Spectrochimica Acta Part A 72 (2009) 654662

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Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy
j our nal homepage: www. el sevi er . com/ l ocat e/ saa
Spectroscopic analysis and DFT calculations of a food additive Carmoisine
M. Snehalatha
a,1
, C. Ravikumar
a
, I. Hubert Joe
a,
, N. Sekar
b
, V.S. Jayakumar
a
a
Center for Molecular and Biophysics Research, Department of Physics, Mar Ivanios College, Thiruvananthapuram, 695015 Kerala, India
b
Institute of Chemical Technology, University of Mumbai, Matunga, Mumbai 400019, India
a r t i c l e i n f o
Article history:
Received 2 July 2008
Received in revised form 3 November 2008
Accepted 10 November 2008
Keywords:
E122
FT-IR
FT-Raman
UVvis
TD-DFT
Conjugation
-Electron delocalization
NLO property
Intramolecular charge transfer
Intramolecular hyperconjugative
interactions
NBO analysis
a b s t r a c t
FT-IR and Raman techniques were employed for the vibrational characterization of the food addi-
tive Carmoisine (E122). The equilibrium geometry, various bonding features, and harmonic vibrational
wavenumbers havebeeninvestigatedwiththehelpof densityfunctional theory(DFT) calculations. Agood
correlationwas foundbetweenthe computedandexperimental wavenumbers. Azo stretching wavenum-
bers have beenlowereddue to conjugationand-electrondelocalization. Predictedelectronic absorption
spectra from TD-DFT calculation have been analysed comparing with the UVvis spectrum. The rst
hyperpolarizability of the molecule is calculated. Intramolecular charge transfer (ICT) responsible for the
optical nonlinearity of the dye molecule has been discussed theoretically and experimentally. Stability of
the molecule arising from hyperconjugative interactions, charge delocalization and CH O, improper,
blue shifted hydrogen bonds have been analysed using natural bond orbital (NBO) analysis.
2008 Published by Elsevier B.V.
1. Introduction
Azo dyes are synthetic organic colorants with pure chro-
mophoric properties, high molar extinction coefcient, and ne
staining qualities. They nd a wide range of applications in the
textile, paper, food, cosmetics, agrochemical, and pharmaceuti-
cal industries. Recently, metal complex dyes have also attracted
increasing attention due to their interesting electronic and geo-
metrical features inconnectionwiththeir applicationfor molecular
memory storages, nonlinear optical elements, printing system, etc.
[15]. They are characterized by the presence of the chromophoric
azo group (N N) attached to the substituents, mainly benzene or
naphthalenederivatives containingelectronwithdrawingor donat-
ing groups or both. The low-lying azo-centered
*
molecular orbital
is responsible for the intense long-wavelength absorption (dye
function) and the nonlinear optical properties (information stor-
age function). Aromatic side groups around the azo bond help to
stabilize the N N group by making it part of an extended delocal-

Corresponding author. Tel.: +91 471 2340767; fax: +91 471 2530023/2532445.
E-mail addresses: hubertjoe@sancharnet.in, hubertjoe@gmail.com
(I. Hubert Joe).
1
Permanent address: Department of Physics, Christian College, Kattakada, Kerala,
India.
izedsystem. This alsohas theeffect of makingmanyazocompounds
coloured; as delocalized or conjugated systems often absorb visible
frequencies of light. Azo dyes act as electron acceptors. Azo com-
pounds are reduced by the intestinal anaerobic bacteria through
scission of azo bonds to form aromatic amines, which are toxic to
living organisms [6]. Sulfonation of azo dyes resulted in decreased
carcinogenicity and mutagenicity [7]. Sulfonated azo dyes mainly
mono-, di- andtrisulfonatedcompounds are world-wide permitted
for use in foods, cosmetics and as drugs for oral application [8,9].
Azo dyes are stable in the whole pH range of foods, are heat stable
anddonot fadewhenexposedtolight andoxygen. Theyaresuperior
to natural dye extracts in tinctorial power, consistency of strength,
range and brilliance of shade, stability and ease of application.
Carmoisine (Azorubine, Food red 3 or E122 in Europe) is
an articial food additive that belongs to the azo dye class,
which essentially consists of disodium 4-hydroxy-3-(4-sulfonato-
1-naphthylazo) naphthalene-1-sulfonate and subsidiary colouring
matters together with sodium chloride and/or sodium sulfate as
the principal uncoloured components, and appears as a reddish-
maroon powder. As a sulfonated azo dye E122 is mainly used in the
food industry, in the presence of anions and other macromolecules,
where it can give rise to a phenomenon named metachroma-
sia, a characteristic colour change when certain tissue elements
are stained by cationic dyes [10,11]. UVvis, infrared absorption,
Raman, resonanceRamanandalsosurfaceenhancedRamanspectra
1386-1425/$ see front matter 2008 Published by Elsevier B.V.
doi:10.1016/j.saa.2008.11.017
M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662 655
Fig. 1. The optimized structure of E122 molecule based on B3PW91/LANL2DZ basis set.
of various azodyes havebeenreported[1214]. Vibrational spectro-
scopic investigationwiththehelpof quantumchemical calculations
has recently been used as an effective tool in the vibrational anal-
ysis of dye molecules, biological compounds, drug molecules and
NLO-active compounds [1519]. The present work deals with spec-
tral investigations using UVvis, FT-Raman and IR spectra, along
with the density functional theory (DFT) calculations, the time-
dependent density functional theory (TD-DFT) calculations and
natural bond orbitals (NBO) analysis to elucidate the correlation
between the molecular structure and NLO property by investi-
gating the intramolecular change transfer (ICT), -conjugations,
electrondelocalizationand H-bonding of the dye molecule Carmoi-
sine (E122).
2. Experimental
The UVvis absorption spectrum of the sample was measured
using Varian Cary 100 B10 UVvis spectrophotometer. The IR spec-
trum of the sample was recorded using a PerkinElmer Spectrum
One FT-IR spectrometer in the region 4004000cm
1
. For record-
ing FT-Raman spectra powdered form of the sample as well as the
sample dissolved in water was used. Analysis of the sample was
carried out on Bruker Vertex 70 FT-IR-RAM-II FT-Raman module.
For the FT-Raman measurements, the 1064nm line provided by a
Nd:YAG laser was used as the excitation source.
3. Computational details
Density functional theory (DFT) calculation was performed
employing the hybrid B3PW91 [20,21] exchange-correlation func-
tional with the LANL2DZ [22,23] basis set to get optimized
geometry and vibrational wavenumbers using Gaussian98 pro-
gram package [24]. B3PW91 when used with the LANL2DZ basis
set (B3PW91/LANL2DZ) provides excellent results when metallic
atoms are used. Molecular geometries were fully optimized by
Bernys optimization algorithm using redundant internal coordi-
nates. All optimized structures were conrmed to be minimum
energy conformation. At the optimized structure of the molecule
no imaginary frequency modes were obtained, providing that a true
minimumon the potential energy surface was found. The optimum
geometry was determined by minimizing the energy with respect
to all geometrical parameters without imposing molecular sym-
metry constraints. An empirical scaling factor of 0.9567 was used to
offset the systematic error caused by neglecting anharmonicity and
electron correlation. The Raman activities (S
i
) calculated by Gaus-
sian 98 programhave been converted to relative Raman intensities
(I
i
) using the following relationship derived from the basic theory
of Raman scattering [25,26]
I
i
=
f (
o

i
)
4
S
i

i
[1 exp(hc
i
/kT)]
(1)
where
o
is the exciting frequency (in cm
1
),
i
is the vibrational
wavenumber of the ith normal mode, h, c and k are universal
constants, and f is the suitably chosen common scaling factor
for all the peak intensities. The simulated IR and Raman spec-
tra have been plotted using pure Lorentizian band shapes with
a bandwidth of (FWHM) of 10cm
1
. The optimized geometry of
the molecule is presented in Fig. 1. The time-dependent den-
sity functional theory (TD-DFT) [27] was usually found to be a
robust and accurate method for describing low-lying excited states
of conjugated molecules. Electronic transitions for the molecule
were calculated from excited state calculations using the time-
dependent DFT methodB3LYP/DZ[28]. The rst hyperpolarizability
was calculated using B3LYP/LANL2DZ basis set on the basis of the
nite-eld approach. The components of the rst hyperpolarizabil-
ity can be calculated using the following equation:

i
=
iii
+
1
3
(
ijj
+
jij
+
jji
), (i / = j) (2)
Using the x, y and z components, the magnitude of the rst
hyperpolarizability tensor can be calculated by:
= (
2
x
+
2
y
+
2
z
)
1/2
(3)
The complete equation for calculating the magnitude of rst
hyperpolarizability from Gaussian 98W output is given as follows
[29]:
=[(
xxx
+
xyy
+
xzz
)
2
+(
yyy
+
yzz
+
yxx
)
2
+(
zzz
+
zxx
+
zyy
)
2
]
1/2
(4)
To calculate the hyperpolarizability, the origin of the Carte-
sian coordinate system was chosen as the center of mass of
the compound. The calculated rst hyperpolarizability (Table S1)
(Supplementary material) of E122 is found to be 1.8910
30
e.s.u,
which is 13 times that of urea.
Bytheuseof thesecond-order bondantibond(donoracceptor)
NBO energetic analysis, insight in the most important delocaliza-
tion schemes was obtained. The change in electron density (ED)
in the (
*
,
*
) antibonding orbitals and E
(2)
energies have been
656 M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662
Table 1
Optimized geometric parameters of food dye E 122 based on B3PW91/LANL2DZ.
Bond length (pm) Bond angle (

) Dihedral angle (

)
C
1
C
2
142.2 C
1
C
2
C
3
120.2 C
1
C
2
C
3
C
4
0.02
C
2
C
3
138.7 C
2
C
3
C
4
119.7 C
2
C
3
C
4
C5 0.2
C
3
C
4
141.9 C
3
C
4
C5 120.9 C
3
C
4
C5C
6
0.1
C
4
C5 139.8 C
4
C5C
6
120.7 C
2
C
1
C
6
C7 179.8
C5C
6
142.1 C
1
C
6
C7 117.4 C
1
C
6
C7C
8
0.5
C
6
C7 143.5 C
6
C7C
8
123.2 C
6
C7C
8
C
9
0.2
C7C
8
137.1 C7C
8
C
9
119.2 C7C
8
C
9
C
10
0.2
C
8
C
9
142.1 C
8
C
9
C
10
119.8 C
4
C
3
C
2
H
11
179.7
C
9
C
10
140.4 C
3
C
2
H
11
121.4 C
1
C
2
C
3
H
12
179.7
C
2
H
11
108.5 C
2
C
3
H
12
120.3 C
6
C5C
4
H
13
179.8
C
3
H
12
108.6 C5C
4
H
13
119.7 C
3
C
4
C5H
14
179.0
C
4
H
13
108.6 C
4
C5H
14
120.3 C
9
C
8
C7S
15
179.1
C5H
14
108.2 C
8
C7S
15
114.4 C
6
C7C
8
H
16
179.9
C7S
15
186.6 C7C
8
H
16
120.8 C
1
C
10
C
9
N
17
179.9
C
8
H
16
108.6 C
10
C
9
N
17
114.0 C
8
C
9
C
10
O
18
179.9
C
9
N
17
140.4 C
9
C
10
O
18
120.0 C
9
C
10
O
18
H
19
0.0
C
10
O
18
136.8 C
10
O
18
H
19
107.9 C
8
C7S
15
O
20
127.8
O
18
H
19
99.1 C7S
15
O
20
109.7 C
8
C7S
15
O
21
120.5
S
15
O
20
167.3 C7S
15
O
21
109.2 C
8
C7S
15
O
22
3.4
S
15
O
21
167.0 C7S
15
O
22
106.0 C7S
15
O
21
Na
23
135.8
S
15
O
22
162.0 S
15
O
21
Na
23
91.9 C
10
C
9
N
17
N
24
179.1
O
21
Na
23
230.1 C
9
N
17
N
24
116.5 C
9
N
17
N
24
C
25
179.5
N
17
N
24
128.8 N
17
N
24
C
25
116.5 N
17
N
24
C
25
C
26
4.1
N
24
C
25
142.0 N
24
C
25
C
26
124.2 N
24
C
25
C
26
C
27
179.1
C
25
C
26
139.4 C
25
C
26
C
27
120.5 C
25
C
26
C
27
C
28
0.4
C
26
C
27
140.9 C
26
C
27
C
28
119.3 C
26
C
27
C
28
C
29
0.5
C
27
C
28
138.3 C
27
C
28
C
29
123.2 C
27
C
28
C
29
C
30
1.1
C
28
C
29
142.4 C
28
C
29
C
30
117.0 C
28
C
29
C
30
C
31
179.2
C
29
C
30
144.2 C
29
C
30
C
31
119.0 C
29
C
30
C
31
C
32
0.4
C
30
C
31
142.6 C
30
C
31
C
32
120.7 C
30
C
31
C
32
C
33
0.5
C
31
C
32
138.5 C
31
C
32
C
33
120.3 C
31
C
32
C
33
C
34
0.6
C
32
C
33
142.2 C
32
C
33
C
34
120.5 C
30
C
25
C
26
H
35
179.8
C
33
C
34
138.4 C
25
C
26
H
35
119.4 C
29
C
28
C
27
H
36
179.6
C
26
H
35
108.5 C
28
C
27
H
36
119.2 C
26
C
27
C
28
S
37
177.8
C
27
H
36
108.6 C
27
C
28
S
37
114.1 C
32
C
33
C
34
H
38
177.9
C
28
S
37
187.3 C
33
C
34
H
38
120.6 C
29
C
34
C
33
H
39
179.7
C
34
H
38
108.2 C
34
C
33
H
39
120.0 C
30
C
31
C
32
H
40
179.9
C
33
H
39
108.7 C
31
C
32
H
40
119.9 C
33
C
32
C
31
H
41
179.5
C
32
H
40
108.6 C
32
C
31
H
41
121.0 C
27
C
28
S
37
O
42
132.3
C
31
H
41
108.3 C
28
S
37
O
42
119.4 C
27
C
28
S
37
O
43
115.9
S
37
O
42
167.1 C
28
S
37
O
43
108.7 C
27
C
28
S
37
O
44
7.6
S
37
O
43
162.0 C
28
S
37
O
44
106.0 C
28
S
37
O
43
Na
45
134.6
S
37
O
44
166.9 S
37
O
43
Na
45
92.4
O
43
Na
45
229.5
calculated by natural bond orbital (NBO) analysis [30] using DFT
method to give clear evidence of stabilization originating from
various molecular interactions. NBO analysis has been performed
on E122 in order to elucidate intramolecular hydrogen bonding,
intramolecular charge transfer (ICT), delocalization of electrons
of the naphthalene ring. The hyperconjugative interaction energy
was deduced from the second-order perturbation approach [31].
E(2) = n

| F|
2

= n

F
2
ij
E
(5)
where |F|
2
, or F
2
ij
is the Fock matrix element between i and j
NBO orbital,

and
*
are the energies of and
*
NBOs, and n

is the population of the donor orbital.

4. Results and discussion
4.1. Geometry optimization
The E122 structure was optimized using B3PW91 method with
LANL2DZ basis set. The calculated structural parameters are given
in Table 1. The molecule E122 consists of two separate ring sys-
tems, viz. the naphthalene (1) ring and naphthalene (2) ring
connected to each other by the azo chromophore group (N N).
The azo naphthalene (2) ring moiety is essentially coplanar
[N
24
N
17
C
9
C
10
=179.1

and N
24
N
17
C
9
C
8
=1.0

] and naph-
thalene (1) ring is almost coplanar with the azo chromophore
[N
17
N
24
C
25
C
26
=4.1

and N
17
N
24
C
25
C
30
=176.3

] as evi-
dent from the torsion angles. The hydroxyl group is planar and lies
in the same plane of the naphthalene (2) ring moiety which can
be seen from the torsion angle [C
9
C
10
O
18
H
19
=0.1

]. Another
feature is the presence of an OH group ortho to azo in this com-
pound providing an extra potential hydrogen bonding or metal
complexing site so as to interact intramolecularly with azo group
to provide the possibility of tautomerism to the keto-hydrazone
as is found in commercial monoazo dyes [32]. X-ray studies on
diazo dyes [33] have shown that the sodiumsulfonate groups lie on
the opposite sides of the conjugated azo linkages. This is revealed
by the C
9
N
17
N
24
(116.5

), C
8
C
9
N
17
(126.1

) and C
10
C
9
N
17
(114.1

) calculated angles, the difference between the C

9
N
17
and
N
24
C
25
bonds being a 180

rotation. The optimized structure indi-

cates intramolecular CH O S hydrogen bonding. The hydrogen
bonding parameters are as shown in Table 2. C
5
H
14
and C
34
H
38
bond distance (108.2pm) are shorter than the average calculated
CH bond length (108.6pm). The angles between CN bond and
naphthalene rings appear to be distorted by a steric repulsion [34]
between azo group and naphthalene rings [N
17
C
9
C
8
=125.9

and
N
24
C
25
C
26
=124.2

]. The bond length between the azo-N

17
and
naphthalene (2) ring C
9
(C
9
N
17
) is 140.6pm, which is less than
azo-N
24
and naphthalene (1) ring C
25
(C
25
N
24
) 142.3pm which
M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662 657
Table 2
Intramolecular hydrogen bonding parameters based on B3PW91/LANL2DZ basis set.
DH A DH (pm) H A (pm) D A (pm) DH A (

)
C5H
14
O
20
C5H
14
H
14
O
20
C5 O
20
C5H
14
O
20
108.2 229.3 308.6 128.6
C
34
H
38
O
42
C
34
H
38
H
38
O
42
C
34
O
42
C
34
H
38
O
42
108.2 226.5 307.2 129.8
supports intramolecular charge transfer (ICT) from the naphtha-
lene (2) ring and localization at the azo bond [35] which enhances
the optical nonlinearity of the dye. As shown in Table 1, the average
CCbondlengths of the naphthalene ring (2) is 140.9pmwhichis in
between the length of a CC single bond (154pm) and that of a C C
double bond (134pm). Similarly average CN distance (141.4pm)
in the calculated molecular structure is also intermediate between
those of a CN single bond (148pm) and of a C N double bond
(128pm). Therefore the calculated data suggests an extended -
electron delocalization over the naphthyl azo system [36] which
is responsible for the nonlinearity of the molecule. Usually N N
bond length is 125.0pm [37,38] whereas the azo N
17
N
24
distance
of 128.8pm in the title compound is appreciably elongated. This
implies that the hydroxyl group can donate some electron density
via naphthalene (2) ring into the
*
orbital of the azo moiety which
results in decreasing the bond order of the N N mode and length-
ening the bond. This shows that the substituent, having electron
donating property on the naphthalene (2) ring at the ortho position
plays a signicant role on the bond order of the azo bond [39].
4.2. Natural bond orbital analysis
Natural bond orbital analysis provides an efcient method for
studying intra- and intermolecular bonding and interaction among
bonds, and also provides a convenient basis for investigating charge
transfer or conjugative interaction in molecular systems. Some
electron donor orbital, acceptor orbital and the interacting stabi-
lization energy resulted from the second-order micro-disturbance
theory are reported [40,41]. The larger the E
(2)
value, the more
intensive is the interaction between electron donors and electron
acceptors, i.e. the more donating tendency from electron donors
to electron acceptors and the greater the extent of conjugation
of the whole system. Delocalization of electron density between
occupied Lewis-type (bond or lone pair) NBO orbitals and for-
mally unoccupied (antibond or Rydgberg) non-Lewis NBO orbitals
correspond to a stabilizing donoracceptor interaction. NBO anal-
ysis has been performed on the molecule using NBO 3.1 program
as implemented in the Gaussian 98 package at the DFT/B3PW91
level in order to elucidate the intramolecular hydrogen bond-
ing, rehybridization and delocalization of electron density within
the molecule. The corresponding results have been tabulated in
Tables 3 and 4. The second-order perturbation theory analysis
of Fock matrix in NBO basis of E122 show strong intramolecular
Table 3
Selected second-order perturbation energies E
(2)
(donor acceptor).
Donor (i) Type ED/e Acceptor (j) Type ED/e E
(2)a
(kJ mol
1
) E(j) E(i)
b
(a.u.) F(i, j)
c
(a.u.)
O
18
LP (1) 1.97918 C
9
C
10

*
0.44915 29.04 1.17 0.081
O
18
LP (2) 1.84318 C
9
C
10

*
0.44915 200.71 0.38 0.099
C
1
C
6
1.52135
C
2
C
3

*
0.22060 68.10 0.31 0.067
C
4
C5
*
0.22846 62.05 0.30 0.063
C
9
C
10

*
0.44915 90.29 0.28 0.070
C
2
C
3
1.73070 C
1
C
6

*
0.43302 71.76 0.29 0.066
C
4
C5
*
0.22846 75.94 0.31 0.067
C
4
C5 1.72656 C
1
C
6

*
0.43302 78.66 0.30 0.069
C
2
C
3

*
0.22060 69.45 0.31 0.065
C7C
8
1.78936 C
1
C
6

*
0.43302 72.63 0.33 0.071
C
9
C
10

*
0.44915 50.75 0.31 0.057
C
9
C
10
1.56407 C
1
C
6

*
0.43302 55.69 0.32 0.060
C7C
8

*
0.25971 93.68 0.31 0.076
N
17
N
24

*
0.21169 97.53 0.23 0.063
C
25
C
26
1.69620 N
17
N
24

*
0.21169 50.54 0.22 0.049
C
27
C
28

*
0.28751 87.40 0.30 0.071
C
30
C
31

*
0.45771 72.80 0.31 0.068
C
27
C
28
1.75045 C
25
C
26

*
0.27661 60.88 0.33 0.062
C
29
C
34

*
0.46589 76.11 0.32 0.072
C
29
C
34
1.51722 C
27
C
28

*
0.28751 81.76 0.26 0.068
C
30
C
31

*
0.45771 95.77 0.27 0.071
C
32
C
33

*
0.43379 113.89 0.27 0.078
C
30
C
31
1.51214 C
29
C
34

*
0.46589 101.71 0.27 0.071
C
25
C
26

*
0.27661 86.15 0.27 0.071
C
32
C
33

*
0.43379 112.76 0.27 0.077
C
32
C
33
1.52269 C
29
C
34

*
0.46589 114.81 0.27 0.076
C
30
C
31

*
0.45771 113.85 0.27 0.077
C
1
C
6

*
0.43302 C
2
C
3

*
0.22060 692.08 0.02 0.078
C
4
C5
*
0.22846 796.51 0.01 0.080
C
9
C
10

*
0.44915 C
1
C
6

*
0.43302 856.51 0.02 0.080
O
20
LP (2) 1.89955 C
34
H
38

*
0.02388 13.01 0.81 0.046
O
42
LP (2) 1.89956 C5H
14

*
0.02373 13.81 0.81 0.047
a
E
(2)
means energy of hyperconjugative interactions (stabilization energy).
b
Energy difference between donor and acceptor i and j NBO orbitals.
c
F(i, j) is the Fock matrix element between i and j NBO orbitals.
658 M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662
Table 4
NBO results showing the formation of Lewis and non-Lewis orbitals by the valance hybrids corresponding to the intramolecular CH O hydrogen bonding of E122.
Bond (AB) ED/energy (a.u) ED
A
% EDB% NBO s% p%
C5H
14
1.97393 61.60 38.40 0.7848(sp
2.43
)C 29.19 70.81
+
0.53079 0.6197(s) H 100.00

*
C5H
14
0.02373 38.40 61.60 0.6197(sp
2.43
)C 29.19 70.81
+
0.50023 0.7848(s) H 100.0
C
34
H
38
1.97404 61.36 38.64 0.7834(sp
2.44
)C 29.09 70.91
+
0.52602 0.6216(s) H 100.0

*
C
34
H
38
0.02388 38.64 61.36 0.6216(sp
2.44
)C 29.09 70.91
+
0.50439 0.7834(s) H 100.0
hyperconjugative interactions, which are presented in Table 3. The
intramolecular hyperconjugative interactions are formed by the
orbital overlap between (CC) and
*
(CC) bond orbitals which
results intramolecular charge transfer (ICT) causing stabilization
of the system. These interactions are observed as an increase in
electron density (ED) in CC antibonding orbital that weakens the
respective bonds. There occurs a strong intramolecular hypercon-
jugative interaction of electrons from C
2
C
3
, C
4
C
5
and C
7
C
8
bonds to the
*
(C
1
C
6
) bond of the naphthalene (2) ring which
increases the ED (0.43e) leading to stabilization of 74kJ/mol.
This enhanced
*
(C
1
C
6
) NBO further conjugates with
*
(C
2
C
3
)
and
*
(C
4
C
5
) resulting to an enormous stabilization of 692 and
797kJ/mol, respectively. The most important interaction energy,
related to the resonance in the molecule, is electron donation from
LP (2) O
18
to the antibonding acceptor
*
(C
9
C
10
) of the naphtha-
lene (2) ring (201kJ/mol). This enhanced
*
(C
9
C
10
) NBO further
conjugates with
*
(C
1
C
6
) resulting to an enormous stabilization
of 857kJ/mol. The -electron delocalization is maximum around
the C
29
C
34
, C
30
C
31
, C
32
C
33
of the naphthalene (1) ring which is
revealed by the ED at the three conjugated bonds (1.52e) and

*
bonds (0.46e) of the naphthalene (1) ring leading to stabiliza-
tion of 113kJ/mol. These intramolecular charge transfer (n
*
,

*
and
*

*
) can induce large nonlinearity to the molecule.
According to the NBO second-order perturbative estimates of
theinteractionenergies betweendonor andacceptor -NBOs, there
is considerable resonance effect in the molecule operating between
its azo groupandthe two naphthalene rings. The interactionenergy
between the empty antibond orbital
*
(N
17
N
24
) and the lled
bond orbital (CC) in the naphthalene (1) and naphthalene (2)
rings are 51 and 98kJ/mol respectively as shown in Table 3. The
lone pair electrons of the azo group are not included in localization
since lone pairs lie inthe molecular plane whichis orthogonal tothe
system. The azo group being coplanar with the naphthalene (2)
ring increases conjugation between them which supports electron
delocalization from naphthalene (2) ring to the azo group which
is revealed by the high value of the interaction energy (98kJ/mol)
between the azo group and naphthalene (2) ring. These NBOresults
conrm that the electron delocalization is from the oxygen of the
hydroxyl group via naphthalene (2) ring to the azo moiety which
results inbondelongationwithconcomitant redshift of azostretch-
ing wavenumber.
There has been considerable interest in various types of
intramolecular and intermolecular interactions. This is under-
standable, as these interactions play important roles in crystal
engineering, molecular recognition, supramolecular assemblies
and conformational equilibrium. A number of CH O, CH N
and CH [4245] complexes have been investigated, in which
one of the interesting aspects is the frequency blue shift for the
CH stretching vibration. In the present study the intramolec-
ular CH O hydrogen bonds are exposed in the NBO analysis
results shown in Table 3 by the interaction between the oxygen
lone pair and CH antibonding orbital (LP (2)O
20

*
C
5
H
14
, LP
(2)O
42

*
C
34
H
38
). Notwithstanding the fact that the energetic
contribution (13 and 14kJ/mol) of hyperconjugative interactions is
weak, these E
(2)
values are chemically signicant and can be used
as a measure of the intramolecular delocalization. The strength-
ening and contraction of CH bonds (CH=108.2pm) is due to
rehybridization [46], which is revealed by the lowvalue of electron
density (0.023e) in the
*
CH orbital (Table 4). The NBO results,
optimized geometrical parameters and corresponding up shift in
CH stretching wavenumber (3176cm
1
) predict the blue shift of
improper hydrogen bonding. It is observed as a shoulder band in IR
at 3090cm
1
and a weak band at 3100cm
1
in Raman spectrum.
4.3. Electronic spectra
The chemical structure of dyes is composed of a conjugated sys-
tem of double bonds and aromatic rings. All these structures allow
strong
*
transitions in the UVvis region with high extinction
coefcients that allow us to consider these structures dye chro-
mophores. Natural bond orbital analysis indicates that molecular
orbitals are mainly composed of atomic orbital, so above elec-
tronic transitions are mainlyderivedfromthe contributionof bands

*
. UVvis absorption spectrumof the sample in water is shown
inFig. 2. The visible bandobservedaround510nmcanbe attributed
tohighdelocalizationof -electrons inthe azochromophore group.
The band observed at 335nm may be ascribed to the excitation of
the -electrons which is localized on the naphthyl rings. The TD-
DFT is particularly well suited to low energy valence excited states
that can be described by combinations of single excitations. Elec-
tronic transitions determined fromexcited state calculations using
the TD-DFT method are listed in Table 5 for the three lowest energy
transitions of the molecule. These are identied with the calculated
Fig. 2. The UVvis absorption spectrum of E122 molecule.
M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662 659
Table 5
Calculated electronic absorption spectral data of E122 molecule.
Excitation CI expansion coefcient Wavelength (nm) Oscillator strength (f) Energy (eV)
Calc. Expt.
Excited state 1
106109 0.29654 488 510 0.0032 2.5404
107109 0.52049
108109 0.26554
Excited state 2
106109 0.15973 400 0.5780 3.0985
107109 0.21958
108109 0.59219
Excited state 3
106109 0.58438 366 335 0.0097 3.3884
107109 0.33275
transitions at 488 and 366nm. In this case the energy transitions
are in reasonable agreement with experimental results.
4.4. Vibrational spectral analysis
The analysis of the vibrational spectra (Table 6) is based on the
FT-IR spectrum, FT-Raman and the vibrational wavenumbers com-
puted at B3PW91/LANL2DZ level with their scaled wavenumbers.
Vibrational mode assignments were made by visual inspection of
modes animated by using the Molekel 4.2 software [47]. A good
correlation was found between the computed and experimental
wavenumbers. The observedFT-IR, FT-Ramanspectra (powder) and
simulated theoretical spectra calculated at B3PW91/LANL2DZ level
are given in Figs. 3 and 4 for visual comparison. The FT-Raman
spectrum of the sample dissolved in water (Fig. 5) is also used for
the analysis. The vibrational analysis is performed based on the
characteristic vibrations of hydroxyl, azo, sulfonate and naphthyl
groups.
Table 6
FT-IR, FT-Raman and computed vibrational bands of E 122 and their assignments.
IR (cm
1
) Raman powder (cm
1
) Raman solution (cm
1
)
cal.
(cm
1
) IR intensity Raman intensity Assignments
3436vvs 3448 72 1734 O
18
H
19
stretch
3090sh 3100vw 3176 11 663 CH stretch
1632 s 1614m 1613s 1610 115 692 Naph (2) ring stretch+O
18
H
19
i.p. bend
1604s 1593s 1605 52 129 Naph (1) ring stretch
1572m 1573vvs 1574vs 1577 69 83 Naph (2) ring stretch+O
18
H
19
i.p. bend
1554s 1559 10 52 Naph (1) ring stretch
1516m 1516vs 1516vs 1519 50 980 Naph (2) ring stretch
1500vs 1490 15 49 O
18
H
19
i.p. bend
1474s 1449vs 1450vs 1486 74 191 Naph (1) ring stretch
1436m 1439vs 1436 4 17 CH Naph (2) i.p. bend+C
9
N
17
N
24
i.p. bend
1409w 1410m 1407m 1410 4 16 CH Naph (1) i.p. bend+Naph (2) stretch
1367m 1366vs 1365vs 1369 98 1180 N
17
N
24
stretch+Naph (2) stretch
1337w 1338s 1337s 1344 11 208 CH Naph (1,2) i.p. bend+(CN NC) asym. stretch
1296sh 1296sh 1313 7 84 CH Naph (2) i.p. bend
1277vs 1280s 1280vs 1271 31 73 C
9
N
17
stretch+CH Naph (2) i.p. bend
1238s 1237s 1231 166 107 C
10
O
18
stretch+(CN NC) asym. Stretch
1206sh 1200sh 1212 237 15 C
10
O
18
stretch+O
18
H
19
i.p. bend
1188vvs 1190 213 82 CH Naph (2) i.p. bend+C
25
N
24
stretch+SO
3
asym. stretch
1164w 1160 1167 10 87 CH Naph (1) i.p. bend+C
25
N
24
stretch
1154s 1155w 1150 33 324 (CN NC) stretch+CH i.p. bend Naph (1,2)
1124m 1123w 1131 2 1 CN i.p.b. +CH Naph (1) i.p. bend
1045vvs 1052m 1052s 1081 20 7 SO
3
sym. stretch+Naph rings (1,2) def
1020vs 1025 23 130 CN i.p. bend+CH Naph (1) i.p. bend
1006s 1006w 1007m 1005 5 32 (CN NC) i.p. bend+Naph rings (1,2) def
970w 990vw 985vw 987 7 1 CH Naph (2) o.p. bend
940m 948 32 11 CN N i.p. bend+Naph rings (1,2) def
897w 899 37 9 Naph rings def +CN N i.p. bend+SO
3
asym. bend
850vw 867 65 6 CN N i.p. bend+SO
3
asym. bend
816m 821vw 820vw 821 9 0.33 Naph (2) ring o.p. bend+O
18
H
19
bend
785vw 785vw 784 259 0.24 Naph (1) ring o.p. bend
752s 763 64 0.31 SO
3
sym. bend+Naph rings o.p. bend
729w 733 114 0.20 SO
3
sym. bend+Naph rings def
687vs 683vw 680w 693 74 0.67 SO
3
sym. bend+Naph rings def
654s 657m 658w 664 98 0.09 O
18
H
19
o.p.b
624s 618vw 631 9 0.85 (CN NC) i.p.b+Naph rings i.p. bend
596s 585vw 585m 591 14 0.85 Naph rings def. +(CN NC) torsion
558m 563 18 2 Naph rings def. +SO
3
bend
535w 534m 534 9 0.15 Naph rings def. +SO
3
wagging
495w 505m 504m 510 10 3 SO
3
wagging+CN torsion
467w 470m 469m 465 166 0.65 SO
3
wagging+OH bend+Naph rings torsion
380vw 380vw 383 4 0.10 SO
3
rocking+Naph rings torsion N
17
N
24
torsion
300vw 300vw 305 24 0.10 SO
3
rocking+N
17
N
24
torsion+Naph rings torsion
58s 58s 61 7 0.001 SO
3
torsion+Naph rings torsion
660 M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662
Fig. 3. (a) The FT-IR spectrum of E122 molecule in the wavenumber range
4000400cm
1
. (b) The simulated IR spectrum of E122 molecule computed at
B3PW91/LANL2DZ basis set.
4.4.1. Hydroxyl vibrations
The free hydroxyl group absorbs strongly in the region
37003584cm
1
, whereas the existence of intermolecular hydro-
gen bond formation can lower the OH stretching frequency to
the 35503200cm
1
region with increase in intensity and breadth
[48,49]. It was well established that the presence of an OH group
ortho to azo provides an extra potential hydrogen bonding site
in similar compounds. The IR spectrum in the high wavenumber
region shows a broad intense band at 3436cm
1
attributed to
hydrogen bonded OH stretching vibrations. It is possible that the
OHgroupmayparticipateinintermolecular hydrogenbondingwith
a neighbouring molecule. The in-plane OH deformation vibration
usually appears as strong bandinthe region14401260cm
1
inthe
Fig. 4. (a) The FT-Raman spectrum of E122 molecule (powder) in the wavenum-
ber range 400050cm
1
. (b) The simulated Raman spectrum of E122 molecule
computed at B3PW91/LANL2DZ basis set.
spectrum [50]. The very strong band at 1500cm
1
in IR spectrum
corresponds to in-plane-bending vibration of OH group. The OH
out-of-plane deformationvibrationlies inthe region280312cm
1
for free OH and in the region 600720cm
1
for associated OH
[51]. The strong band at 654cm
1
in the IR and medium intense
band at 657cm
1
in Raman spectra correspond to out-of-plane-
bending mode of hydroxyl vibration. The calculated values of OH
group vibrations show good agreement with the experimental
results.
4.4.2. Azo chromophoric group (CN NC) vibrations
Azo chromophoric group, viz. (CN NC), can be treated as
a single unit. However, this group contains two bonds, viz. CN
and N N and each has a well-known characteristic vibrational
wavenumber of its own. N N stretching vibration, which due to
its symmetry has a very characteristic and intensive band in the
Raman and they are difcult to observe in the infrared spectrum.
But the change of N N bond length in the molecule which has
Fig. 5. The FT-Raman spectrum of E122 molecule (solution) in the wavenumber range 400050cm
1
.
M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662 661
two unequivalent CN parts causes a change in dipole moment.
Thus the N N stretching mode is IR active and is predicted to be
mediumstrength. Thebandoccurringbetween1450and1380cm
1
corresponds to the N N stretching of an azo compound [52]. CN
stretching vibrations of azo compounds are expectedto occur inthe
region 12001130cm
1
[53,54]. These bands shift in wavenumber
and intensity in a complex fashion, depending on the neighbouring
groups, conjugationeffects, H-bonding andmolecular tautomerism
[54]. Moreover, substituents on conjugated naphthalene groups
inuence both the peak wavenumber and intensity. The most
intense band observed at 1366cm
1
in the Raman spectrum and
the medium band in IR at 1367cm
1
are attributed to the azo
stretching vibration of the molecule. The azo stretching vibration
undergoes a large downshift in wavenumber due to greater con-
jugation and -electron delocalization [55]. From the theoretical
calculation the azo (N
11
N
28
) distance in the molecule is appre-
ciably elongated (128.8pm) and the corresponding wavenumber
of this mode is down shifted to 1369cm
1
supporting the exper-
imental ndings. The very intense band at 1277cm
1
(IR) and at
1280cm
1
(Raman) originate from the stretching mode of CN
group connected to naphthalene (2) ring. This band has contri-
bution from CH in-plane-bending vibration of naphthalene ring
(2) ring. The weak Raman band at 1164cm
1
is attributed to the
stretching mode of CN group connected to naphthalene (1) ring
coupled with CH in-plane-bending vibration of naphthalene (1)
ring. The strong band in the Raman appear at 1238cm
1
is assigned
to asymmetric stretching of (CN NC) chromophore group com-
bined with stretching vibration of CO group. The intense band at
1006cm
1
inIRandweakbandat 1006cm
1
inRamanis attributed
to the in-plane-bending vibration of (CN NC) group.
4.4.3. Sulfonate group vibrations
Asymmetric stretching vibrations of SO
3
group of sulfonic
acid salts usually occur at 12501140cm
1
[50]. The band due
to symmetric stretching vibration is sharper and occurs at
11301080cm
1
. SO
3
symmetric deformation modes give strong
bands in the region 550660cm
1
[56,57]. The sulfonic group does
not affect the conjugated system irrespective of the substitution
position in the naphthalene rings. Changes in the electron density
are relatively low at the carbon atoms to which sulfonic groups are
substituted [58]. Furthermore, the participation of sulfur d orbital
in the conjugated system is very low, and the contribution to
CS bond is practically negligible. The asymmetric stretching mode
of SO
3
group is mixed with CN stretching, CH in-plane-bending
giving a very broad intense band at 1188cm
1
in IR spectrum.
The intense band at 1054cm
1
in IR and medium intense band at
1052cm
1
in Raman have been assigned as symmetric stretching
vibration of SO
3
group. These vibrations are mixed with naph-
thalene ring deformations. SO
3
symmetric bending vibrations are
coupledwithout-of-plane-bendingvibrations of naphthalenerings
giving a broad intense band in IR at 752cm
1
. The mediumintense
Raman bands at 505 and 470cm
1
correspond to SO
3
wagging
vibrations. The same mode appears at 495 and 467cm
1
in IR spec-
trum. Weak bands at 380 and 300cm
1
in Raman are assigned to
SO
3
rocking vibrations which are mixed with torsion vibrations of
both naphthalene rings and azo group. The strong Raman band at
58cm
1
is attributed to torsion vibrations of SO
3
group and naph-
thalene rings.
4.4.4. Naphthalene ring vibrations
Naphthalene ring stretching vibrations are expected in the
region 16201390cm
1
whereas naphthalene CH bending modes
give rise to bands [59,60] in the region 1230970cm
1
. Naphtha-
lene ring vibrations are found to make a major contribution in
the IR and Raman spectra. For naphthalene (2) ring, CC stretch-
ing mode is observed as strong bands at 1632cm
1
in IR and at
1614cm
1
in the Raman. The IR and Raman spectra give strong
bands corresponding to stretching vibration of naphthalene (1)
ring at 1604 and 1593cm
1
, respectively. The intense Raman
bands at 1573 and 1516cm
1
and medium IR bands at 1572 and
1516cm
1
originate from the CC stretching vibration of naphtha-
lene (2) ring. These vibrations are mixed with in-plane-bending
vibration of OH group. The CC stretching vibration of naphtha-
lene (1) ring appears at 1474cm
1
(IR) and 1449cm
1
(Raman) as
strong bands. The stretching vibrations of naphthalene rings do not
couple with each other because of the nonuniformity in their sub-
stituents. The C C stretching is an important marker band and its
frequency is a genuine measure of the degree of the conjugation
through the -electron chain [61], hence can be used to follow
the nonlinear polarization of the -electrons. The intramolecular
charge transfer (ICT) from the donor to acceptor group through
singledouble bond conjugated path can induce large variations
of both the molecular dipole moment and molecular polarizabil-
ity making simultaneous activation of C C stretching modes of the
naphthalene rings in IR and Raman spectra. The simultaneous acti-
vation of C C stretching modes of the naphthalene rings in IR and
Raman spectra (1632:1614, 1604:1593, 1572:1573, 1516:1516, and
1474:1449cm
1
) provide evidence for the charge transfer inter-
action between the donors and acceptor groups through the
system which make the molecule highly polarized enhancing the
NLO property of the food dye. CH in-plane-bending vibration of
naphthalene (1) ring gives bands at 1409 and 1020cm
1
in IR and
the Raman counterpart is observed as medium bands at 1410 and
1124cm
1
. Naphthalene (2) ring gives CH in-plane-bending vibra-
tions at 1436, 1277 and 1188cm
1
in IR spectrumand a strong band
in Raman spectrum at 1439, 1296, 1280, and 1164cm
1
. The IR
bands at 1337 and 1154cm
1
and the Raman bands at 1338 and
1155cm
1
are assigned to the CH in-plane-bending vibration of
both naphthalene rings. These vibrations are coupled with CN
stretching vibrations. Bands below 1000cm
1
correspond to ring
deformation modes of naphthalene rings [60]. Strong IR bands are
observed at 1006, 940, 897, 729, 687, 596 and 558cm
1
for naph-
thalene ring deformationmodes andthe same vibrationis observed
in Raman at 1006, 683, and 585cm
1
. CH out-of-plane vibrations
of naphthalene have absorption bands in the region 770740cm
1
for four adjacent aromatic hydrogen atoms and in the region
850810cm
1
for two adjacent aromatic hydrogen atoms [50]. The
IR bands at 970, 816, and 752cm
1
and the very weak Raman
bands at 990, 821 and 785cm
1
are attributed to the CH out-
of-plane-bending vibrations of naphthalene rings. Strong Raman
bands appear at 58cm
1
corresponds to naphthalene ring torsions
coupled with SO
3
torsions.
5. Conclusion
Vibrational spectral analysis is carried out using FT-IR and
Raman spectroscopy for the nonlinear food additive E122. Assign-
ments of the vibrational spectra have been facilitated by DFT
calculations. A good correlation was found between the computed
and experimental wavenumbers. The N N stretching wavenum-
ber of the azo group have been lowered due to conjugation and
-electron delocalization. Predicted electronic absorption spec-
tra from TD-DFT calculation have been analysed comparing with
the UVvis spectrum and they are mainly derived from the con-
tribution of bands
*
. Optimized geometry indicates CH O
hydrogen bonding in the molecule. Vibrational spectra and NBO
analysis conrm the occurrence of blue shifting hydrogen bond in
the molecule. The calculated rst hyperpolarizability is found to be
1.8910
30
e.s.u, which is 13 times that of urea. Simultaneous IR
and Raman activation of the naphthalene ring modes provide evi-
dence for the charge transfer interaction between the donor and
the acceptor groups. Vibrational analysis and NBO analysis conrm
662 M. Snehalatha et al. / Spectrochimica Acta Part A 72 (2009) 654662
that intramolecular charge transfer (ICT) must be responsible for
the optical nonlinearity of the dye molecule.
Acknowledgements
The author M. Snehalatha thanks the University Grants Com-
mission (UGC), India, for the award of a Teacher Fellowship under
FIP scheme leading to the Ph.D. degree. The authors also thank Dr.
Shreeram Oak, Product Manager, Niulab Equipment Co. Pvt. Ltd.,
Mumbai, for recording the Raman spectra.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.saa.2008.11.017.
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