone to decay in the X-ray beam. Scan speeds for data coJlection can be
increased res ulti ng in less X-ray exposure and ultimately in a greater number of
data sets being collected.
17-11 COMPUTERS
M any crystallographic facilities are moving away from large mainframe com-
puters to mini, micro, or even personal computers. Most crystallographic software
can be run on a variety of computer platforms. The usual laboratory setup
ineludes one computer that is used for both data collection and data reduction.
Graphics terminals, color printers/ plotters, and laser printers enable one to
produce publication quality output without the necessity of employing specialized
services such as a draftsperson.
17-12 AREA DETECTORS
The field of protein crystallography is growing steadily. Because of the necessit y
to determine the structures of large macromolecules, area detectors wer
developed. Standard diffractometer practice is to collect one reflection at a ti me
and record the intensity using sorne type of sci ntillation counter. Area detectors
are able to measure the intensities of many refleetions simultaneously. This is of
part icular importance si nce it is necessary to measure a far greater number of
reflections for macromolecules. Also, measuring many refl ections at once results
in less ueeay of the crystal. This is obviousl y a major concern when exposi ng
e:

of
tal
19,
,ly
:he
ID
OW
lis.
ing
at
:ed.
hat
be
r of
om-
are

lon.
e to
lZed
sity
were
time
r of
lSults
osing
biological samples to X-rays. Future advances in this area will result in the
elucidation of larger and more complex crystal structures. As the resolution of
area detectors improves, they may also provide advantages for small-molecule
work as well.
17- 13 X-RAY VERSUS NEUTRO N DIFFRACTION
X-ray and neutron diffraction can be used as complimentary techniques because
of both similarities and differences between them. Whereas X-ray diffraction relies
on scattering by electrons, neutrons are scattered by nuc\ei. O ne of the most
common uses of neutron diffraction is to locate hydrogen atoms wi th high
accuracy beca use the degree of scattering by nuc\ei does not vary significantly
with atomic number. In fact, because hydrogen has a negative scattering factor
for neutrons, whereas that for deuterium is posit ive, they are easily distinguished
from one another. A disadvantage of nel1tron diffraction is that much larger
crystals are required than for an X-ray analysis.
17- 14 SYNCHROTRON RADIATION
A highly specialized type of X-ray so urce is available through the use of particle
accelerators. Synchrotron produced by high energy electrons in a
storage ring when a magnetic field is applied, causing their path to bend. The
energy emitted is 100 to 10
4
times as in tense as a conventional X-ray tube. The
wavelength of synchrotron radiation can be tuned for a particular experiment,
typically in the 0.8 to 2.0- range desired by crystallographers. The main
disadvantages of synchrotron radiation is that there are a limited number of
installations and expenses are high.
17- 15 CRYSTAL CLASSES
A unit cell is designated by the six lattice parameters a, b, e, rx, {J, and y. These
correspond to the axial lengths and the angles between them. rx is the angle
between b and e, {J is the angle between a and e, and y is the angle between a
and b. (See Fig. 17-12.) The unit-cell volume, V may be obtained from
of""'-+--+---i----r
c"'---
Monoclinic cell Orthorhombic cell
(A) (B)
17-15 Crystal Classes 701
Symmetry and
Related Concerns
FIGURE 17- 12 Monoclinic
and orthorhombic unit cells
showing the axial lengths
and angles between them.
v = abc(l - cos
2
a - cos
2
f3 - cos
2
y + 2 cos a cos f3 cos 1')1
1
2
The values of the six parameters may be either unique or they may be constrained
due to the symmetry of one of the seven crystal classes listed in Table 17-3.
The symboJ of should be read "not constrained to equal," since it is possible for
TABLE 17-3. The Seven Crystal Classes
No. Independent LaHice
Crystal $ystem Parameters Parameters Symmetry
triclinic
monoclinic
orthorhombic
6
4
3
a#- b #- e; IX #- fJ #- Y
a #- b #- e; IX = Y= 90 o; fJ #- 90 o
a #- b #- e; C( = f3 = y + 90
T
2/ m
mmm
tetragonal
rhombohedral
2
2
a = b #- e; IX = fJ =
a = b = e; IX = fJ =
y = 90
y #- 90
4/ mmm
5m
hexagonal 2 a = b #- e; IX = fJ = 90 ; Y = 120 6/ mmm
cubic 1 a = b = e; IX = f3 = y = 90 m3m
Cubic
Tetragonal
p
F
p
Hexagonal P Rhombohedral R
Orthorhombic
e F P
Monoclinic
a a
P e
Triclinic P
FIGURE 17...;.13 The fourteen Bravais lattices distributed among the seven crystal
systems. The pr imitive lattice (P) has 1 equi valent point per unit cell at (000); the
body centered lattice (C) has 2 equivalent poi nts per unit cell at (000 ; H O); and the
face-center ed lattice has 4 equi valent poi nts per unit cell at (000; oH; o ~ ; ~ ~ O . AII
equivalent latt ice points are related to eaeh other by pure translation and have
identieal environments .
2
17-16 Space Groups 703
accidental equalities to occur, but this is rare. Addition offace and body centering
to the seven crystal systems leads to the 14 Bravais lattices shown in Fig. 17-13.
17- 16 SPACE GROUPS
The point-group operations of rotation, mirror reflection, and inversion discussed
in Chapter 1 define the 32 unique point groups. Combining the 32 point groups
with the 14 Bravais lattices result in 230 space groups that are a group of symmetry
operations that describe how molecules are arranged, pack, interact , etc., in the
y unit cel! of a crystal lattice. It is now necessary to define two additional
"space-symmetry opera tors" that account for translational motion. These addi-
tional operators are the screw axis and the glide plane.
An n-fold screw axis is produced by combining a rotation axis and a
translation parallel to this axis. The rotation is (360/ nt and the translation is a
fraction (m/ n) of a unit translation. The integer 11 may take the values 1, 2, 3, 4,
or 6. The screw axis defined by the symbol 3
1
means that a point is rotated
around the axis by 120 (360/ 3) and then translated by one-third of a unit
translation. This is shown graphicall y in Fig. 17- 14. The points represented by
2 and 3 result from successive 3
1
operations. Point l' is indis tinguishable from
1 since it is the result of a 3/ 3 or unit translation.
A glide plane is the result of combining a translation parallel to a mirror
plane with subsequent reflect on across the mirror. The t ransl ation is either along
a cell edge or a face diagonal. Glide planes are designated as a, b, e, 11, or d
depending on the translation. An a-glide is shown in Fig. 17-1 5. The translation
for glides a, b, and e is one-half of the axial length, for l1-glides it is one-half of
the diagonal length. Diamond or d-glides occur for centcred lattices and
correspond to a one-fourth diagonal translation. Since all glide planes translate
either by one-half or one-fourth, after either two or four glide operations, the
resulting point corresponds to a unit transl atio n. A glide operation inverts
chirality; a screw does not.
' n addition to screw axes and glide planes, centering operations may also
be present. P or primitive lattices havc no centered lattice points. A, B, and e
lattices have lattice points centered on their respective cell faces. 1 lattices have
a lattice point at the center of the cell and F iattices have lattice points on aIl
faces, Centered lattices are shown in Fig. 17 13.
AIl 230 space groups are compiled in the International Tables, Vol I(7b)
Equivalent positions, special positions, and reflecti on conditions for each are
listed. The reflection conditions observed for the diffraction data are used to
determine the space grou:, lor a given crystal structure. UnfortunateJy, several
space groups have identical reflection conditions (usually referred to as systematic
absences) and are not di . tinguishable from one a nother solcl y on t his basis. Table
17-4 lists symmetry elements and their associated systematic absences. This table
may be used to determine the space group of a crystal structure based on the
fact that symmet ry elements give rise to specific systematically a bsent refl.ections.
The equivalent pos tions (fractional coordi na tes where two identical molecules
are located in the unit cel!) for the monoclinic space group P2 are iHu trated in
Fig. 17-16. The 2( screw axis relates every point at xyz to an equivalent point
at - x, y + 1/
2
, - Z. The screw axis is along b such that the equpoint - x, y + 1/
2
,
- z results from rotation a bout b and tben translation of one-hal f of a unit ceH
(t he sign of y remai ns lhe same, whereas x and z becom negative).
Unit
translation
CD
FIGURE 17- 14 Three-fold
screw axis. (Reproduced with
permission from G. H. Stout
and L. H. Jensen, "X-Ray
Structure Determination. A
Practical Guide." 2nd ed.
John Wiley & Sons, New
York, 1989.)
FIGURE 17- 15 Glide plane
a. (Reproduced with
permission from G. H. Stout
and L. H. Jensen, " X-Ray
Structure Determination. A
Practical Gui de." 2nd ed.
John Wiley & Sons, New
York, 1989.)
r-_____--,b
y
P 2 \, equivalent positi ons
(1) x, y, Z, (2) X, y + -1', z
FIGURE 17- 16 Equivalent
position in space group P2, .
from G. H. Stoul and L. H.
Jensen, "X-Ray Structure
Determi nation. A Practical
Guide. " 2nd ed. John Wi ley
704 Chapter 17 X-Ray Cryslallography
TABLE 17-4. Symmetry Elements and Reflection Conditions
Affected
Symmel ry Element Rellection
2-fold screw (2J}
4-fold screw (4
2
) alo ng
6-fold screw (6
3
)
3-fold screw (3
1
, 3
2
)} 1
6-fold screw (6 , 6 ) a ong
2 4
4-fold screw (4
1
, 4
3
) along
6-fold screw (6
1
, 6
5
) along
Glide plane perpendicular to
translation b/ 2 (b glide)
e/2 (e glide)
b/2 + e/2 (n gl ide)
b/ 4 + e/4 (d glide)
Glide pl ane perpendicul ar lo
translation a/2 (a glide)
t/2 (egli de)
a/ 2 + e/2 (/1 glde)
a/4 +c/4 (d glde)
Glide pl ane per pendi cular to
translalion a/2 (a glide)
b,'2 (b glide)
a/2 + b/2 (/1 glde)
a/4 + b/ 4 (d glde)
A-centered lattice (A)
B-cenlered lattice (B)
C-cenlered lattice (C)
Face-centered lattice (F)
Body-cen tered lattice (0
a hOO
b OkO
e 001
ca
00/
a hOO
b OkO
e 001
c 001
a
Okl
b
hOI
e
hkO
hkl
Condlll on lor Systemallc
Absenca 01 Refl ectl on
h = 2/1 + 1= odd
k = 2n + 1
1= 2n + 1
1= 3n + 1, 3n + 2,
i.e., notevenlydivisibleby 3
h = 4/1 + 1, 2,or J
k = 4/1 + 1, 2, or 3
1= 4n + 1,2, or J
1=6n + 1, 2, J, 4, or 5
k = 2n + 1
1= 2n + 1
k + 1=2n + 1
k + /= 4n + 1, 2, or 3
h = 2n + 1
1= 2n + 1
h + f = 2n + 1
h + 1=4n + 1, 2, or J
h = 2n + 1
k = 2n + 1
h + k = 2n + 1
h + k = 4n + 1, 2, or 3
f{ +1= 2n + 1
h + f = 2n + 1
h + k 2n + 1
h + k = 2n + l}i.e., h, k, 1 nol
h + f = 2/1 + 1 allevenorall
k + 1= 2n + 1 odd
h + k -1 = 2n + 1
a Note that in the crystal cl asses in whi ch 3- and 6-rold screws occur as cell axes, these are
co nventi ona lly assigned LO be e, so only the 00/ reftectio ns need be considered.
17-17 SPACE-GROUP DETERMINATION
Despite the possible need to choose from among 230 options, In fact , most
molecularspecies crystallizeinjustafew different spacegroups: pI, P2j e, e2/e,
P2 2 1, Pbea, and Pnma account for about 85% ofaH structures. .
ThefoHowing twoexampleswill illustratehowtodet erminethespacegroup
ofacrystalfrom thediffractionsymmetryandsystematicabsences.Thediffraction
symmetry may be determined using photographs and the systematically a bsent
reflecti ons may be determined from the intensi ty data.(Refer to Table 17-4 for
the symmetry el ment/systematic absences relationships.)
Case l. The diffraction symmetry is 2/m (a twofold rotation axis with a
mirrorplaneperpendiculartoit),indicatingamonocliniccrystalsystem.
There areno reflectioncondt ions consistentwitha centeringoperation
so the lattice is primiti e P. Reflections ofthe type hOI are absent when
1is odd and theOkO reflections are absent when k is odd. According to
17- 18 Avoiding Crystallographic Mistakes 705
It
1I
Table 17-4, the hOl absence is a result of a c-glide plane perpendicular
to the b axis and the OkO absence is indicative of a 2, screw axis along
b. The space group is uniquely defined as P2/c.
Case 2. The diffraction symmetry is 2/m indicating a monoclinic ceU. The
only systematic absences observed are for hkl reflections when the value
of h + k is dd. This information is consistent with a C-centered lattice.
Since there is no screw axis or glide plane indicated, the only possible
space groups are C2, Cm, or C2/m. These space groups are indis-
tinguishable from one another and it may be necessary to examine each
by trial st ructure solutiollj refinement to determine which is the correct
space group.
Case 2 represents a sit uation where one must make a choice between
centrosymmetric and non-centrosymmetric space groups (C2/m is cent ric, Cm
and C2 are acentri c). If a structure contains an equal mi x of left - and right-handed
molecules, it must crystall ize in a centrosymmetric space group. This is true even
if the molecule is asymmetric. The handedness or chirality of a crystal means
that a structure cannot be superimposed on its mirror image. If a crystal is known
to be chiral and resol ved, it must not be centrosymmetric. When more than one
space group is possible, this information may assist one in determining whether
a centric or non-centric space group is most likely the correct choice.
17-18 AVOIDING CRYSTALLOGRAPHIC MISTAKES
The aforementioned problem of determining whether a crystal is best described
as centrosymmetric or non-centrosymmetri c requires further discussi on. Since
centric/ acentric space group " pairs" (e. g., C2/m, Cm, C2) ha ve the same systematic
absences, these are of no help i n sorting out the ambiguity.
Consider the monoclinic space groups P2 J m and P2, that are centrosym-
metric and non-centrosymmetric, respectively. The only systematically absent
reflections are the OkO when k is odd (twofold screw axis perpendicular to b). If
a structure is solved in P2 ,/m, it may al so be descri bed in P2 , wit h a doubli ng
of the Z value (The Z value refers to the number of molecules in the unit cel !.
The Z value for P2, /m with one molecule in a general posi tion is 4, whereas for
P2, it is 2.) If a structure has molecul ar symmet ry such Ihat a mirror plane relates
one-half of the moJecule to the other, then it is possible (but not required) that
the molecule possesses the same crystallographic symmetry and be located on
the crystallographic mirror plane in P2/m. This struct ure could al so be described
in P2" but all atoms would have to be located. (The discussion of molecular
versus crystallographic symmetry wiU illustrate the requirement to !ocate onl y
the symmetry unique atoms for naphthalene.)
Frequently, a structure wiU be described as ordered in a non-centrosymmetric
space group rat her than as disordered in a centrosymmetric one.(9) When this
situation occurs, it may be more correct to describe the structure as centrosym-
metric and disordered, indicating that only the "average" st ructure has been
determined. Several truct ures have been " republished " after investigation of the
original work revealed that the space-group assignment was lncorrect(' O)
An example of a st ructure that was originally described in a non-centrosym-
metric space group and later shown to be more correctly described as centric is
C6
FIGURE 17-17 Isotropic
thermal pl ot of
[(1,4,7,10-
tetrathiacyclododecane)
copper(ll) bis-perchlorate-
monohydratel .
taken from reference 9. The structure of[(1 ,4,7, 10-tetrathiacyclododecane) cop-
per(IT)bis- perchlorate-monohydrateJ(Fig. 17- 17)wasdescribedin thenon-centric
orthorhombic space group Pbe2. Potential problems that should have been
carefully considered were:
1. A pseudomirror plane perpendicular to the e-axis that would be
consistent with the mirror plane in Pbem (centric).
2. Problems in least-squares refinement ofheavy atom positions.
3. Refi nement of S atoms with anisotropic temperature factors led to
unrealistic bonddi stances requiringisotropicrefinement oftheseatoms.
(An ani sotropic temperature factor is an exponential expression that
accounts for the vibrat ion ofan atom. This vibration is described as an
ellipsoid rather than sphericallysymmetric or isotropic.)See Fig. 17- 19
foranexampleofamoleculerefined withanisotropicthermalparamet ers
and Fig. 17-17 for the isotropic plot of [(1,4,7,10-tetrathi acy-
clododecane)copper(JI)bis-perchlorate-monohydrateJ.
4. A high R value of 12. 7% (R values are quantities that are used to
compare observed and calculated structure factors .See Section 17- 20.
5. Largeranges for theCu-S and S-Cdistances2.30(1) to2.37(1 )and 1.73(4)
to 1.9(4) .
6. Short C-C distances 1.41(3) .
Refinement in the centrosymmetric space group Pbem yielded the following
significant results.
l. Statis! icallyequivalen!Cu-S[2.325(3)J andS-C[1.815(9)J distanceswith
esd 's aboLl t one-halfas large as the original.
2. A much lower R value of6.8% with all atoms anisotropic.
There is considerable disorder in the Pbcm structure ' the three S-C-C-S
groupings aredi sordered across planarconformationsand thereis a high degree
ofdisorderfor the two perchlorate ion (a common problem). it is clear that (he
ordered Pbc2 structure is j ust one ofmany possible orientations oflhestructure
that is b tter d scribed by the " average,. Pbem m del.
The moralofthe foregoi nge ampleis to examineeach possi bJc spacegroup
carefully when a choice must be made between a centrosymmetric or non-
centrosymmetric model. .ome ofthe following things to note are:
1. Does the molecule po sess any molecular symmetryas a mirror plane,
inversion center, or rotation axis that may also be crystalIographic?
2. How many molecules are in the asymmetric unit ?What is the expected
and observed Z-val ue?
3. Are pairs ofatom coordinates similarsuch that they may be rel ated by
sorne symmetry oper tor ?
4. Ar in! ratomicdi stancesandanglesconsistent wi thin accepted ranges ?
5. Are the hapes ofthermal ellipsoids reasonable?
The be t rule to foll ow when one has a choice of centrosymmetric or
non-centrosymmet ri c space groups is to test th ccntrosymmetric group fi rst. If
thest ruct ure cannot be sol ved orrefi ned properly thcn attemptthesolution wit h
thenon-centrosymmetricspacegroup.Tfanyoftheforegoingproblemsarenoted
orif the tructure fail s to refi ne well,then investigate thecentrosymmetricgroup
again untl it is c1ear that the structure can only be described in the non-
centr ymmetric space group.
17-20 Quality Assessment 707
17- 19 MOLECULAR VERSUS CRVSTALLOGRAPHIC SVMMETRV
There are often relationships between a structure's molecular and crystallographic
symmetry. consider the case of naphthal ene and pyrene (Figs. 17- 18(A) and
17-18(8)). Both molecules are highly symmetric with planar structu res. Viewing
Figs. 17-17(A) and 17-17(B), it is c1ear that both molecules possess mmm
molecular symmetry (three perpendicular mirror planes), inversion centers, and
rotation axes. Naphthalene may be described as having mirror planes (1), the
m--t-
Cl C5'
---+-----t--
C5
m
- m-
~
(A)
(8)
FIGURE 17-18 8all-and-stick drawings 01 (A) naphthalene and (8) pyrene
plane of the molecule, (2) a mirror along C3-C3', which would relate each hal f
of the molecule to itself, and (3) aplane bisecting th Cl -CS, C3-C3', and Cl' -CS'
bond . There are also twofold rotation axes perpendicular to these mirrors that
relate hal ves of the molecule. In addition, there i a n inver- ioo center midway
between C3-C3' that interconvert thc two ri ngs. Whereas naphthal ne exhibits
a high degree of molecular symmetry, the only observed cry taIlographic
symmetry is the inversion center between C3-C3' . Table 17- 5 lists atom
coordinat es for the inversion-related atom pairs. The inversion center is located
at (O, O, O). When solving the st ructure of naphthalene, only one-half of the total
number of atoms needs to be located a nd refined since the ol her half is related
by symmetry. AH of the aforementioned noted molecul a r ymmelry elements are
also present for pyrene. This would lead 00 to expeet thal at I a t sorne of these
elements are present in the crystal struct ur ; however. pyrene ha no crystallo-
graphic symmetry and all atoms must be located and inc111ded in t he refinemcn l.
These two examples shoul d illustrate the fael that molecul ar symmetry does not
necessa rily lead to crystallographic ymm try.
17- 20 QUALlTV ASSESSMENT
X- ray di ffractio n experiment produce resuJts t hat are usuall y believed implicitly.
After all , there is a pict ure of the mol eule so it must be eorreet and well done.
Although most X-ray studies are accurate, one should remember that t he derivcd
~
-m
TABLE 17-5. Atomic Coordinates and Their Inversion-
related Pairs for Naphthalene
Axes
Atom x y z
e l 0.08232 0.01856 0.32836
e 2 0.11295 0.16382 0.22289
e 3 0.04799 0.10518 0.03714
e 4 0.07656 0.25183 -0.07582
e 5 -0.01320 -0.19021 0.25460
H1 0.12420 0.05890 0.45540
H2 0.17870 030560 0.27110
H3 0.14180 039070 -0.02360
H4 -0.03330 -0.29520 0.33130
Inverslon-related Atoms
e l ' -0.08232 -0.01856 -0.32836
e 2' -0.11295 -0.16384 - 0.22289
e 3' -0.04799 -0.10518 -0.03714
e 4' -0.07656 -0.25 183 0.07582
e S' 0.01320 0.19021 - 0.25460
H l ' -0.12420 -0.05890 -0.45540
H2' -0.17870 -0.30560 -0.27110
H3' -0.14180 - 0.39070 0.02360
H4' 0:03330 0.29520 -0.33130
results were obtained experimentally and that errors may occur either in the
diffraction experiment or in the interpretation of results. The following discussion
focuses on what to loo k for in a crystallographic paper and how to decide whether
or not the reported results are correct.
The two quantities that should be examined to determine the accuracy of
a crystal structure are the R values and the estimated standard deviations (esd 's)
of derived parameters. The conventional R value is gven by equation (17-8).
(17-8)
where Fo are the observed structure factors derived from the measured reflection
intensities and Fe are the structure factors calculated for the refined model. rom
equation (17-8) it would appear that the lower the R value, the better the structure
since the observed and calculated F's will be in better agreement. Although this
is generally true, th R value may be artificially lowered using a number of
techniques. The moSl common way of reducing the R value of a structure is to
omit weak reflections. This is an accepted practice by most crystallographers
since all crystals exhibit weak reftections at higher diffraction angles and a cutoff
intensity (J or F) should be included in the papeL An intensity cut off of 1 > 3a(J)
means that only refl ction with intensities greater than 3 times their me,\sured
deviation (sigma) will be used in calculations (3a(J) corresponds to 6a(F) since [
is proportional to F
2
) . One should regard as suspect papers that report a data
cutoff greater than the 3a(J) or 6a(F) threshold. In addition to the R (or RF
val ues), one should be awa re ofthe weighted R (also listed as wR or R
wF
)' Weighted
R values are based not only on F values but on the sigma of F as well. Reftections
17-20 Quality Assessment 709
with higher (JF will be downweighted from those with lower (JF values. A typical
weighting scheme is given by equation (17-9).
(17-9)
where g is a small value (0.01 to 0.001). The resulting weighted R value is shown
in equation (17-10).
(17-10)
Since the weighted R value is based on more informa tion (JF), it is the better
value on which to base the accuracy of the structure determination. If it is reported
that a structure was refined using " unit weights " (all reftections weighted equally),
this structure should be reviewed carefully since a proper weighting scheme will
usually lead to lower esd 's for derived pa rameters.
The best criterion on which to judge the accuracy of a crystal structure
determination is found in the derived parameters and their esd 's. If interatomic
distances and angles fall within expected ranges and their esd 's are small, then
it is reasonable to assume that the structural study was done properly. Omitting
too many weak reftections will lead to increased esd's so this should be avoided.
Failing to measure enough data will also result in higher esd's since the
data-to-parameter ratio will be low. A data-to-parameter ratio of at least 8 to
10: 1 should be considered a lower limit for a well-defined structure, although
this is not always achievable.
Since all structural reports should include a plot of the molecule, the reliability
of derived parameters may often be determined simply by looking at the picture.
The molecular plot should be a thermal ellipsoid plot such as that shown in Fig.
17-19( 11) rather than ball and stick plots as shown in Figs. 17- 18(A) and 17-18(B).
The thermal motion of an atom is represented by an ellipsoid within which the
electrons of the atom have a probability of being. This probability, which is
usually 50 %, shouJd be noted on the plot. The molecule in Fig. 17-19 shows a
high degree of thermal motion for the carbon atoms (particularIy the methyl
carbons) of the pentamethylcyclopentadienyl ligands even though the data set
was collected a t 173 K. Since these ligands can rotate freely, it is understandable
that the carbon atoms show this high degree of libration. If an atom is disordered
(more than one possible position for an atom-static disorder), a la rge thermal
motion may either alert one to this possibility or may serve to "smear out" the
disordered components.
A few ions that are often disordered are Et
4
N+, CIO 4 - , BF4 - and PF6-.
Et
4
N I usually exhibi ts static disorder between the alpha carbon atomsof the
ethyl groups, whereas ClO; , BF4 -, and PF6 - show spherical disorder due to
their spherical nature. Figure 17-20 shows a disordered Et
4
N- ion.o 2) Whenever
possible, these ions should be avoided when attempting to grow single crystals
for a diffraction study since it may not be possibJe to completely resolve the
resulting disorder problems. Sorne alternati ve counter ions that can be employed,
and that are usually ordered, are triftate, B(C
6
H
s
)4 -, C6Hs)3P)2N . , a nd
(C
6
H
s
)4As +.
710 Chapler 17 X-Ray Crystallography
C32'
C41
C21", .
C11'
C12
Ce21
C22
FIGURE 17- 20 Disorder 01
the ethyl groups in Et
4
N+
As the result of the co-crystallization of two c10sely related compounds, a
crystal will not be pureo Often the contaminant will be present at only a few
mole percent. This can give rise to another kind of disorder: composi tional
disorder. An example is found in the structure of cis,jac-(R
3
Ph Mo(=O)CI
2
,
which is now known to contain small quantities of fac-( R
3
Ph MoCJ3' An earlier
report of "anomolously" long Mo-O bond distances in the former complex
has been reinterpreted as the superimposition of the Mo- O bond wil h a
previously unrecognized small percentage of longer Mo- CI bonds.
13
17-21 CRYSTALLOGRAPHIC DATA
The advent of fast computers and automated data collection routines has resulted
in an ever-increasing amount of structural data being generated and published.
Fortunately, there are a number of computer databases and collections of printed
material that one can access to utilize this structural information.
The largest compilation of structural data is tbe Cambridge Structural
Database ( SD) operated by Cambridge ni versit y (England). AIl published or
directly deposited organic and organometallic complexes characterized byeither
x-ray or neutron diffraction are inc1uded. The CSD is far more than a reference
database. Tn c1uded are atomic coordinates, unit cell parameters, space groups,
R values, and esd 's. Cambridge has also developed the computer programs
necessary to access the database. A graphical user interface allows one easy access
to all structural information as well as the ability to generate molecular geometries
and plots. The database contained over 82,000 entries in 1989 with 8000 to 9000
new ent ries yearly (Table 17- 1).
The Protein Dala Bank of the Brookhaven Nalional Laboratory contains
atomic coordinates for proteio and nucl eic aci d structures. The lnorganic Cryst al
Structure Data Base is composed of all compounds lacking carbon-carbon or
carbon-hydrogen bonds but doe inc1ude metal carbides. (See also reference 4.)
Exercises 711
1. The Newsletter of che Cambridge Structural Database Syscem, Cambridge Crystallo- REFERENCES
graphic Data Centre, Cambridge, u.K.,April 1990.
CITED
2. H. Hope, and B. G. Nichols, Acta Cryst., B3 7, 158-161 (1981).
3. G. H. Stout,and L. H.Jensen,"X-Ray Structure Determination. A Practical Guide,"
2nd ed., Wiley, New York, 1989.
4. 1. P. Glusker and K. N.Trueblood, "Crystal Structure Analysis. A Primer," Oxford
University Press, Oxford, u. K., 1985.
5. D. Brodalla,D. Moot z,R. Boese, and W.Osswald,1. Appl. Cryst.,18, 316-319(1985).
6. M. C. Etter, and P. W. Baures, J. Amer. Chem. Soc., 110, 639-640 (1988).
7. a. "International Tables for X-Ray Crystallography," Vol. I1I,eds. C. H. Macgillavry
and G. D. Rieck, Kynoch Press, Birmingham, England, 1962.
b. "InternationalTables for X-RayCrystallography,"Vol. 1,eds. N.F.M. Henryand
K. Lonsdale, Kynoch Press, Birmingham, England, 1952.
8. H. Hope, University ofCalifornia, Davis. Personal communication to 1. Ziller, 1987.
9. R. E. Marsh, Acta. Cryst. , B42, 193-198(1986).
10. R. E. Marsh, and F. H. Herbstein, Acta. Cryst. , B44,77-88 (1988).
11. W. 1. Evans, R. A. Keyer, and 1. W. Ziller, Organometallics,9, 2628-2631 (1990).
12. M. R. Churchill, and S. W.-Y. Chang, Inorg. Chem., 13,2413-2419 (1974).
13. K. Yoon, G. Parkin, A. L. Rheingold, 1. Am. Chem. Soc., 113, 1437-1439(1991).
1. Acrystalof[In1Mes
2
J2 is monoclinicwith reciprocallattice parametersa* = 0.038930,
b* =0.058389,c* =0.127765 and P* = 75.298. Calcula te thedirectcellparametersand
unit-cell volume. (Mes is mesityl).
2. Thedensity oftheaboyecomplex is 1.792 mgj m
3
Thenumber ofmolecules in the unit
cell may becalculated using: n = [(density)(V)J j [(Avogadro constant)(MW)]. What is
n (2value) for the complex?
3. The systematic absences observed for the aboye complex are hkl for h +k = 2n +1
and hOI for 1= 2n +1. Whatare the two possible monoclinicspacegroups? Given the
calculated 2 value, is it possible for the molecule to lie on a general position in both
space groups? What point symmetry is possible in one of these space groups? (See
International Tables.)
4. Determine the space group(s) consistent with the following systematic absences and
crystal class.
a. Monoclinic: OkO for k = 2n +1; hOI for h +1= 2n +1.
b. Orthorhombic: hkl for h +k, k +1; Okl for k +1=4n +1; hOI for n +1=4n +1;
hkO for h +k = 4n +1
c. Orthorhombic: hkl for h +k +I= 2n +1; Okl for k = 2n +1; hOI for h = 2n +1
d. Orthorhombic: Okl for k = 2n +1; hOI for 1=2n +1; hkO for h = 2n +1
e. Same as for(d) but also hkl for h +k +1= 2n +1
f. Triclinic: hkl for h +k +I= 2n +1
EXERCISES
S. Whatis theabsorptioocoeffl cieo t(J1) for(MeSCS)3Smgiveo thedensityis 1.375 mg/m
3
?
6. What is the oumber ofaccessible reftectioos for the complex io questioo (1) [or both
Mo aod Cu radiation aod how many octets ofdata will oeed to be collected? Why
may the resulting number of reflections appear to be less than required? How maoy
reftectioos will there be for Mo radiation with a 2-theta limit of55 degrees?
7. Ifa molecuJehas a chiral center and is known to be resolved, what is a specific reason
why it may not crystallize io space group P2 /c?
8. What wilJ be the maximum and minimum a bsorption effects 00 the reftectioos [rom
thecrystalioproblem5ifthecrystal meas urementsare0.10 x 0040 x 0.80mm?Should
a correction be made? Should thi s crystal be used in the X-ray diffractioo study?
APPENDIX
Character Tables for
Chemically Important
A
Symmetry Groups
1. THE NONAXIAL GROUPS

ATl
e, E (Jh
A' x, y, Ro x
2
, y2,
Z2 , xy
A" -1 z, RX , R,. YZ,xz -1 x, y, z
xy, xz, yz
2. THE en GROUPS
A 1 z, Ro x
2
, y2, Z2, xy
B -1 x, y, Rx, Ry yz,xz
e 2
f, = exp (2n if3) E e
3 3
e
3
X2 + y2 , Z2
1 1 1 A z, Rz
e
(X2 _ y2, xy)(yz, xz) E (x, y)(R " R) g
e*
:*}
e
4
E e
4
e
2
e 3
4
A 1 z, R:
X2 + y2 , Z2
B 1 -1 -1
X2 _ y2 , xy
E
{:
-i
-1
-1 -a
(x, y)(R x, R) (yz, xz)
713
714 Appendix A Character Tables lar Chemically Important Symmetry Groups
2. THE en GROUPS (continued)
e 2
S
e 3
S
e 4
S
8 = exp (2ni/5)
8
8*
;2
8
2
*
;2
8
2
*
8*
8
8
2
*
8
2
8
8*
z, R,
(x, y)(R
x
, R) (yz, xz)
e 2
3
e s
6
8 = exp (2ni/6)
A
B
1
1
g
g
1
-1
8
8*
- 6*
- 8
- 8*
- 6
-8
-6*
1
-1
-1
-1
- 8
- 8*
- 6*
- 8
1
-1
:*}
-8 }
- 6*
(x, y)
(R" R)
(xz, yz)
E
e 2
7
e 3
7
e 4
7
e s
7
e 6
7
8 = exp (2nif7)
A
8*
z, Rz
(x, y)
(R
x
' R)
(xz, yz)
e 3
4
e 3
8
e s
8
e 7
8
8 = exp (2ni/8 )
A 1 1 1 z, R,
B - 1 -1 -1 -1
6
6* - 1
-1
-1
- ; - 8*
-8
-6
- 8*
:*}
(xz, yz)
-i
- 8*
-8*
-1
-1
-i
1
- 1
-1
- 1
- 1
-1
-i
8*
8
- i
6
8*
-; }
-8*}
- 6
3. THE Dn GROUPS
1
-1 -1
-1 1 -1
-1 -1 yz
1 -1 z, R,
(X2 - l , xy)(xz, yz) -1 o (x, y)(R
x
' R)
Appendix A CharacterTables lor Chemically ImportantSymmetry Groups 715
D4 E 2C
4
C
2
(=C/) 2C
l
' 2C
l
"
Al
A
2
BI
B
2
E 2
-]
-1
O -2
-1
1
-1
O
-1
- 1
1
O
z, R.
(x, y)(R" R)
X2+yl,z2
x2 _ y2
xy
(xz, yz)
3.
Ds
Al
Al
El
El
D6
Al
A
2
BI
Bl
El
E
2
4.
Cl v"
Al
Al
BI
Bl
THE Dn GROUPS (conlinued)
E 2C
s
2C
S
2
5C
2
1
- 1
2 2 cos 72
0
2 cos 144
0
O
2 2 cos 144
0
2 cos 72
0
O
Z, Rz
(x, y)(Rx, R)
E 2C
6
2C, C
2
3C
l
' 3C
l
"
1
- 1 -]
1 -1 -1
2 - 1 - 2
2 -1 -1 2
THE e
nv
GROUPS
E C
l
aJxz) au'(yz)
-1 - 1
-1 -1
-1 -1
1
-1 - 1 z, R,
1 -1
-1 ]
Xl + yl, Z2
(xz,yz)
(x
2
_ yl, xy)
O O (xz, yz) (x, R,.)
(Xl _ yl, xy) O O
z
Rz
x, Ry
y, Rx yz
"Foraplanar molecule the x-axis is taken perpendicular to the
plane.
C,u
E 2C, 3a
u
Al z
Xl + y2, Zl
Al 1 -1 Rz
E 2 -1 O (x, y)(R
x
' Ry)
(Xl _ y2, xy)(xz, yz)
a
E 2C
4
2a
u
2a
d
C
4u
C
l
X
l
+,yl,z2 z Al
-1 - 1 R. Al
Xl _ yl
- 1 1 -1
BI
xy 1 -1 -1 1 .Bl
E 2 O - 2 O O (xz, yz) (x, y)( R
x
' Ryl
"Ifthe e,v contains a square array ofatoms, the (Jv planes should pass
through the larger number ofatoms ofthe square array or should intersect thelargest
possible number ofbonds.
71 6 Appendhc A Character Tables lorChemically ImportantSymmetry Groups
C
sv
Al
A
2
El
E
2
E 2C
s
2C
S
2
5a
v
1
X2 +y2, Z2
Z
1 -1
Rz
2 2cos 72 2cos 144 O (xz, yz) (x, y)(Rx, R)
(x
2
_ y2, xy)
2 2cos 144
0
2cos 72 O
C
6v
E 2C
6
2C
3
C
2
3a,) 3a
d
Al
A
2
Bl
8
2
El
E
2
1
2
2
-1
-1
1
-1
1
1
-1
-1
-1
-1
- 2
2
1
-1
1
-1
O
O
-1
-1
1
O
O
z
Rz
(x, y)(Rx. R)
X2+y2,Z2
(xz,yz)
(x
2
_ y2,xy)
5. THE C
nh
GROUPS
C
2h
E C
2 ah
Ag Rz
x
2
,y2, Z2, xy
B9
-1 -1 Rx, Ry XZ, yz
Au
-1 -1 z
Bu
-1 -1 x,y
C
3h
A'
E'
A
n
En
C
4
/1
Ag
Bg
Eg
Au
Bu
Eu
{;
E C
3
C
3
2
ah S3
S
3
s
1 1
8*
: *}
8* 10 *
1 -1 -1 -1
8* -1 - e
-8*}
{;
8* -1 - 8* - 8
E
C 3 S
R=
(x, y)
z
(R
x
' Ry)
3
C
4
C
2 4 4 a/l
g
1
1 - 1 -1 -1
-1 - i -1
- [ -1 1 -i -1
1 1 1 -1 -1 -1
1 - 1 -1 -1 1 -1
- 1 - i - 1 -i
{: -i - 1 -1
e= exp (2rrij 3)
X2+y2,22
(x
2
_ y2,xy)
(xz, yz)
S4
1
-1
-:}
- 1
1
-;}
Rz
(Rx,Ry)
z
(x, y)
X2+y2, Z2
X2 _ y2, xy
(xz, yz)
Appendix A Character Tables tor Chemically Important Symmetry Groups 717
e
s
, E
S 7
5
S 3
5
S 9
5
e = exp (2ni / 5)
A'
Rz
E
l
'
c* e
e*
e
2
e
2
*
:* }
(x , y)
E
2
'
e
2
eh
e*
e e*
e
2
*}
e
2
A" -1 -1 -1 -1 -1 z
E "
l
- 1
-1
- e
- e*
_e
2
_ e
2
*
_ e
2
*
_ e
2
- e*
- e
(xz, yz)
E
2
"
-1
-1
_ e
2
_ e
2
*
- e*
- e
- e
-8*
_e
2
*}
_ e
2
E e,
S 5
3
s S
6
F. =ex p (271i {6)
{:
- 1
8*
- 0*
- c
- 1
-1
- 1
- 8
-8*
1
-1
8*
-1
8*
- c*
- o
1
-1
-1
-1
- 8
- c*
1
-1
~ L
R,
(R, . R,.)
(x z, yz )
{:
1
1
e
e
- 8*
- c
-1
c*
- 0*
- c
- 8
- e*
- .s *
- c
- c
- c*
-1
-1
-1
- c*
- o
- 6
- 6*
- c*
- c
- f.
- c*
- 1
0*
- o
- 0*
-1
-1
-[
-1
-1
-1
- 8*
- c
-1
I
- c
-c*
c*
-8
- c*
-1
-1
0*
0*
-1
-1
-1
- ; *
- o
-1
-1
c*
c*
- 8 }
- 8*
-1
- 8*}
- 8
:* }
(x, y )
(x
2
_ y' , xy)
A,
B,
Elll
6. THE Dnh GROUPS
(J( XY) (J( xz) (J(Yz) E
1 1
-1 - 1 1 - 1 -1
- 1 -1 -1 - 1
-1 -1 -1 -1 1 YZ
1 - 1 -1 -1 -1
-1 -1 - 1 -1 Z
- 1 1 -1 -1 1 -1 1 y
-1 -1 - 1 1 -1 x
y2, Z2
y2,xy
E
-1 1 - 1 Rz
2 -1 o 2 -1 o (x , y)
Al" -1 -1 - 1
Az"
-1 - 1 -1 1 Z
E" 2 -1 o -2 o
(R" R)
(XZ , yz)
-
.
,
J

.
.
.
.
.
.

e
x
:>

D
4
h
Q
l
g
2
g

B
l
g

B
2
g

E
g

A
l
u

A
l
u

B
l
u

B
2
u

E
u
2
C
4

C
l

2
C
l

'
2
C
l

"

2
S
4

(
J
h
2
(
J
u
2
(
J
d
1

2

1

2

1

-
1

-
1

O

1

1

-
1

-
1

O

1

-
2

1

-
2

-
1

-
1

O

-
1

-
1

O

-
1

-
1

1

O

1

-
1

-
1

1

O

2

-
1

-
1

-
1

-
1

-
2

1

-
1

-
1

O

-
1

-
1

1

1

O

1

-
2

-
1

-
1

-
1

-
1

2

1

-
1

-
1

O

-
1

1

-
1

1

O

-
1

-
1

1

O

-
1

1

-
1

O

I

R
,
(
R
'
R
y
)
Z

(
x
,
y
)
X
2

+

y
2
,
Z
2

X
2

_

y
l

x
y
(
x
z
,
y
z
)
(
J
u
p
a
s
s
e
s

t
h
r
o
u
g
h

t
h
e

a
t
o
m
s

a
n
d

(
J
d
b
i
s
e
c
t
s

t
h
e

b
o
n
d

a
n
g
l
e
s
.

2
D
S
h
2
C
2
C
S
C
l

(
J
h
2
S
2
S
s
3
S
(
J
,
.
A
'
1

A
'
2

E
1
'
E
2
'
1
"
"
2

E
"1

E
"2

1

2

2

1

2

2

2

c
o
s

7
2

0

2

c
o
s

1
4
4

0

1

2

c
o
s

7
2

o

2

c
o
s

1
4
4
0

2

c
o
s

1
4
4
0

2

c
o
s

7
2

0

1

2

c
o
s

1
4
4
0

2

c
o
s

7
2

-
1

O

O

-
1

O

O

1

2

2

-
1

-
1

-
2

-
2

2

c
o
s

7
2

0

2

c
o
s

1
4
4
0

-
1

-
1

-
2

c
o
s

7
2

0

-
2

c
o
s

1
4
4

0

2

c
o
s

1
4
4
0

2

c
o
s

7
2

0

-
1

-
1

-
2

c
o
s

1
4
4

0

-
2

c
o
s

7
2

0

-
1

O

O

-
1

1

I
O

O

R
,
(
x
,
y
)
z

(
R
x
'
R
)
X
2

+

y
l
,

Z
2

(
X
l

_

y
l
,
x
y
)
(
x
z
,
y
z
)
D
6
h

A

1
9

A
2
g

B
1
9

B
2
9

E
1
9
E
2
g

A
l
u

A

2
u

B
l
u

B
2
u

E
l
u

E
2
u

E

2
C
6
2
C
3
C
2
3
C
2
'
3
C
2
"
2
S
3
2
S
6
a
h

3
a
d

3
a
u

1
X
2
+

y
2
,

Z
2
-
1
-
1
-
1
-
1
-
1
-
1
1

-
1
-
1
1

-
1
-
1
-
1
-
1
-
1
1

-
1
-
1
-
1
-
1
-
2
-
1

-
2
I

(
x

z
,

y
z
)

(
R
x
'
R
,
)

2
-
1
-
1

2
-
1
-
1
(
x
2

_
y
2
,

x
y
)

-
1

-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1

-
1
-
1
-
1
1

1
I

Z
-
1
-
1

1

-
1
-
1

-
1
-
1

1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
2
-
2
-
1
(
x
,

y
)

2
-
1
-
1
-
2
-
2
6
.

T
H
E

D
n
h

G
R
O
U
P
S

(
c
o
n
t
i
n
u
e
d
)

D
g
h

A

1
9

A

2
u

B

1
9

B
2
9

E
l
g

E
2
g

E
3
g

A
l
u

A
2
u

B
l
u

B
2
u

E
l
u

E
2
u

E
3
u

E

2
C
g
2
C
g
3
2
C
4
4
C
_
2
'
4
C
2
"
2
S
g
2
S
4
a
C
2
8
2
S
4
a
h

4
a
d

u

1
X
2
+

y
2
,

Z
2
1

-
1
-
1
-
1
-
1

-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1

1
1
2

-
1
2

O
-
2
1
2

-
1
2

O
-
2
I

(
R

x
'
R
,
)

I

(
x
z
,

y
z
)

2
-
2
-
2
(
x
2

_
y
2
,

x
y
)

2
-
1
2

1
2

O
-
2
-
1
2

1
2

O
-
2
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
I

z

-
1
-
1
-
1
-
1
1

-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
-
1
1

-
1
1
2

-
J
i

O
-
2
-
2
-
1
2

1
2

O
I

(
x
,

y
)

2
-
2
-
2
-
2
-
1
2

1
2

O
-
2
-
2
1
2

-
1
2

O
-
....J
-
.
1
.
c
.
o

720 Appendlx A Character Tables lor Chemically Important Symmetry Groups
7. THE Dnd GROUPS
Du E 2S
4
C
2
2C
2
' 2(Jd
Al
A
2
-1 -1
Bl -1 1 - 1
B
2
-1 -) 1
E O - 2 O O
R,
Z
(x, y),
(R x, R,)
X2 + y2, Z2
X2 _ y2
xy
(xz, yz)
D4d
E 2Sa 2C
4
2Sa3 C
2
4C
2
' 4(Jd
Al 1 1 X2 + y2, Z2
A
2
1 1 -1 -1 R,
Bl - 1 1 -1 1 -1
B
2
-1 1 - 1 1 - 1 1 z
El
E
2
2
2
fi
O
O
- 2
- fi
O
-2
2
O
O
O
O
(x, y)
(x
2
_ y2, xy)
E3 2
- fi
O
fi
- 2 O O (Rx, R) (xz , yz)
DSd
E 2C
s
2C
S
2
SC
2
2S
I0
)
2S
I0
SUd
A l.
A
2
,
El.
E2.
Al'
A
2
,
El,
E
2
,
1
2
2
1
2
2
2 cos 72
0
2 cos 144
0
1
2 cos 72
0
2 cos 144
0
2 cos 144
0
2 cos 72
0
1
2 cos 144
0
2 cos 72
0
1
-1
O
O
- 1
O
O
I
2
2
-,1
- 11
- 2
-2
2 ,Cos 7J.D
.2 ,005 144
0
- f
-U
-l cos 71
0
- 2 .cos 144 o
lcos 144
0
.2 cos 72
0
-1
-1
- 2 cos 644
0
- 1,nos 711
0
-1
O
O
-1
'1
O
1')
R,
(R,., Rr)
z
,(x, y)
X2 + y2 , Z 2
(xz, yz)
(x
2
_ y2, xy)
Appendix A Character Tables lar Chemically Important Symmetry Groups 721
7. THE D nd GROU PS (continued)
D6d
E 2S
12
2C
6
2S
4
2C
3
2S
12
5
C
2
6C
2
' 6a
d
Al
X2 + y2, Z2
A
2
1 1 -1 -1 R,
Bl -1 -1 - 1 1 - 1
B
2
-1 -1 1 - 1 -1 1 z
El 2
j3 O -1 -j3 -2 O O (x, y)
E
2
2 1 -1 -2 -1 1 2 O O (x
2
_ y2, xy)
E3
2 O -2 O 2 O - 2 O O
E4
2 -1 -1 2 -1 -1 2 O O
Es
2
-j3 1 O -1
J3
-2 O O (R" Ry) (xz, yz)
8. THE Sn GROUPS
S4 E S4 C
2
S4
3
A
Rz
X2 + y2, Z2
B 1 - 1 -1 z
x
2
_ y2,xy
E
{:
-1
-:} (x, y); (R
x
' Ry) (xz, yz)
- ; -1
1; = exp (2ni/3) S6
E C
3
C/
S
6
5
S6
X2 + y2, z 2 1 1 R, Ag
8* (x
2
_ y2, xy);
Eg (R
x
' Ry)
{: :*}
8* 8* (xz ,yz)
z 1 -1 -1 -1 Au
e* -1 - 8
n *
-e*}
(x,y) Eu
1; *
e -1 - 1; -e
Ss
A
B
El
E
2
E3
9.
E
Ss
C
4
S 3
s
C
2
Ss 5
C 3
4
S 7
s
1
1 -1 - 1 -1 -1
~ e* - ;
- 8*
- 1;
-1
-1
-1;
- 1; *
- 1
:*}
{:
- ;
- 1
- 1
- i
- i
- 1
-1
-; }
g
- 1;*
- 1;
- 1 1;
e*
-1
- 1
1;*
- ;
-e}
- 1;*
THE CUBIC GROUPS
Rz
z
(x, y);
(R x ' RJ
1; = exp (2ni/8)
X2 + y2, z2
(x
2
_ y2, xy)
(xz, yz)
T E 4C
3
4C/ 3C
2
e= ex p (2ni/3)
A 1 1 X2 + l + Z2
E
g
e
1;*
1;*
1; :}
(2z2 _ X2 _ y2,
X2 _ y2)
T 3 O O -1 (R
x
' R
y
, Rz); (x, y, z) (xy,xz, yz)
722 Appendlx A Character Tabl es l ar Chemically Important Symmetry Groups
9.
7;,
Ag
A"
Eg
Eu

T"
THE CUBIC GROUPS (conlinued)
E 4C
3
4C/ 3C
2
4S
6
4S
6
5
30"h
1 1 1
1 - 1 - 1 -1 - 1
8* 1 8 8*
{:
8
:} 8* 8 8* 8
8 8*
- 1 - 8 - 8*
- I}
{:
-1
8*
-1 - 8* - 8
3 O O -1 O O -1
3 O O -1 - 1 O O
(R
x
' Ry, R, )
(x, y, z)
O E 6C
4
3C
2
(= C/) 8C) 6C
2
Al
A
2
E 2
- 1
O
1
1
2 - 1
-1
O
TI
T
2
3
3
1
- 1
-1
-1
O
O
-1
1
(R" Ry, Rz); (x, y, z)
O. E 8C) 6C
2
6C. 3C
2
(= C/) 6S. 8S
6
3a. 6a
d
A l.
A
2
,
E,
1
2
1
-1
I
-1
O
-1
O
1
1
2 2
-1
O - 1
1
2
-1
O
TI,
T
2
,
Al"
A 2"
Eu
TI"
T
2u
3
3
1
1
2
3
3
O
O
- 1
O
O
- 1
1
- 1
O
- 1
-1
- 1
O
-1
- 1
- 1
1
2
- 1
- 1
3
3
-1
-1
-2
-3
-3
- 1
-1
1
O
-1
O
O
- 1
-1
1
O
O
- 1
-1
-1
-1
-2
- 1
-1
1
O
- 1
8 = exp (2ni/ 3)
X2 + y2 + Z2
(2z
2
_ x.z _ y2,
X2 _ y2)
(xz, yz, xy)

E 8C) 3C
2
6S
4
60"d
Al 1 X2 + y2 + Z2
A
2
E 2 - 1
1
2
- 1
O
- 1
O
(2z
2
_ X2 _ y2,
X 2 _ y2)
TI 3 O -J - 1 (Rx, Ry, R.)
T
2
3 O - 1 -1 1 (x , y, z) (xy, xz, yz )
X2 + y2 + Z2
(2z2 _ X2 _ y2,
X2 _ y2)
(xy, XZ, yz)
X2 + y2 + Z2
(R" R" R ,)
(2z2 _ X2 _ y2,
X2 _ y2)
(xz, yz, xy)
(x , y, z)
Appendix A Character Tables lor Chemically Important Symmetry Groups 723
10. THE GROUPS C
ro v
ANO O ooh FOR LINEAR MOLECULES
C""V
E 2C",<D C/J (J,.
Al L+
Az-L- 1 -1
E=O 2 2 cos <1> O
Ez-I'l
E) =<1>
2
2
2 cos 2<1>
2 cos 3<1>
O
O
E 2C""<D OO(J v
D"" h
L +
9
L -
9
Og
I'lg
1
2
2
2 cos <1>
2 cos 2<1>
-1
O
O
Lu +
L" -
O"
I'lu
2
2
2 cos <1>
2 cos 2<1>
-1
O
O
Z
Rz
(x, y); (R
x
' Ry)
2S"" <D
2 - 2 cos <1>
XZ + y2, Z2
(xz, yz)
(x
2
_ yZ, xy)
ooC
z
-1 Rz
O (R
x
' R)
2 2 cos 2<1> O
-1 -1 -1 z
-1 -1 1
-2 2 cos <1> O (x, y)
-2 - 2 cos 2<1> O
X2 + yZ, Z2
(xz, yz)
(XZ _ y2, xy)
11. THE ICOSAHEDRAL GROUPS
a
1, E 12C, 12C, ' 20C, 15C, I 12S, 0 12S,0
3
20S. 15a
Xl + y l + Z2 1 1 1 1 1 1 1 1 1 1 A,
T;, 3 (1 - .../5) t(1 + Js) O -1
3
~ 1 + Js) -)( 1- Js) O -1 (R
x
R,. R,)
3
T" 3 (l + j5) 1(1 - Js) O -1
G,
1(1 - Js) -l< 1 + Js) O -1
4 -1 -1 1 O 4 -1 -1 1 O
(2z' - X2 -
X2 _ y2.
5 O O -1 1 5 O O -1 1 H,
I
xy. yz. zx)
1 1 1 1 1 -1 -1 -1 -1 -1
A"
3
T," (x. y. z) t(1 + Js) ~ 1 - Js) O -1 -3 -i(l - Js) -t( 1 + Js) O 1
T,"
3
~ 1 - J s -l< 1 + Js) O -1 -3 -t(1 + Js) - t(1 - Js) O 1
G"
4 -1 -1 1 O -4 1 1 -1 O
5 O O -1 1 -5 O O 1 -1
H"
'" Fo r the pure ro tation group 1, [he outlined section in the upper len IS {he cha ractcr cable; he 9 subscript s should, of course, be dropped and (x. y, z)
assi gned lO (he TI represent atio n.
APPENOIX
B
Character Tables for
Sorne Double
Groups
GROUP e
3
'
e'
3
E R
e 2
3
A' r
l
E'
r
2
r
3
W
Z
-w
W
Z
-w
-w
W
Z
- w
)2
z, Lz
} x, y, Lx, Ly
El /Z'
r
4
rs
B3/ Z
,
r
6
-1
-1
- 1
w
_ w
z
-1
- w
w
2
W
Z
-w
_ w
z
W
-1
w = exp (in/3 )
D3
,
E R
e
3
e/R
e
3
Z
e
3
R
3e
z
' 3e
z
'R D3
,
e
3v
,
E R
e
3
e/R
e
3
2
e
3
R
3u
v ~ u v R e
3 v
,
Al
,
r
Az
,
r
z
E' r
3
... ................
1
1
2
......
1
1
2
. . . . . . .
1
1
- 1
. . . . .. . . .
1
1
-1
. . . . . . . . . .
1
-1
o
. . . . . . . . .
1
-1
o
. . . . . . . . . .
z, Lz
x, y, Lx, Ly
............... .
z
Lz
x, y, Lx, Ly
. .............. .
E
31z
,
{(Al')
r
4
(Az') r s
EI / z
(E' ) r
6
1
1
2
-1
-1
- 2
- 1
-1
1
1
1
-1
i
-i
o
-i
i
o
724
Appendix B Character Tables for Some Double Groups 725
C'
4
E R C
4
C
4
R C
4
2
C/R C
4
3
C
4
3
R C
4
,
S'
4
E R S4 S4
R C
2
R C
2
S4
3
S4
3R S'
4
A' r
B' r
2
E ' {r 3
r
4
...... .......
E / 2
{r
s
r
6
E3/2
r
7
re
1 1 1 1 1 1 1
1 1 - 1 -1 1 1 -1
1 1 i i -1 -1 -i
1 1 -i -i -1 -1 i
....................... . . ..............
1 -1 w - w i -i w
3
1 -1
_ w
3
w
3
-i i -w
1 -1 - w w i - i
_w3
1 - 1
w) _ w3
-i i w
1
-1
- i
i
o
_w
3
w
w
3
-w
z
Lz
} x iy
Lx iLy
......o o., "
Lz
z
} x iy
Lx iLy
. .........",.
w = exp (inj 4)
GROUP
TI
3C
2
T' E R 4C
3
4C)R 4C/ 4C/R
3C
2
R
A' r
2 2
w w w w
r
2
E'
r)
2 2
1 w w W w
T' 3 3 -1 O O O O x, y, z, Lx, Ly, Lz r
4
............ . ......... . ............. o
E/2 r s
2 - 2 O -1 -1
2
_ w
2
, 2 -2 O w - w w
r
6
G
3/ 2
2 - 2 O w
2
_w
2
W -w r
7
W = exp (2nij 3)
GROUPS O' ANO T';
O' E R
4C) 4C)' 3C.' 3C. 3C.' 3Cl'
O'
4C)'R 4C)R 3C/ R 3C.'R 3C. R 3C,'R
T' E R
4C) 4C) l
3C.' 3S. 3S.' 60'd
T'
d
4C/R 4C)R 3C/R 3S. 'R 3S.R 60'd R
d
A ' , r , 1 1 1 1 1 1 1 1
A' , r
l
1 1 1 1 1 - 1 -1 -1
E' r) 2 2 -1 -1 2 O O O
T '

r
4
3 3 O O -1 1 1 -1 x, y, z, L" L,., L, L" L,. , L,
T ' , r
5
3 3 O O - 1 -1 -1 1 x,y, z
. . . . . . . . . . . . . . . . . ... ..... .............
(E,' )
E1/"
r
6
2 - 2 1 -1 O
fi -fi
O
(E,') E
Si2
r, 2 - 2 1 -1 O
-fi fi
O
(C') C
3
.',' r
8
4 - 4 -1 1 O O O O
726 Appendlx B Character Tables for Some Double Groups
GROUP D4'
D '
4
A
[
' r[
A
2
' r
2
B '
[
r
3
B '
2
r
4
E '
[ rs
E '
2
r
6
E '
3
r
7
E
1
2
2
2
R
1
2
- 2
-2
C
4
C
4
3
R
- 1
- 1
O
Ji
-Ji
C 3
4
C
4
R
1
-1
-1
O
- Ji
Ji
C
2
CIR
1
-2
O
O
2C
2
'
2C
I
' R
1
-1
1
-1
O
O
O
2C
2
"
2Cz"R
-1
-1
1
O
O
O
APPENDIX
Normal Vi bration
Modes for Common
e
Structures
Pyramidal XY3 Molecules.
x
YI
v(A)
Tetrahedral XY
4
Molecules.
x
"3 (E')
Planar XY
3
Molecules.
727
728 Appendlx e Normal Vibration Modes tor Common Structures
v{A 1)
x
C
3v
ZXY3 Molecules.
y
~ I \ ...
~ ~ , ' \ .........
, ,
~ \
" ,
, ,
, : , - , , ~ ~
, .
"' ... \
Octahedral XY6 Molecules.
Appendix e Normal Vibration Modes lor Common Structures 729
Square-Planar XY4 Molecules.
Z
v(A)
1'2(A 1) V3(A 1)
X
Y Y
+
v4(B2)
I'5(B2) I'6.(BI)
+ +
Planar ZXY
2
Molecules.
730 Appendlx e Normal Vibrati on Modes lor Common Structures
y
y
y
y
v(A')
<l
vaf E'")
Trigonal Bipyramidal XY
5
Molecules.
Ethane-Type X
2
Y
s
Molecules.
Appendix e Normal Vibration Modes lor Common Structures 731
XI Xl
VI
Y
I Yl
T\
v(XX)
",(XY)
Planar (C2v) Al(p)
Al(p) A{p)
Non- planar (C
l
) A(p)
A(p) A(p)
~
;.\
V4
- \.
v .. (XY) .,(YXX)
p,(XY)
Hl(dp)
R
2
(dp) A ~ ( d p )
lJ(dp) 8(dp) A(p)
Nonlinear X
2
Molecules (p: Polarized; dp: Depolarized). Y
2
APPENDIX
Tanabe and Sugano
D Diagrams for Oh Fields*
al
"
40
30
10
'A,
'E
IE:....__~ __---!___---!___.....::)T, (d;)
2 3
DqfB
Energy diagram for the configurat ion d
2
.
These are complete energy diagrams for the configurations indicated, reproduced from Y. Tanabe
and S. Sugano, 1. Phys. Soco Japan, 9, 753, 766 (1954).
Y refers to the ratio of the Racah parameters Cj B. Heavy lines perpendicular to the Dqj B axis in
d4 , d5, d6, and d
7
indicate transitions from weak to strong fields. The calculation of and the assumptions
inherent in the ca1culations are contained in the original paper. The diagrams do not apply to any
particular complex but give a qualitative indication of the energies of the various states as a function
732 of DqjB.
50
40
4 T I d ~ d)'J
a:>
a:>
I
'-..
'-..
TI
....
JO
I
T
,
lE
Dq/B
Energy diagram for the configuration d
3
.
4
.
2
DqjB
5
. Energy diagram for the configuration d
6
.
734 Appendlx D Tanabe and Sugano Diagrams for Oh Fields
SO
lr (dSd!)
1 ~ Y
40
~
~
....
"-
....
'A,
3
Energy diagram fof the configuration d
8
40
30
!o
2p
lH
20
7
.
30
lO
~ ~ - - ~ - - - - - - - E
2
DqjB
APPENDIX
Calculation 01
(1 0Dq) and fJ lor
Oh Ni
ll
and T
d
COII
Comp exes
CALCULATION OF A ANO PFOR OCTAHEORAL
Ni
2
+ COMPLEXES
The data in Table 10--6 for the Ni[(CH
3
}zSO]6(Cl0
4
)2 complex will be employed
to illustrate the calculation of A, [3, and the frequency for the 3A
29
--+ 3Tg(F)
bando The value for A, or lODq, is obtained directly from the lowest energy
transition, 3A
29
--+ 3T
29
, which occurs at 7728 cm-
l
Equation (10--12),
[6Dqp - 16(Dqf] + [ -6Dq - p]E + E
2
= O,
is employed to calculate the experimental 3 P energy value, that is, p of equation
(10--12). The quantity pis equal to lSB for nickel(lI), where Bis a Racah parameter.
Racah parameters indicate the magnitude ofthe interelectronic repulsion between
various levels in the gaseous ion. The quantity B is a constant that enables one
to express the energy difference between the levels of highest spin multiplicity in
terms of some integer, n, times B; that is, nB. Both n and B vary for different
ions; in the case of Ni
2
+, the energy difference between 3F and 3p is lSB. The
same term adjusted for the complex is 1SB'. To use equation (10--12) it is necessary
to employ the energy values for the 3Tg(P) state. This is the energy observed
for the 3Tg(P) transition (24,038 cm - ) plus the energy of the 3 A
29
level, because
E observed for transition (24,038 cm - ) = energy of 3 T g(P) - energy of 3 A 2g
so
energy of 3T/P) = E for transition + E of 3 A
29
Thus, combining this with equation (10--11) (E of 3A
2g
= -12Dq ; note lhat
Dq = 7728/ 10 773), we obtain
E of 3Tg(P) = 24,038 cm - - 12Dq = 14,762 cm-
The value of E = 14,762 cm - is employed in equation (10--12) along with
Dq = 773 to yield a value
p = 13,818 cm- = 1SB' 735
736 Appendlx E Calculalion 01 L1 (10Dq) and fJ lar Oh Ni " and T
d
Ca" Complexes
The gaseous ion Ee P) vaJue for Ni 2+ is 15B = 15,840 cm -1 and {3 is [equation
(10-14) or (10-13)]:
13,818 15B'
{3 = 15840 = 15B = 0.872
,
or
po = 15,840 - 13,818 x 100 = 12.8 o;;
15,840 o
To calculate the energies for the 3T
I 9
(F) and 3T
I9
(P) states, the values p = 13,818
cm -1 and Dq = 773 cm - 1 are substituted into equation (10-12) and the equation
is solved for E. Two roots, E = 14,762 cm - 1 and E = 3,694 cm - 1, are obtained.
Since the transition is 3 A
29
--> 3T
I 9
(F) or 3T
I9
(P), the absorption bands will
correspond to the differences
and
or
[ 3 A
2g
--> 3T g( F)] = 3,694 - [ -12(773)] = 12,970 cm - 1
and
[3A
2g
--> 3T
I9
(P)] = 14,762 - [ -12(773)] = 24,038 cm - 1
The agreement of the calculated and experimental values for the 12,970 cm -
band supports the {3 and Dq values reported aboye.
CALCULATION OF A ANO FOR T
d
Co2+ COMPLEXES
In a field of tetrahedral symmetry, the 4 F ground state of Co2+ is split ioto 4 A
2
,
4T
z
, and 4T(F). The transitions 4A
2
--> 4T
2
, 4Az --> 4T
1
(F), and 4Az --> 4T
1
(P) are
designated as v, V
2
, and V
3
, respectively. The following relationships are used
to calculate and {3:
(E-1)
= + 7.5B' - Q (E-2) V
z
V
3
= + 7.5B' + Q (E-3)
.Q = [(O.M - 15B'? + (E-4)
where B' is the effective value of the Racah interelectronic repulsion term in the
complexo To repeat equations (10-14) and (10-13),
{3 =
Brree ion
Appendlx E Cal culatian al l!. (10Dq) and {3 lar Oh Ni" and T
d
Ca" Camplexes 737
or
B B'
{J o = fre e ion - complex X 100
(E- S)
Bfr ee ion .
To demonstrate the calculation, let us consider the spectrum of tetrahedral
Co(TMG)42+ (where TMG is tetramethylguanidine).(1) The band assigned to v
3
is a doublet with maxima at 530 m. (18,867 cm -1), ; = 204, and 590 m. (16,949
cm-
I
), ; = 269. The near infrared spectrum yields V
2
as a triplet: 1204 m. (8306
cm-
I
) , ; = 91.5 ; 1320 m. (7576 cm-
I
), ; = 85.0; and 1540 m. (6494 cm-
I
),
; = 23.5. The TI states are split by spin-orbit coupling to the following extent(2) :
- 9/
4
X, +%X, and +15/
4
X. The energy of 4Az --> 4T,(F) is obtained by averaging
the three peaks for the V
2
band, using the aboye weighting factors.
(6494) = 14,612
(7576) = 11,364
(8306) = 31,148
30
Totals 57,124
4
The average energy of V
2
is thus 57,124 -7- 3/4 = 7617 cm-
l
The energy of the
transition from 4Az to 4T, (P) (i.e., v
3
) is obtained by averaging the two peaks to
produce 17,908 cm -l. The series of equations (E- l) to (E-4) are now solved to
obtain and (J. Adding equations (E-2) and (E-3) produces:
= V
z
+ V
3
- 15B'
3
and substituting V
z
and for Co(TMG)/ + produces = 5(1702 cm -1 - B' ). v
3
Subtracting equation (E-2) from (E-3) produces
Squaring both sides of equation (E-4) and rearranging produces
(E- 6)
Substituting Q= 5146 cm-
I
and = 5(l702 cm-
I
- B') into equation (E-6)
yields an equation that can be sol ved from B'. One root is 821 cm - 1, and the
other root is negative. When the positive root is substituted into = 5(1702
cm -1 - B'), the value of = 4405 cm -1 is obtained ; f3 is evaluated from equation
(E-S).
738 Appendlx E Calculat ion 01 (10Dq) and f3 lor Oh Ni" and T
d
Co" Complexes
REFERENCES 1. R. S. Drago and R. L. Longhi , Inorg. Chem., 4, 11 (1965).
2. R. Stahl -Broda and W. Low, Phys. Rev., 1J3, 775 (1959).
CITED
APPENDIX
Conversion of
Chemical Shift F
Data
The chemical shifts, (j (in ppm), relative to (j = Ofor tetramethylsilane for sorne
compounds often employed as external standards are: cyc1ohexane, -1.6;
dioxane, -3.8; H
2
0 , -5.2; CH
2
Cl
2
, -5.8; C
6
H
6
, -6.9; CHCl
3
, -7.7; and
H
2
S0
4
(sp. gr. 1.857), -11.6 ppm. (The larger negative value indicates less
shielding.) These shifts are obtained on the pure liquids re1ative to an external
standard. As a result, they can be employed to convert data and alIow comparison
of results between the various materials as external standards. To convert (j
obtained toward C6H6 as a reference to Si(CH
3
)4 (external standard), subtract
6.9 ppm from the C6H6 value. One should check to be sure that the sign convention
for Ll is that described for protons (crs - cr R)'
The conversion of results obtained relative to an external standard to an
internal standard is not quite as straightforward. If chemical shift values at infinite
dilution in CCl" are converted to Si(CH
3
)4 as a reference by using the aboye
data, T values do not result. This procedure converts the data to the reference
pure Si(CH3)4 ' The difference in (j for Si(CH 3)4 in the pure liquid and at infinite
dilution in CCl
4
is about 0.4 ppm. The pure liquid is more shie1ded.
For fiuorine shifts, F 2 = O ppm is often taken as the standard. Shifts, in
ppm, for other liquids relative to F 2 are SF6,375.6; CFCl
3
, 414.3; CF3Cl, 454.2;
CF4,491.0; CF
3
COOH, 507.6; C
6
H
s
F, 543.2; SiF4,598.9; and HF,625, where
the positive value indicates a more highly shielded fiuorine.
Many phosphorus chemical shifts have been reported relative to 85 % H
3
PO4
as the standard.
739
APPENDIX
G
Sol ution of the
Secular Determinant for
the MR Coupling of
the AB Spin System
To evaluate these matrix elements for a second-order, AB system in Section 7-20
we need to know how the lA' lB operator works. This problem is simplified by
defining the so-called raising and lowering operators. We shall have occasion to
use these operators in other problems. Remember that
(G-1)
but that we can only find simultaneously P and the component in one direction.
The raising and lowering operators, 1+ and 1_, are defined by taking linear
com binations ofx and 1y such that:
1+=lx+ i y (G- 2)
1_=lx-iy (G-3)
These operators have the property that when they operate on a wave function
11, mI ) (i.e., one defined by quantum numbers 1 and mI) we get:
1 + 11,m{) = [I(l +1) - m{(m{ + 1)J1 f211,m[ +1)
1 _11,m[ ) = [(J(l +1) - m[(m[ - 1)]
1f2
11,m[ - 1)
Then we find that these operators work on la) and 1[3) as follows :
1+ la) = O (we cannot raise a +1/
2
spin by 1 when 1 = 1/
2
)
L la) = 1[3)
1+1[3)=la)
1_1 [3) = O (a - 1/
2
spin cannot be lowered by 1 when 1 = 1/
2
)
The lA' 1B operator for a two-spin AB system is given by:
lA . lB = IZA ' 1 ZB +1XA .]XB +YA' 1 YB
~ ~ ~ ~ ~ ~
740 = IZA 'l
ZB
+( /2)(1 +A1_B +1_
A
1+B) (G-4)
Appendlx G Solution 01 the Secular Determinan! lor the NMR Coupling 01 the AB Spin System 741
Equation (8- 18) in terms of the raising and lowering operators can be derived
by solving equations (8-16) and (8-17) for Ix and l
y
and substituting this result
into the equation for lA l
s
in terms of X, Y, and Z components. In operating
on the basis set (etet, etc.) with the lA 1s operator, the lA spin operator acts only
on the A nuc1eus (the first spin function Iisted) and the 1s operator acts only on
the B nuc1eus (the second one listed). Accordingly,
while
The general Hamiltonian for the coupled AB system, equation (8-15), becomes
equation (G-5) when expressed in terms of the raising and lowering operators.
H AS = - v
o
(1 - a
A
)l
ZA
- v
o
(1 - a
s
)l
zs
+ J AS IZA l
zs
+ e/
2
)JASO +) -S + 1_)+S) (G-5)
Now we return to the evaluation of the matrix elements in the secular
determinant given earlier. To evaluate <eta I H laa), we need to evaluate the effect
of H on l aa) and then simply multiply by <aa l . Thus, we shall proceed by first
evaluating H leta), H letf3 ), H If3a ), and H I1313 ).
Hlaa) = [ - vo(l - aAle/2 ) - vo(l - a
S
W/2 ) + e/4)J] laa)
The e/4)J arises from IZA 1zs laa) for both 1+ Al _s laa) and 1_Al +s laa) equal
zero, since 1+Aleta) = Oand J+s laa) = O. Rearranging the aboye expression for
Hlaa ), we have
= [ - vo(aA - as) - J} f3a ) + Jlaf3 )
H I1313) = [ - vo(1 - aA) ( - D-vo(l - as) ( - D+ J} 1313 )
= [vo( 1 - aA - as) + J} 1313)
With these quantities evaluated, it is a simple matter to multiply them by
aa, af3, etc. , and thus to evaluate all the matrix elements in the secular determinant.
742 Appendix G Solution 01 the Secular Determinant lor the NMR Coupling 01 the AB Spin System
Forexample, <fJIXI fIIXfJ) = O+ 1/2J . The results for all the matrixelements are
contained in Table G-l. The result offIIXIX) is seen to yield IIXIX) back again,
so this wavefunction is aneigenfunctionoftheHamiltonian,asis I fJfJ). However,
IfJIX ) and IIXfJ) a re not eigenfunctions. Accordingly, we find off-diagonal values
ofe/2)J connecting IXfJ and fJIX. The determinant is block diagonalized, with two
frequencies given as:
(G-6)
(G-7)
TheenergiesofE
2
and E3 are obtained by solving the2 x 2 block.Thissolution
can be simplified by making a few definitions. The definitions to be made are
notobviousa priori choices.Theycomewithexperiencein solvingdeterminantal
equationsand trying to relate the results to observed spectra. Wewill substitute:
TABLE G-l . Evaluation 01 the Matrix Elements lor the Coupled AS System
aa
ap
prx
pp
{J'X flfi
[ a
A
aBJ J E
Vo - I + 2 + 2 + 4" - h
O O O
/
/
1 J E J
O
+ 2: vO(aA - as) - 4" - h
2
O
J I J E
O
2
- 2: VO(O"A - as) - 4" - h
O
O O O \{1- a; - ] + _
and
J . e
2: = eSITI 2
where e = e /2)(J
2
+ The geometrical relation ofthese defined quantities
is shown in Fig. G-l. With these definitions the 2 x 2 block of the secular
determinant becomes :
2C J
- ecos2e -
1
- J -
E
- e si n 2e
4 h
28
=0
e sin 2e ecos2e -
1 E
- J - -
4 h
Appendix G Solution 01 the Secular determinant lor the NMR Coupling 01 the AS Spin System 743
The solutions to this determinant are
1 E
2
-=--J-C (G-8)
h 4
E3 1
-=-- J+C (G-9)
h 4
To get the wave functions for these two states, we substitute the energies one at
a time into the determinant given above. The matrix corresponding to this
determinant (this matrix has the same form as the determinant) is multiplied by
a column matrix (vector) of the coefficients. The product is zero. Expa nsion
produces the two resulting, linearly dependent equations, which can be solved
for C
l
and C
2
when the normalization requirement is imposed. In general, this
is done for each energy. The procedure is similar to that used in Chapter 3 when
Hckel theory was discussed. The wave' functions 1/12 and 1/1
3
so obtained are
Jisted below along wi th 1/1 1 and 1/1 4'
I/Il=letet)
1/12 = cos el etP)- sin el pet)
1/1
3
= sin elaP)+ cos elPet)
1/14=IPP)
(G-lO)
(G-ll)
(G- 12)
(G-13)
/
Index
Al symmetry, 169
AB molecule spectrum, relative magni-
tudes ofJ and delta, 263-264
AB spin system, nuclear magnetic reso-
nance coupling, solution of secular
determinant, 740-743
Absorption band, effects giving rise to,
154--156
Activation enthalpy , nuclear magnetic res-
onance, 290-295
Adi abatic electron affinity , M- , 666
Allyl, interrnediate neglect of differential
overlap, 80-81
Allyl radical
pi system, 69
wave function, 76-78
Altemately double bonded hydrocarbon,
molecular orbital theory, 83-84
Ammonia, ultraviolet photoelectron spec-
troscopy, 673
Angular momentum, 213
Angular overlap model, 452--458
Anharmonic vibration, 149-150
Ani on, ambidentate, 198
Anionization, secondary ion mass spec-
tromet ry , 678
Anisotropy
g value, 380-383
hyperfine coupling, 383-390
A.O. basis set, nitrite ion, 61
Appearance potential, 655, 664--665
Asymmetric stretch, 154
Asymmetric top, 190-191
Asymmetry parameter, 269, 606
Atom, equivalent, 12-13
Atom r, q;, electron density, 72-73
Atomic force microscopy, 680-681
Atomic transi tion , 92-95
Auger electron spectroscopy, 679
Band assignment, 156-160
criteria, 118-119
Base-iodine addition compound, molecular
orbital, 134
Base-iodine solution, spectra, 133
Basis set, 36
Bending vibration , 92
Benzene, molecular orbital, 116
Beta calculation, OhNi(JI) complex, 438-
443
Bimetallic system, nuclear magnetic reso-
nance, 543-552
Bloch equation, 218-220
Block diagonalized, 34
Blue shift, 118-119
Boltzmann const ant, 95
Bond di ssoc iation energy , force constant,
152
Bond order, 73, 74
Bond strength , frequency shift, 194--202
Bonding parameter, 450-458
tetragonal complex, 450--452
Born-Oppenheimer approximation, 94
Bragg's law, 690
Bravais lattice, 703
DC magnetic resonance, 319-323
Cl>'point group, character table , 114
Cambridge Crystallographic Database,
689
Cambridge Structural Database , 710
Carbon dioxide, fundamental vibration
modes, 155
Carbonyl compound, 131
Cartesian basis set, 36
Cartesian coordinate system, 30--43
Cationization, secondary ion mass spec-
trometry, 678
Character table, 35-36, 41--43
C
2v
point group, 114
double group, 724--726
symmetry group, 712-723
Charge-transfer spectrum, solvent polarity,
135-137
Charge-transfer transition, 127-128
Chemical exchange, spectral line width,
95-98
Chemical ionization, 654
Chemical shift
data conversion, 739
fluorine, 235
interpretation, 232-240, 241-243
local effects, 232-238
measurement, 229-232
remote effects, 238-240
Chromophore, heme, 171
Circular dichroism, 137- 141
C10sed shell system
antishielding, 615
shielding, 615-616
CO
2
molecule
symmetric stretching vibrat ion,
polarizability change, 165
vibrations, 155
Cobalt-substituted carbonic anhydrase, 543
Cobalt(l!)
diastereoisomerism, 535-537
diastereotopism, 535-537
Co(Meacacen), electron paramagnetic reso-
nance spectrum, 563
Complete neglect of differential over lap
(e DO) , 80
Concentration, determination, 99-103
Configuration interaction, 117-118
Conjugate, 22
Constant-acid, constant-base frequency
shift-enthalpy relati ons , 195
Contact shift , 507-508
factoring, 512-514
spin density, 514--518
Contrast agent, nuclear magnetic reso-
nance, 530-531
Coordinate, normal, 93
Coordinate system, NH) location , 63
Coordination
donor molecule spectra change, 196-198
spectra and symmetry changes , 198-
202
Copper (11) complex, 590
Coupling, quantum mechanical descrip-
tion , 259-263
Coupling combination band, symmetry,
176
Coupling constant, determining signs,
268-269 J
Crystal, 695-698
classes, 701
growth, 695
745
746 Index
Crystal (colltillued)
liquid-diffusion vessel, 695
vapor diffusion, 695
mounting, 697-698
selection, 696-697
size, 696
X-ray absorption, 696-697
Crystal field, 416--432
Cu,Co, superoxide dismutase, 545
Cu,Co,SOD derivative, IH mur spectrum,
546
Curie relaxation, equations, 523-524
Curie temperature, 471
Cytochrome C peroxidase, X-band spec-
trum, 585
d orbital, 126-127
d orbital energy, ligand, 416--419
symmetry, 419--427
d orbital energy level, distortion, 443--447
di, 578- 579
cP, 579
d
3
, 579-581
er, 581
d
5
, tetragonal field, 585
' high spin, 583-586, 590
d
5
low spin, 581-583
cf ,590-591
Decomposition formula, representation,
44--46
Degenerate representation, 38--40
Delta, formal charge, 73
Depolarization ratio, 169
Depolarized line, 169
Diamagnetic tenn, 234
Diamagnetism, 471--473
Diastereoisomerism, 535
cobalt(Il), 535-537
Diastereotopism, cobalt(l!), 535-537
Diatomic molecule , 190
electronic energy level, 109--110
energy state, 94
Morse energy curve, 109-110
vibrational energy level, 1\O
Differential overlap, intermediate neglect,
78-83
Diffraction pattem, 693
Diffractometer, 697, 698
Dimeric complex, IH mnr, 544-545
Dimeric copper adenine complex, 592
1,2-Dimethyl imidazole, Mssbauer spec-
troscopy, 635
Dipolar hyperfine coupling, electrons in d
orbitals, 575
Dipolar relaxation, equations, 522-523
Dipole moment, 13-14
Direct dipolar coupling, 340-341
Direct lattice, monoclinic cell, 690-692
Direct product, 46
Distance, polarizability, 167
Distortion, d orbital energy level, 443--447
Doppler energy, 627
Double group, 427--429
character table, 724-726
Double resonance, nuclear quadrupole res-
Double resonance electron paramagneti c
resonance, 594
Double resonance experiment, 267- 268
t?Qq, nuclear quadrupole resonance spec-
troscopy, 616-617
crystal lattice effects, 617
data interpretation, 616-617
Effective spin Hamiltonian, 363
Eigenvalue, 53, 81-82
Eigenvector, 81-82
Electric field gradient, 605
molecular structure, 612-616
Electric quadrupole, intensity, 127
Electromagnetic radiation, plane-polari zed ,
91
Electron correlation, 80
Electron density, 72-73
atom r, q ~ 72-73
Electron-electron interaction, 409--413
term symbols, 409-410
Electron ionization, 654
Electron loss, secondary ion mass spec-
trometry, 678
Electron paramagnetic resonance (epr)
spectroscopy, 360-399
anisotropic effects, 380-399
applications, 397-399
Co(Meacacen) , 563
line width, 394-396
metal cluster, 591-594
principies, 360-363
spectrum presentation, 368-370
transition metal ion complexes, 559-
594
first-row survey, 578-591
triplet state, 390-392
Electron relaxation, spin-orbit coupling,
578
Electron spin, 503-507
Electron spin state, zero-field splitting,
573
Electronic absorption spectroscopy, 109-
143
nomenclature, 113-116
Electronic energy level, diatomic mole-
cule, 109--110
Electronic relaxation time, 527-530
Electronic spectrum
energy curve, 111- 112
oxo-bridged dinuclear iron center, 458-
459
structural evidence, 447--450
Electronic state, change, 92
Electronic transition , intensity, 120-130
Electrons in d orbitals, dipolar hyperfine
coupling, 575
ENDOR experiment, 594
Energy curve, electronic spectrum, 111-
112
Energy state, diatomic molecule , 94
Equivalent atom, 12
Et.N+, ethyl group disorder, 710
Ethylmethyl sulfide, Mssbauer spectros-
Ethylpyridine , mass spectra of 3 isomers ,
658
Eulerian cradle, 698- 699
Expectation value, 53, 504-507
Extended X-ray absorption fine structure,
681
Far infrared vibrational frequency correla-
tion chart, 188-189
Fast atom bombardment , 654
Fast chemical reaction, spectrum effect,
257-258
Fast nuclear relaxation, two-dimensional
spectrum, 532-533
57Fe
magnetic splitting, 634
non-cubic electronic environment, 632
quadrupole splitting, 634
Fe,S, ferrodoxin, IH nrnr spectrum, 546-
548
oxidized, 547
reduced, 547
Fe3(CO)12
Mssbauer speclroscopy, 640
structure, 640
FeFe(CN)6, Mssbauer spectroscopy, 629
Fermi contact contribution, 576
Fermi contact coupling, 501
Fermi resonance, 155-156
symmetry, 176
Ferrimyoglobin, X-band spectrum, 585
Field desorption, 654
glutamic acid, 663
Field gradient
pyridine, 619
semiempirical approach, 615
Field gradient q, 269
Field gradient tensor, principal axis sys-
tem, 605-606
Field ionization, 654
glutamic acid, 663
Field ionization technique, 662-663
Fine splitting, 572
Fingerprinting, 106, 130-132, 184-186
carbonyl compound, 131
inorganic system, 132
mass spectrometry, 657-659
saturated molecule, 130-131
First overtone, 151
Fluorine, chemical shift, 235
Force constant, 149, 151-153
bond dissociation energy, 152
Force constant matrix, comp1iance con-
stants, 160
Formal charge, 73, 75-78
delta, 73
Formaldehyde
molecule shapes, 114
spectrum, 123-124
Fourier transform epr , 594
Fourier transform ion cyclotron resonance
technique, 665-667
Fourier transform nrnr, 309-319
experiment optimization, 314-315
multipulse methods, 328- 340
onance spectroscopy, 620-622 copy, 635 other nuclei, 323-325
principies, 309-314
relaxalion, 326--328
selective excitation and suppression,
333-334
sensitivity-enhancement methods, 331-
332
spectral density, 326--328
T, measurement, 315-316
Franck-Condon factor, 672
Franck-Condon principie, 111
Free induction decay, 621
Free ion, spin-orbit coupling, 413-416
Free ion electronic state, 409-416
Frequency shift, bond strength, 194-202
Fundamental frequency, 151
Fundamental vibration frequency, 150
g --> u, 123
g value, anisotropy, 380-383
Gamma ray, 626, 627
Gas, spectra, 186--192
Geometric transformation, 30-34
Glide plane, 11
Glutamic acid, 663
Goniometer, 698
Goniometer head, 697
Gross atomic population, 75
Group H order, 20
Group multiplication table, 19-25
element classes, 23-25
propertics, ,19-22
Group theory, 18-35
element rules, 19
generation ofsymmetry combinations,
18
zero quantum mechanical integrals, 18
Group vibration, 160-162
limitations, 161
'H oror spectrum
CU2C02S0D derivative, 546
Fe2S2 ferrodoxin, 547
H
2
, equivalent orientations , 1
H20 molecule, internal coordinates, 157
Hahn spin-echo experiment, 328
Harmonic oscillator approximation, 156
Harmonic vibration, 149-150
Hckel procedure, 68-72
extended, 74-78
molecular orbital, 68-72
Heme, chromophore
ultraviolet (Soret), 171
visible, 171
Heme Raman spectmm, 170-171
Hemin-imidazole-cyanide, 538-539
Hemoglobin, schematic formula, 582
High melting solid, vapor over, 663
High resolution electron energy 10ss spec-
troscopy, 679-680
High resolution infrared spectmm,
Mo(CO)5Br, 201
High resolution nmr, solids, 347-348
High spin-low spin equilibrium, magne-
tism, 489-490
Higher-state mixing, 117
Hooke's law constant, 149
Hybridization of ligand, 577
Hydrocarbon system, pi orbital, 68
Hydrogen atom, 363-368
Hydrogen-bonded phenol , infrared spectra,
194
Hydrogen bonding solvent, blue shift,
119
Hyperfine coupling, 571-576
anisotropy, 383-390
Hyperfine coupling constant, isotropic sys-
tem, 374-379
Hyperfine splitting, nitroxide, 399
Hypsochromic shift, 118-119
i, properties, 224-225
Identity, 2
Identity element, 19
Infrared group frequency range, 186--187
Infrared line, symmetry, 172- 176
Infrared spectra, 194
Infrared spectroscopy
inorganic structure, 192-194
procedures , 179-184
Inorganic anion, characteristic absorption
maxima, 132
Inorganic Crystal Stmcture Data Base, 710
Inorganic material, infrared group frequen-
cy range, 186--187
Inorganic structure, 192-194
Inorganic system, fingerprinting, 132
Integral zero, 121
Integrated intensity, 120
Intensity
electric quadrupole, 127
magnetic dipole, 127
spin-orbit, 124-126
spin-orbit coupling, 124-126
vibronic coupling, 124-126
Interaction force constant, 157
Interatomic ring current, 241
Intermediate neglect ofdifferential over-
lap, aHyl, 80-81
lntervalence electron transfer band, 459-
461
Inversion center , 2
lodine
molecular addition compound, 133-
135
spectra, 133
Ion pair, N-methylpyridinium iodide, 136
Ion pairing, 538
lonization, 650-682
Ionization efficiency curve, 664
lonization potential, 664-665
Iron(lI) complex
Mssbauer spectroscopy, 638
partial quadmpole splitting parameter,
644
Iron(lIl) compiex, Mssbauer spectros-
copy, 638
Iron (111) complex
spectmm, 584
splitting of energy levels, 584
lron porphyrin, spin delocalization, 539-
543
lron-sulfur compound, center shift, 641
Index 747
Irreducible representation, 34-35
wave function, 59-60
Isomer shift, Mssbauer spectroscopy,
630-631
Isomolar solution, Job' s method, 106
Isosbestic point, 103-106
Isotope, mass spectnlm, 660-662
Isotropic system, hyperfine coupling con-
stant, 374-379
Jahn-Teller effect, 429-430
Job's method, isomolar solution, 106
Kramers' doublet, 559
rhombic symmetry, 586
Kramers' rule, 559
Lanthanides, 510-512
Laser desorption, 654
Lattice plane
Miller indices, 690-691
direct, 691
reflection, 691
Lattice vibration, 183
Ligand, d orbital energy, 416-419
symmetry, 419-427
Ligand hybridization, 577
Ligand hyperfine coupling, 576--578
Line width
chemical exchange processes, 561
electron paramagnetic resonance spec-
troscopy, 394-396
Linear combination of atomic orbitals-
molecular orbital method, 54
Linear molecule
bending mode, 154
normal modes of vibration, 153
rotational mode, 154
Linear polyalOmic molecule, 190
Local symmetry, 124
Longitudinal relaxation, 216
Low energy electron diffraction, 678-679
M-, adiabatic electron affinity, 666
Magnetic behavior , types, 471-476
Magnetic coupling, metal ion cluster,
430-432
Magnetic dipole, intensity, 127
Magnetic field
magnet in, 213-214
nuclear quadmpole resonance spectros-
copy, 611-612
T state, 570
Magnetic splitting, 57Fe, 634
Magnetic susceptibility, measurement ,
490-491
Magnetism, 469-494
high spin-Iow spin equilibrium, 489-
490
intramolecular effects,4 86-489
susceptibility measurement applications,
483-486
Magnetization vector, 215-216
Magnetocircular dichroi sm, 141-143
Marginal oscillator, peak, 609
Mass spectrometer , 653
748 Index
Mass spectrometric shift rule, 660
Mass spectrometry, 650-665
fmgerprint, 657-659
instrument operation, 650-665
interpretation, 659-660
isotope, 660-662
molecule high energy electron combina-
tion, 655-657
presentation, 650-665
Mattix, 27-30
Matrix formulation, molecular orbital
calculation, 56--57
Mattix multiplication, 27-28
cis MB.A2
coordinates, 643
geometries, 643
trans MB.A2
coordinates, 643
geometries, 643
Metal ion cluster
electron paramagnetic resonance spec-
trum, 591-594
magnetic coupling, 430-432
l-Methyl imidazole, Mbssbauer spectros-
copy, 635
N-Methylpyridinium iodide, ion pair, 136
Microstate configuration, 409
Microwave spectroscopy, 177-179
Miller indices, lattice plane, 690-691
direct, 691
Mirror plane, 4--5
Mo(CO)sBr, high resolution infrared spec-
trum, 20I
Molar absorptivit y, 118-119
Molecular addition compound, iodine ,
133-135
Molecular orbital
base-iodine addition compound, 134
benzene, I16
calculations, 68-72
Hckel procedure, 68-72
projecting, 60-68
Molecular orbital calculation, matrix
forrnulation, 56--57
Molecular orbital theory, 52-85
altemately double bonded hydrocarbon,
83-84
Molecular structure
electtic field gradient, 612-616
shift reagent determination, 550
Molecular transition, 92-95
Molecular vibration
radiation absorption, 150-15I
synunetry, 172-179
Molecular weight deterrnination, 662-
663
Molecule
asymmetric, 13
dissymmetric, 13
structures of exci ted states, 137
Monoclinic cel! lattice, 690-692
Morse energy curve, diatomic molecule,
109-110
Morse potenti al, 109
Mssbauer emission spectroscopy, 635
Mssbauer isotope, 637
Mssbauer spectroscopy, 626--645
I,2-dimethyl imidazole, 635
ethylmethyl sulfide, 635
Fe,(CO)'2, 640
FeFe(CN)6' 629
iron(Il) complex, 638
iron(lIl) complex, 638
isomer shift, 630--631
I-methyl imidazole, 635
non-cubic electronic environment , 632
piperidine, 635
principies, 626--629
pytidine, 635
quadrupole interaction, 631-633
3N-6(5) rule, 153-154
14N quadrupole transition, pyridine, 619
Naphthalene, 707
atomic coordinates, 708
Neighbor anisotropy, 238-239
Nel temperature, 471
Net atomic population, 74
Neutron diffraction, 70I
NH) location, coordinate system, 63
Nickel, planar-tetrahedral equilibrium,
534--535
Nitrite ion
A.O. basis set , 61
pi-molecular orbital, 63
Nitrogen, ultraviolet photoelectron spec-
troscopy, 672
Nitroxide, hyperfine splitting, 399
NO, photoelectron spectrum, 676
NOj, vibrational mode symmetry
C2. structure , 198
correlation chart, 198
C
s
struct ure, 198
Non-diagonal representation, 36--40
Non-equivalent proton, 246
Non-linear polyatomic molecule, 190-192
Nonlinear molecule
bending mode, 154
normal modes of vibraton, 153
rotational mode, 154
Normal coordinate, 93
Normal coordinate analysis, 156--160
Normal mode, 92
Normal vibraton, 92
NSF" vibration, fundamental frequencies,
193
Nuclear hyperfine splitting, 363-379
more than one nucleus, 370-374
Nuclear magnetic resonance (nmr)
activation enthalpy, 290-295
bimetallic system, 543-552
contrast agent, 530-531
f1u xional behavior , 300-305
intramolecular rearrangements, 300-305
liquid crystal solvent studies, 342-347
paramagnetic substances in solution,
500-552
quadrupolar nucleus, 319
rate constant, 290-295
reacti on order determination, 295-297
relaxation, 227-243
solid studies , 341-342
thermodynamic data evaluation, 290-
291
NMR coupling, AB spin system, solution
of secular determinant, 740-743
NMR kinetics, 201- 309
NMR spectroscopy, 211-270
quantum mechanics, 224--227
second-order systems, 265-266
slow passage experiment, 220-224
transi tion, 217-218
Nucl ear Overhauser effect , 306--309, 531-
532
Nuclear quadrupole interaction, 392-394
Nuclear quadrupole moment, 605
Nuclear quadrupole resonance (nqr) spec-
troscopy, 604--622
applications, 616--620
double resonance, 620-622
e
2
Qq, 616--617
crystal lattice effects, 617
data interpretation, 616--617
magnetic field, 611-612
structural inforrnation, 618-620
Nuclear relaxation, paramagnetic system,
519-524
Nuclear spin quantum number, 626
O-S-O bending mode, 154
Octahedral complex, vibration, 126
Octahedral iron (lll) complex
spectrum, 584
splitt ing ofenergy levels, 584
Octahedral symmetry, deviations, 582
Oh field
electronic spectra survey, 433-438
Tanabe and Sugano diagram, 732- 734
OhNi(lI) complex
beta calculation, 438-443, 735-737
Dq calculation, 438-443, 735-737
One electron molecular orbital, 54
Operator, 52- 56
OPF
3
, vibration, fundamental frequencies,
193
Optical activit y, 13
Optical rotary dispersion, 137-141
Orbital, nitrite ion, 63
Order of group h, 20
Organic material, infrared group frequency
range , 186--187
Orgel diagram, 427
Oscillator strength, 120
Overhauser effect, 306--309
Overlap popul at ion, 74--75
Oxo-bridged dinuclear iron center,
electronic spectrum, 458-459
Oxygen
ultraviolet photoelectron spectroscopy,
674
vertical ionization data, 675
Oxyhemerythrin, resonance Raman analy-
sis, 171
P-branch, 191
P orbital, 126--127
Index 749
P
AB
, bond order, 73-74
Parallel band, 190
Paramagnetic compound, properties, 500--
503
Paramagnetic Mssbauer spectrum, 633-
635
Paramagnetic substances in solution, nmr,
500--552
Paramagnetic system, nuclear relaxation,
519--524
Paramagnetic term, 233
Paramagnetism, simple system, 473-476
Partial quadrupole splitting parameter,
iron(lI), 644
Peak assignment, T" 317-319
Perturbation theory, 57-59
Phenol, infrared spectra, 194
Phonon mode, 183
Photoacoustic Fourier transform spectros-
copy, 182
Photoelectron spectroscopy, 667
Photoemission, 669
Pi orbital, hydrocarbon system, 68
Pi system, allyl radical, 69
Piperidine, Mssbauer spectroscopy, 635
Planar-tetrahedral equilibrium, nickel,
534-535
Planck's constant , 150
Plasma desorption, 654
Point group, 8- 11
symmetry element, 9
Polarizability
distance, 167
vibration, 165-167
Polarized absorption spectra, 128-130
Polarized line, 169
Polyatomic mOlecule, vibration, 153-162
Product, 19
Product ground state wave function, 84-
85
Projection operator, 60
Protein Data Bank, 710
Protonation, 119
Pseudocontact shift, 508-510
factoring, 512- 514
Pyrene, 701-
Pyridine
field gradient, 619
Mssbauer spectroscopy, 635
'4N quadrupole transition, 619
Q-branch, 190, 191
Quadrupolar nucleus, nmr, 319
Quadrupole energy level
axiaIl y symmetric field, 607
spherical field, 607
Quadrupole interaction, Mssbauer spec-
troscopy, 631-633
Quadrupole moment nucleus, 269-270
Quadrupole splitting, 57Fe, 634
Quadrupole transi!ion, energies, 607-
611
Quantum mechani cs
nrnr spectroscopy, 224-227
symmetry, 59--68
Quasi-equilibrium theory, 660
R-branch, 191
Radiation
allowed transitions, 95
corresponding energies , 91-92
forbidden transitions, 95
nature, 90--91
selection rules, 95
wave numbers, 92
Radiation absorption, molecular vibration,
150--151
Raman line
depolarized, 168-169
polarized, 168-169
symmetry, 172-176
Raman spectroscopy, 162-171
inorganic structure, 192-194
procedures, 184
selection rules, 164--168
Rapid nuclear quadrupole relaxation, 269
Rate constant, nmr , 290--295
Reciprocal lattice , monoclinic cel!, 690--
692
Reciprocal space, 691-692
Reflectance technique, 181
Reflection, 691- 692
lattice plane, 691
Relaxat ion, 215-216
Fourier transform nmr, 326-328
nmr, 227-243
spectral line width, 95-98
Relaxometry, 524-527
Representation, 30--34, 43-44
decomposition formula, 44-46
degenerate , 38-40
irreducible, 34-35
non-diagonal, 36-40
Resonance Raman analysis,
oxyhemerythrin, 171
Resonance Raman spectroscopy, 170-- 171
Rhombic symmetry, Kramers' doublet,
586
Rot ating axis system, 214-215
Rotating frame, 214-215
Rotation axis, 2-4
dissymmetric, 13
improper , 5
proper, 2
Rotation-reflection axis, 5-7
Rotational line, Zeeman splitting, 179
Rotational Raman spectrum, 179
Rotational state, 94
S=1/2 system, orbitally non-degenerate
ground states, 565-569
Saturated mOlecule, fingerprinting, 130--
131
Scanning tunneling microscopy, 680--681
Scattering factor curve, 694
SCF-INDO, 78-83
Screw axis, 11, 703
Second-order spectra, 259
Second overtone, 151
Secondary ion mass spectrometry, 654,
677-678
aluminum target, 677
anionization, 678
cationization, 678
electron loss , 678
sputtering, 678
vs. mass number/ion charge, 677
Self-consistent field, 79
Shift reagent, 549- 552
Simple harmonic motion, 149
Single crystal study, polarized, 129-
130
Site symmetry, 183
S02, infrared spectrum, 154
Solvent , Z-values , 136
Solvent polarity, charge-transfer spectrum,
135-137
Space symmetry, II
Spectral density, Fourier transform nmr ,
326-328
Spectral line width
chemical exchange, 95- 98
relaxation, 95-98
Spectroscopy, 90--106
See a/so Electronic absorption spectros-
copy
Spherical top, 190--191
Spin delocalization, iron porphyrin, 539-
543
Spin density, contact shift , 514-518
Spin echo, 329- 331
Spin Hamiltoni an, 396-397, 573- 574
Spin-Iattice relaxation, 216
Spin-orbit coupling, 117, 48-3-486
electron relaxation, 578
free ion, 413-416
intensity, 124-J26
large, 569-571
T state, 571
Spin-polarization, 375
results, 576
Spin saturation labeling, 305-306
Spin-spin coupling
bond nature, 247-249
bond number, 247-249
scalar mechanisms, 249-251
structure determination, 252- 257
Spin-spin relaxation, 216
Spin-spin splitting, 243-270
spectrum effect, 243-246
Spin temperature, 621
Spin-tickling experiment, 267-268
Sputtering, secondary ion mass spec-
trometry, 678
Square matrix, 27
Square planar Schiff base ligand, 590
Stemheimer effecr, 615
Stokes line , 169
Stretching vibration, 92
Structure deterrnination, spin-spin cou-
pling, 252-257
Sublimation heat, 663
Sulfur dioxide, three fundamental vibra-
tions, 155
Superparamagnetism, 491-494
Superregenerative oscillator, peak, 608-
609
Surface science technique , 667-681
750 Index
Susceptibility measurement applications,
magnetism, 483--486
Symmetric stretch, 154
Symmetric stretching vibration, CO
2
molecule, polarizability change,
165
Symmetric top, 190-191
Symmetry
center, 2
coupling combination band, 176
definition, I
Fermi resonance, 176
infrared line, 172-176
plane of, 4--5
quantum mechanics, 59---68
Raman line, 172-176
X-ray crystallography, 701-710
molecular vs. crystallographic , 707
See a/so Space symmetry
Symmetry element, 2-7
equivalent , 12-13
point group, 9
Symmetry group, character table , 712- 723
Symmetry operation. 12
Symmetry species of state, 115
Synchrotron radiation, 701
T state
magnetic field, 570
spin-orbit coupling, 571
TI, peak assignment, 317-319
Tanabe and Sugano diagram, 426
Oh field, 732-734
T,Co" complex, ca\culation of delta(lODq)
and beta , 735-737
Tetragonal complex , bonding parameter,
450--452
pi, 450--452
sigma, 450--452
Tetragonal field, cf5
strong, 585
weak, 585
Thermal desorption, 654
Thermodynamic data evaluation, nmr,
290-291
Thiocarbonyl compound
carbonyl compound, 131
spectra, 131
Through-space dipolar coupling, 501
Total ioni zation unit, 652
Transition metal ion, 409--462
g-values, 564-570
Transition metal ion complexes, epr spec-
trum, 559-594
first-row survey, 578-591
Transition moment integral, 120-122
Transition probabilities, 225-227
Transmission infrared, 181
Transverse relaxation time . 216
Triplet state, epr spectroscopy, 390-
392
Two-dimensional nmr, 334-340
Two-dimensional spectrum, fast nuclear
relaxation, 532-533
u->g,123
Ultraviolet photoelectron spectroscopy,
671-677
ammonia, 673
nitrogen, 672
oxygen, 674
Ultraviolet radiation, 94
Unit matrix, 27
Unpaired electron density, 375
Van Vleck's equation, 476--483
Variation energy, 55
Variational principie, 55
Vector, 25-26
Vibration, 92-94
bending, 92
harmonic, 149- 150
nomenclature, 172
normal, 92
normal modes for common structures ,
727-731
NSF), fundamental frequencies, 193
octahedral complex, 126
OPF), fundamental frequencies, 193
polarizability, 165-- 167
polyatomic molecule, 153-162
stretching, 92
symmetric . 165
See also Specific type
Vibrational energy level, diatomic mole-
cule, 110
Vibrational energy state, 92
Vibrational mode symmetry, NO)'
C
2v
structure, 198
correlation chart, 198
C, structure, 198
Vibronic coupling, intensity, 124--126
Wave function, 52
allyl radical, 76-78
irreducible representation, 59-{j0
mixing p-character, 127
properties derived from, 72-74
symmetrized, 84-85
X-ray
atom and structure scattering, 693-695
diffraction, 690
X-ray absorption near-edge structure,
681
X-ray crystallography , 689-710
area detectors. 700-70I
avoiding crystallographic mistakes, 705-
707
computers, 700
crystallographic data, 710
diffraction equipment , 698
diffract ometer data collecti on, 698-
700
future developments. 700-701
methodology, 698- 700
principies, 690-695
quality assessment, 707-709
reflection conditions , 704
space-group determination, 704--705
space groups, 702-703
symmetry, 701-710
molecular vs. crystaJlographic, 707
symmetry elements, 704
vs. neutron diffraction , 701
X-ray photoelectron spectroscopy, 668-
671
Z-axis compression, in D
4h
, 564
Zeeman Hamiitonian, 565
Zeeman splitting, rotational line , 179
Zero-field splitting, 391, 571-576
anisotropic, 573
electron spin state, 573
SELECTED CONSTANTS*
V,.!!:a
Symbol Quantlly cgs Unlts SI Unlts
k Boltzmann constant 1.3807 x 10-
16
erg K - J 1.3807 X 10-
23
J K -
I
h Planck constant 6.6262 x 10 -
27
erg S 6 fi262 X 10-34 J S
e speed of Iight in vacuum 2.9979 x 10
10
cm S-I 2.9979 x lOs m S - I
N Avogadro constant 6.0220 x 10
23
mol- 1 6.0220 x 1O
13
mol - 1
1.6022 X 10-
20
emu
e elementary charge or 1.6022 x 10- 19 (' (sA)
4.8032 x lO - lO esu
amu atomic mass unit 1.6606 x 10- 24 g 1.6606 x 10- 27 kg
P(IIB) Bohr magneton 9.2741 x 10-
21
erg G- 9.2741 x 10- 24 J T- I
Pe
Bohr magnetin 4.6685 x 10-
5
cm-
I
G- 1
PN
nuclear magneton 5.0508 x 10-
24
erg G - 5.0508 X 10-
27
J T-
I
me electron rest mass 9.1095 x 10 - 28 g 9.1095 X 10-3 1 kg
mp proton rest mass 1.6726 x 10- 24 g 1.6726 X 10 -
27
kg
lIe
electron magnetic moment 9.2848 x 10- 21 erg G -
I
9.2848 x 10- 24 J T -
I
YH
proton magnetogmic ratio 2.6752 x 10
3
kg -
I
sA
1t 3.14159 26535 89793 23846 26433 83279 50288
T stands for Tesla (kg s - 2 A-1); C stand s fm Coulomb; S = second ; A = ampere; 1 erg = 1 g cm
2
s -2.
CONVERSION FACTORS
1 cal = 4.184 J (Joules)
1 Hz = 6.6262 X 10-
34
J
1 K = 1.3807 X 10-
27
J
1 kWh = 3.6 x 10
6
J
Energy Conversion Factors
erg/molecule ev cm -
1
cal/ mole
erg/molccule ..... . 1 6.242 X 10
1
5.036 X 10
1 5
1.439 X 10
1 6
cv .......... .. ....... . . 1.602 X 10 -
12
1 8,067 23,060
cm- ...... ... ..... . . 1.986 X 10-
16
1.2396 X 10 -
4
1 2.858
cal/ mole .. .... .... .. 6.949 x 10- 17 4.338 X 10-
5
O. Q9 1
900 O>

Physical Methods (Russell S. Drago)

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f

PRO ERTIES OF SELECTED NUCLEI

"- ....... _____A

144 Chapler 5 Electronic Absorption Spectroscopy

268 Chapler7 Nuclear Magnetic Resonance Spectroscopy- Elementary Aspects

addingsodium to naphthalene,contains an odd electron that is delocalized over

' where the subscripts indicate that the ligand-d

The Angular Overlap Model 457

tfz = (1/fi)( ll, -1-

can be accumulated as each component emerges from the column. A partially

Satisfying this equation results in a three-dimensional mapping of the electro n

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