5/.

Symmetry and Infrared (IR) Spectroscopy of Inorganic Molecules

a/. Introduction
Infrared and Raman spectroscopy are common techniques used to study vibrations of
molecules

Electromagnetic Spectrum

red
Sub
Near IR Mid IR Far IR millimeter
1104 cm-1 4000 cm-1 400 cm-1 10 cm-1
 I0 I

Source sample detector

I
I0 % transmittance =
I
I0
%

Electromagnetic wave
The interaction of infrared radiation with a molecule involves interaction of the oscillating electric field
component of the radiation with an oscillating electric dipole moment in the molecule.

Electric dipole in a chemical bond (bond dipole moment) arises from different electron distribution
between the two atoms

Consider a diatomic molecule AB and the atom B is more electronegative than the atom A, the
centroid of the electron charge is closer to B than A.

centroid of nuclear charges

nucleus of atom A nucleus of atom B

r
dipole moment is a vector
(magnitude and direction)
Centroid of electron charge

If the vibration or bending of chemical bonds in a molecule result in the change of the molecule’s dipole
moment, then the molecule will absorb infrared energy at a frequency corresponding to the frequency of the
bond’s natural vibration.

e.g. N‐N stretching in N2 is infrared inactive because of no change in dipole moment but H‐F stretching is infrared 
active. 
b/. 3N-6/5 rule

For polyatomic molecules, there are more than one vibrational modes.

Linear molecules

No. of Vibrational Mode = 3N – 5

N = no. of atoms in a molecule

Non-Linear molecules

No. of Vibrational Mode = 3N – 6

Linear Molecules

e.g. CO2 O C O

A linear molecule with 3 atoms

No. of Vibrational Mode = 3(3) – 5 = 4

Bend
Symmetric Stretch

+ +
Bend Asymmetric Stretch
Non-Linear Molecules
S
e.g. SO2
O O
A non-linear molecule with 3 atoms

No. of Vibrational Mode = 3(3) – 6 = 3

Scissoring (symmetric bend)

Symmetric Stretch

Asymmetric Stretch
 c/. Symmetry and IR Spectroscopy
The symmetry of a vibrational modes determines whether it is infrared
active (absorb IR radiation)

e.g. Why cis and trans isomers of [Pd(NH3)2Cl2] have different number of Pt-N and Pt-
Cl stretching bands?

NH3

Cl Pd Cl

trans NH3

NH3

H3N Pd Cl

Cl
cis

IR spectra of trans- and cis-[Pd(NH3)2Cl2]

 d/. Selection Rules

For a mode of vibration to be infrared (IR) active, it must give

rise to a change in the molecular dipole moment

IR inactive as Dipole moment is a vector.

e.g. sum of the 2
vectors = 0 IR active
CO2

Bend
Symmetric Stretch

+ +
Bend Asymmetric Stretch
IR active IR active
 Character table of the point group of a molecule can be used to
determine whether a particular vibrational mode is IR active

If the symmetry label/irreducible representation (e.g. A1, B1) of

a vibrational mode is the same as the symmetry
label/irreducible representation of either x, y or z in the
character table, then the mode is IR active
e.g. SO2 C2v symmetry A simple way to find the characters of
the vibration mode in all the symmetry
Symmetric Stretch operations (only works for non-
degenerate symmetry A and B)

C2 rotation
 xz reflection

yz reflection

C2v E C2 (z) σv(xz) σv(yz)

1 1 1 1
 “1” means no change, “-1” means a reversal of the direction of the vector

linear,
C2v E C2 (z) σv(xz) σv(yz) quadratic
rotations
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

As the symmetry of the vibrational mode has the same A1 symmetry as

the z. It is IR active

The vibrational mode is said to have A1 symmetry

symmetry of the scissoring mode – how the O-S-O angle or the vectors
is affected by all the symmetry operations of C2v point group

C2v E C2 (z) σv(xz) σv(yz)

A1 1 1 1 1

Scissoring

The scissoring (symmetric bend) has a A1 symmetry and is IR active

2 modes of Pd-Cl stretching and two modes of Pd-N stretching

NH3 symmetric stretch asymmetric stretch

NH3 NH3

Cl Pd Cl
Cl Pd Cl Cl Pd Cl
NH3 IR inactive IR active
NH3 NH3
D2h
NH3 NH3

Cl Pd Cl Cl Pd Cl

NH3 IR inactive NH3 IR active

NH3 NH3 NH3

H3N Pd Cl H3N Pd Cl H3N Pd Cl

IR active IR active
Cl Cl Cl
NH3 NH3
C2v
H3N Pd Cl H3N Pd Cl
IR active IR active
Cl Cl
 Similar analysis can be used to determine whether the stretching of a diatomic
ligand is IR active
e.g. stretching of CO bond in metal carbonyl complexes. CO stretching
band: ~2000 cm-1, sharp and intense
O
Symmetric stretch
L C
L L L L
M M
C C L L
O L O C
O
IR active IR inactive
Cis trans
O
asymmetric stretch
C
L L L
L L M
M L L
C C
O O C
L
O
IR active IR active
The symmetry of the CO stretching modes can be determined by finding the
characters of the vectors in the symmetry operations of the point group

PPh3
D4h O O
C C
Mo IR inactive
C C
O O
PPh3

This symmetric stretch has B1g symmetry

linears,
E 2C4 (z) C2 2C'2 2C''2 i 2S4 σh 2σv 2σd quadratic
rotations
B1g 1 -1 1 1 -1 1 -1 1 1 -1 x2-y2
Give the symmetry of the following three vibration modes:

Cl 2-
Cl 2- - Cl 2-

Cl Pt Cl Cl Pt Cl +Cl Pt Cl +

Cl Cl - Cl

Based on the symmetry of the molecule and the vibrational

modes, determine whether the vibrational modes are infrared
active. Briefly explain your answer.