CHEM2210 Structure Elucidation in Chemistry

Prof Peter Gill

Part 1. Molecular Symmetry Symmetry Operations Point Groups Character Tables & Symmetry Species Orbital Symmetry Part 2. Molecular Orbital Theory General Rules Diatomic Molecules Linear Polyatomic Molecules Non-Linear Polyatomic Molecules Part 3. Molecular Vibrations and Electronic Transitions Reducible and Irreducible Representations Reduction Formula Application to Molecular Vibrations Application to Electronic Transitions

Symmetry Operations
A molecule with symmetry has two or more orientations in space that are indistinguishable from one another.

Molecular symmetry is measured by the number and type of symmetry operations. Five different types of symmetry operations are important to us:

Symmetry Operations
1.! Identity (E). Trivial operation that does nothing. 2.! Proper Rotation (Cn). Rotation by 360/n.

Symmetry Operations
Two-fold C2 (180), three-fold C3 (120), four-fold C4 (90), five-fold C5 (72), six-fold C6 (60), etc. proper rotations are possible. The highest-fold rotation axis is known as the principal rotation axis of the molecule and is generally designated as the molecular z axis. 3.! Reflection (!). A reflection in a mirror plane that maps one half of the molecule onto the other half.

Symmetry Operations
There are three types of mirror planes: Horizontal mirror plane (!h) is a mirror plane which is perpendicular to the principal rotation axis.

Symmetry Operations
Vertical Mirror Plane (!v) is a mirror plane which contains the principal rotation axis.

Symmetry Operations
Dihedral Mirror Plane (!d) is a mirror plane which contains the principal rotation axis and also bisects the angle between two C2 axes or two !v mirror planes.

Symmetry Operations
4. Inversion ( i ). Turning a molecule inside out by moving each atom through a point (the centre of inversion) in a straight line to an identical atom on the other side at the same distance.

Symmetry Operations
5. Improper Rotation (Sn). A proper rotation by 360o/n, followed by reflection through a plane perpendicular to the rotation axis.

S4 Improper Rotation Axis in CH4

Symmetry Operations
Useful Websites for Learning about Symmetry
! ! ! http://symmetry.otterbein.edu/ http://www.reciprocalnet.org/edumodules/symmetry/index.html http://www.staff.ncl.ac.uk/j.p.goss/symmetry/Molecules_l3d.html

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Point Groups
We can categorise molecules into point groups by finding the number and type of symmetry operations that they possess. Here are some examples:

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C1

Only the identity operation E. Examples: CHFClBr and non-planar HOOCl

Point Groups Ci
Only a centre of inversion. Example: 1,2-dichloro-1,2-difluoro-ethane

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Point Groups Cs
Only a mirror plane. Examples: CH2ClBr and HOCl

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Point Groups Cn
Only an n-fold rotation axis. Examples: non-planar H2O2 (C2) and PPh3 (C3)

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Point Groups Cnv n-fold rotation axis and n vertical mirror planes.
Examples: H2O (C2v) and NH3 (C3v)

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Point Groups Cnh n-fold rotation axis and horizontal mirror plane.
Example: trans-C2H2Cl2 (C2h) & B(OCH3)3 (C3h)

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Point Groups Dn
n-fold axis with n perpendicular 2-fold axes. Examples: Ph2 (D2) and Co(en)33+ (D3)

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Point Groups Dnd n-fold axis with n perpendicular two-fold axes

and n dihedral planes Example: staggered C2H6 (D3d)
H C H H C H H H

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C3

Point Groups Dnh n-fold axis with n perpendicular two-fold axes

and a horizontal mirror plane. Examples: C2H4 (D2h) and PF5 (D3h)

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Point Groups Td
Four 3-fold axes and three 2-fold axes. Example: CH4

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Point Groups Oh
Three perpendicular 4-fold axes, four 3-fold axes and a centre of inversion. Example: SF6

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Point Groups
Flow-Chart for Assigning Point Groups
C n?
No Yes Yes

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C 2" C n?

Yes

!h ?
No

Yes

Dnh

No Yes

!?
No

Cs

!h ?
No

Cnh

!v ?
No

Yes

Dnd

i?
No

Yes

Ci

!v ?
No

Yes

Cnv

Dn

C1

Cn

Note: Start by testing for Td , Oh , C!v and D!h groups

Character Tables
Each point group has a character table that summarizes symmetry information for the group.
classes of symmetry operations C2v A1 A2 B1 B2 symmetry species E +1 +1 +1 +1 C2(z) +1 +1 -1 -1 !v(xz) +1 -1 +1 -1 !v'(yz) +1 -1 -1 +1 z Rz x, Ry y, Rx x2, y2, z2 xy xz yz

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a character, $ a representation, #

basis functions

Character Tables

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We will use symmetry species to label molecular properties, e.g. orbitals, electronic states, vibrational modes, etc. Each symmetry species is uniquely defined by a set of characters, $, known as a representation, #. The characters, $, of a symmetry species tell us how an object (e.g. an orbital) is affected by symmetry operations in the point group.

Character Tables

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If an object is symmetric (unchanged) with respect to a symmetry operation, its character is +1.

The dx!-y! orbital is unchanged by the C2(z) operation, so its character $ is +1.

Character Tables

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If an object is antisymmetric (i.e. changes sign) with respect to a symmetry operation, its character is -1.

The px orbital changes sign under the C2(z) operation, so its character $ is -1.

Character Tables
Main symbols for the symmetry species mean: A non-degenerate and symmetric with respect to the principal rotation axis. B non-degenerate and antisymmetric with respect to the principal rotation axis. E doubly-degenerate T triply-degenerate

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Character Tables
C2v A1 A2 B1 B2 C3v A1 A2 E E +1 +1 +2 E +1 +1 +1 +1 C2(z) +1 +1 -1 -1 !v(xz) +1 -1 +1 -1 !v'(yz) +1 -1 -1 +1 z Rz x, Ry y, Rx x2, y2, z2 xy xz yz

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2C3 +1 +1 -1

3 !v +1 -1 0 z x2 +y2, z2 Rz (x, y) (Rx, Ry) (x2 - y2, xy) (xz, yz)

Character Tables
Subscripts: g symmetric with respect to inversion. u antisymmetric with respect to inversion.
C2h Ag Bg Au Bu E +1 +1 +1 +1 C2 +1 -1 +1 -1 i +1 +1 -1 -1 !h +1 -1 -1 +1 Rz Rx, Ry z x, y x2, y2, z2, xy xz, yz

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Character Tables
Subscripts: 1

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symmetric with respect to !v or (in the case of dihedral groups) a C2 axis perpendicular to the principal rotation axis. antisymmetric with respect to !v or (in the case of dihedral groups) a C2 axis perpendicular to the principal rotation axis.
E +1 +1 +2 2C3 +1 +1 -1 3 !v +1 -1 0 z x2 +y2, z2 Rz (x, y) (Rx, Ry) (x2 - y2, xy) (xz, yz)

C3v A1 A2 E

Character Tables
Superscripts:

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! symmetric with respect to !h. " antisymmetric with respect to !h.

D3h A1' A2' E' A1" A2" E" E +1 +1 +2 +1 +1 +2 2C3 +1 +1 -1 +1 +1 -1 3C2 +1 -1 0 +1 -1 0 !h +1 +1 +2 -1 -1 -2 2S3 +1 +1 -1 -1 -1 +1 3 !v +1 x2 + y2, z2 -1 Rz 0 (x, y) (x2 - y2, xy) -1 +1 z 0 (Rx, Ry) (xz, yz)

Character Tables
Examples: A 2" ! ! ! B1u ! ! ! a non-degenerate symmetry species, which is symmetric with respect to the principal axis antisymmetric with respect to "v symmetric with respect to "h a non-degenerate symmetry species, which is antisymmetric with respect to principal axis symmetric with respect to "v antisymmetric with respect to inversion

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Character Tables
Linear molecules with no inversion centre (e.g. CO)
C#v $+ $% & ' : E 1 1 2 2 : C2 +1 +1 %2 +2 : 2C4 +1 +1 0 %2 : #"v +1 z x2 + y2, z2 %1 Rz (xz , yz) 0 (x,y) (Rx,Ry) 0 (x2 - y2, xy)

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Character Tables
Linear molecules with an inversion centre (e.g. CO2)
D#h E $ g+ 1 $ g% 1 &g 2 'g 2 : : $ u+ 1 $ u% 1 &u 2 'u 2 : C2 +1 +1 %2 +2 : +1 +1 %2 +2 2C4 +1 +1 0 %2 : +1 +1 0 %2 #"v +1 %1 0 0 i +1 Rz +1 +2 (Rx,Ry) +2 : +1 %1 z %1 %1 0 %2 (x,y) 0 %2 x2 + y2, z2 (xz , yz) (x2 - y2, xy)

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Character Tables
Do I have to memorize these character tables?
! ! ! No. (Phew!) All can be found in the Symmetry Tables file on Wattle

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In an exam, any required character tables will be provided.

Orbital Symmetry

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The rules for determining the character $ associated with a symmetry operation on an orbital are: 1.! If the operation moves the centre of the orbital, then $ = 0.

Orbital Symmetry
2. If the operation swaps the orbital with another orbital on the same atom, then $ = 0.

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Orbital Symmetry
3. If the operation leaves the orbital unchanged, then $ = +1.

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Orbital Symmetry
4. If the operation changes the sign of the orbital, then $ is -1.

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Orbital Symmetry

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What are the characters of the oxygen 2p orbitals in the C2v water molecule?

Orbital Symmetry

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$ = +1 $ = -1 $ = +1 $ = -1

Orbital Symmetry

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$ = +1 $ = -1 $ = -1 $ = +1

Orbital Symmetry

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$ = +1

$ = +1

$ = +1 $ = +1

Orbital Symmetry
C2v E +1 +1 +1 C2(z) +1 +1 -1 -1 C2 -1 -1 +1 !v(xz) +1 -1 +1 -1 !v(xz) +1 -1 +1 !v'(yz) +1 -1 -1 +1 z Rz x, Ry y, Rx x2, y2, z2 xy xz yz !v'(yz) Species -1 +1 +1 B1 B2 A1

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#(2px) #(2py) #(2pz)

C2v A1 A2 B1 B2 E +1 +1 +1 +1

Orbital Symmetry

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An orbital belonging to a degenerate symmetry species (E or T) will not transform correctly in isolation. Degenerate orbitals must be considered collectively when generating the characters under a symmetry operation. Example: the 4p orbitals on bromine in BrF5 which has C4v symmetry:
C4v A1 A2 B1 B2 E E +1 +1 +1 +1 +2 2C4 +1 +1 -1 -1 0 C2 +1 +1 +1 +1 -2 2 !v +1 -1 +1 -1 0 2 !d +1 -1 -1 +1 0
z Rz x2-y2 xy (x, y) (Rx, Ry) (xz, yz) x2+y2, z2

Orbital Symmetry

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Orbital Symmetry

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Orbital Symmetry
C4v E +1 +1 +1 2 2C4 +1 0 0 0 C2 +1 -1 -1 -2 2 !v +1 +1 -1 0 2 !d +1 0 0 0 Species A1 -% -% E

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#(pz) #(px) #(py) #(px+py)

In generating the above characters, the same !v and !d reflection planes are used for all three p orbitals.

Individually, the px and py orbitals on the Br atom do not transform as a symmetry species of the C4v point group. However, together, they transform as the doubly degenerate E species.

Orbital Symmetry

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The transformation of s, p and d orbitals on the central atom in a molecule can be determined directly from the point group character tables. An s orbital always transforms as the totally symmetric representation (the first listed symmetry species with all $ = +1). The p and d orbitals transform the same as the following basis functions:
Orbital: Basis fn: px x py y pz z dxy xy dxz xz dyz dx!-y! yz x2-y2 dz! z2

In some point groups e.g. C2v, the dx!-y! orbital transforms as two separate functions x2 and y2.