Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 1 7.

Symmetry and Spectroscopy Molecular Vibrations

7.1 Bases for molecular vibrations
We investigate a molecule consisting of N atoms, which has 3N degrees of freedom. Taking
the translations (3) and rotations (3 for non-linear, 2 for linear molecules) into account, we
obtain 3N-6 (5) vibrational degrees of freedom for the non-linear (linear) case. In order to
describe those, we choose an arbitrary set of basis vectors in order to describe the 3N
displacements from the equilibrium position (the choice is arbritrary, but a choice having
simple transformation properties might be advantageous).

Example: BF3 or CO3212 degrees of freedom: 3 translations, 3 rotations, 6 vibrations

displacement basis d:

7.2 Normal modes

We are interested in the collective vibrational modes of the molecules. These collective
modes Q with identical frequency and phase are denoted as normal modes.
As a pictorial representation of the modes, we indicate the set maximal displacements, e.g.:

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 2 As we will see later, normal modes can be classified with respect to the irreps of the point
group of the molecule.
In analogy to the strategy followed in chapter 5 for the electronic structure of molecules, we
can transform the displacement basis of dimension 3N into a symmetry adapted set of
displacement coordinates D:
x1

y
r
r 1
r

D = d with d = z1

x2

M
In the next step we transform the basis D into the basis of normal modes

r
r
Q = D .
In analogy to chapter 5, the matrix is blockdiagonal, i.e. the normal coordinates are linear
combinations of the SALCs of displacements belonging to one irrep of the point group of the
molecule (Wigners theorem).
As an example we classify the normal vibrations of CO32-, BF3
(D3h):
(7.1 Character table D3h).

Note: Q3, 4 and Q5, 6 are transformed into linear combinations

of each other by symmetry operations of the group. They
belong to 2 dimensional irreps.

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 3 7.3 Symmetry of normal modes
We would like to classify the normal modes Qi of the molecules with respect to the irreps
which they belong to. For this purpose, we analyse the 3N dimensional representation of the
displacements with respect to the irreps of the group.

Example: BF3 (C3v), 12 dimensional displacement basis

E: all diagonal elements ii(E)=1 ( E ) = 12

h: x, y, displacements are retained, z displacement changes sign ( h ) = 4

C2: displacements of atoms, which change position do not contribute to ii (off diagonal
elements) ( C 2 ) = 2

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 4 -

x' cos 120 sin 120 x1

( = 1 )
C3: z1 is invariant ( = 1 ), for x1,y1: 1 =
y' 2 sin120 cos 120 y 2

( C3 ) = 0
S3: analogous to C3, but z1=-z1 ( = 1 )
( C 3 ) = 2

v: y, z, displacements at two positions are invariant, x displacement changes sign

( v ) = 2

D3h

2C3

3C2

2S3

3v

12

= A1' + A2' +3E' +2 A2'' + E''

Symmetry of translations and rotations from character table:
Tx ,Ty = E' ; Tz = A2''
Rx ,Ry = E' ' ; Rz = A2'
(7.2 Classify translations and rotations in D3h).

The remaining vibrational normal modes are: vib = A1' +2 E' + A2' '

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 5 (7.3 Excercise: classify the vibrational modes of SF6 with respect to their symmetry, substitute one F by Cl).

7.4 Analysis of normal modes

We assume that we have determined the complete potential energy surface of an N atom
molecule V(r1,r2,...r3N) and expand V into a Taylor series at the equilibrium geometry:
V
1 2V
1 3V

ri +
ri rj +
ri rj rk + ...
ri 0
2 i , j ri rj 0
6 i , j ,k ri rj rk 0
12
3
1
424
3
14243

V = V0 +
{
i
equilibriu m
energy

=0 for expansion
at equilibriu m position

force constants k ij
(harmonic)

anharmonicities

We start from the equation of motion for the molecule

mi &r&i = kij ri
j

and use the ansatz ri = ri 0 eit which yields

mi ri 0 2 = kij ri 0 .
j

Introducing mass weighted coordinates Ri = mi1 / 2 ri this equation is simplified to

Ri 0 2 =
j

kij
Ri 0
1/ 2
mi mi1 / 2
1
424
3
Kij

r
r
R 2 = K R .

or

As usual we solve the set of 3N linear equations by determinig the eigenvalues 2 i and

r
r r
r
r
r
eigenvectors i . By transforming to a new basis Q = R with = 1 , 2 ,..., 3N , i.e. the
basis of normal coordinates, the matrix of force constant = K

r
v
Q 2 = Q

or

becomes diagonal:

Qi 0 2 = ij Q j 0 = iiQi 0 .
j

Thus we obtain a set of 3N decoupled degees of motion (vibrations, rotations, translations). If

we express the total energy

E = T +V =

1
2
1
mi r&i + kij ri rj

2 i
2 i, j

in terms of the new coordinates, we obtain

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 6 -

E=

2
2
1
1
1
1
1
2
2
Q& i + ij Qi Q j = Q& i + ii Qi = Q& i + ii Qi

2 i
2 ij
2 i
2 i
2 i

In a quantum mechanical description we can describe the Hamiltonian as a simple sum over
harmonic oscillators

1
h2 2
1
H = H i with H i =
+ ii Qi2
2
2 i
2 Qi
2
with the well known solutions
i1/ 2 12 hi Qi2
;
vi (Qi ) = N vi H vi 1/ 2 Qi e
hi

E vi = vi + 12 hi ;

i = i1 / 2 ;

vi = 1,2,3,... ;

(Hj(x): Hermite polynomials)

Consequently, the vibrational wavefunction of the molecules is

vib = vi (Qi ) with Evib = Evi .

i

(7.4 Example: normal modes of C2H2)

.

7.5 Symmetry of vibrational wavefunctions: fundamental modes

We consider a molecules with N vibrational modes. The excitation from the vibrational
ground state ( vi = 0; i = 1...N ) to a state with a singly excited normal mode
( v k = 1; vi = 0; i = 1,...k 1, k + 1...N ) is referred to as a fundamental mode of the molecule.
Symmetry of the ground state:
1

vib = Ne

i 2 hi Qi2

Effect of symmetry operation R on

(a) non degenerate modes:
Qi Qi
1

R vib = Ne

i 2 hi (Q )i2

= vib

(a) i = 1..n degenerate modes:

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 7 -

Qi ij Q j with
j

R vib = Ne

1
2h

Qi2

= ik (orthonormalization)

ij

kj

1
2h

ijQ j

= Ne

= Ne

1
2h

Qi2
i

= vib

Thus, the vibrational ground state is invariant under all symmetry operations, i.e. vib,0 = A1 .
Symmetry of the excited state:
1

vib = NQk e

i 2 hi Qi2

Symmetry of wavefunction is equal to symmetry of Qk, i.e. vib,k =1 = Qk .

7.6 Symmetry of vibrational wavefunctions: combination modes

The excitation from the vibrational ground state ( vi = 0; i = 1... N ) to a state with several
normal modes excited by one vibrational quantum each ( v k = 1; vl = 1 ) is referred to as a
combination mode of the molecule.
Symmetry of the excited state:
1

vib = NQk Ql e

i 2 hi Qi2

Symmetry of wavefunction is equal to the direct product of the representations of Qk and Qk,
i.e. vib,k =1,l =1 = Qk Ql .
(7.5 Excercise: symmetry of the combination modes of BF3).

7.7 Symmetry of vibrational wavefunctions: overtones

The excitation from the vibrational ground state ( vi = 0; i = 1... N ) to a state with several
vibrational quanta in one normal mode ( v k > 1 ) is referred to as a overtone of the mode.
Symmetry of the excited state:
(a) non degenerate case

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 8 vib = NUH vk (

1/ 2
k

Qk ) with U = e

2 hi Qi2
i

and k =

k
h

Hermite polynomials:
H 0 (z ) = 1

H1 (z ) = 2 z
H 2 (z ) = 4 z 2 1
H 3 (z ) = 8 z 3 12 z

H 4 (z ) = 16 z 4 48 z 2 + 12
Note: even for even vk, odd for odd vk. Therefore
for vk = 2n
vib
A1 for v k = 2n
or vib =
R vib =
Qk (R ) vib for v k = 2n + 1
Qk for v k = 2n + 1

(a) degenerate case

Similar as for the problem of several electrons occupying the same set of degenerate orbitals
(chapter 6), quantum statistics restricts the number of vibrational states if several vibrational
quanta occupy the same degenerate mode. Thus the problem becomes significantly more
complicated .
We consider the case of a twofold degenerate vibrational mode (Q1, v1; Q2, v2):
1 vibrational quantum:

(v1=1; v2=0) (v1=0; v2=1)

2-fold degenerate

2 vibrational quanta:

(v1=2; v2=0) (v1=1; v2=1) (v1=0; v2=2)

3-fold degenerate

3 vibrational quanta:

(v1=3; v2=0) (v1=2; v2=1) (v1=1; v2=2) (v1=0; v2=3)

4-fold degenerate

n vibrational quanta:

n+1 fold degenerate

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 9 (analogous: n vibrational quanta in three-fold degenerate mode: (v+1)(v+2) vibrational
wavefunctions; see textbooks)

As an example we consider the wavefunctions for v1+v2=3:

3, 0 = NU (8 3 / 2Qa3 12 1 / 2Qa )
2,1 = NU (4Qa2 2 )(2 1 / 2Qb )
1, 2 = NU (2 1/ 2Qa )(4Qb2 2 )
0, 3 = NU (8 3 / 2Qb3 12 1 / 2Qb )

We consider linear combinations Qa, Qb, for which the transformation matrix of a given
symmetry operation R is diagonal (this is always possible for single operation, for other
symmetry operations the transformation is of course not diagonal because the functions
belong to a two dimensional representation):
Qa ' = aaQa
Qb ' = bbQb
As the cubic and the linear terms of the wavefunctions must transform indetically, we only
consider the cubic terms:

3, 0 : Qa '3 = aa Qa
3

2,1 : Qa ' 2 Qb ' = aa bbQa Qb

2

1, 2 : Qa ' Qb ' 2 = aa bb QaQb

2

0, 3 : Qb ' 3 = bb Qb
3

Therefore, the character of the 4 dimensional representation is

3 (R ) = Ra3 + Ra2 Rb + Ra Rb2 + Rb3

Analogous: 2 (R ) = Ra2 + Ra Rb + Rb2 and (R ) = Ra + Rb3

Repeated application of R: (R n ) = Ran + Rbn

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 10 In general, one can show that the general recursion formula is valid (see Wilson, Decius,
Cross): v (R ) =

1
(
(R ) v 1 (R ) + (R v )) .
2

(analogous for triply degenerate normal coordinates:

1
1

2
v (R ) = 2 (R ) v 1 (R ) + (R 2 ) [ (R )] v 2 (R ) + (R v ) , see Wilson, Decius, Cross)
3
2

With this information it is possible to construct the characters of an k-fold excited vibrational
states corresponding to a twofold degenerate normal coordinate and analyse the representation
(notation ()n) which they span in terms of the irreps of the group (similar formulae exist for
higher degenerate normal coordinate, see Wilson, Decius, Cross).
(7.6 Exercise: What is the symmetry of the first and second overtone of an E vibrational mode of CH4?).

The intensity of overtones and combination bands is relatively low in most cases. In some
cases these weak transitions become important. We assume that there is a singly excited state
v1 =1,v2 = 0 and a 1st overtone v1 = 0, v2 = 2 with similar vibrational energy. If both states have the

same symmetry (or contain a component with identical symmetry), a coupling between both
state is possible, i.e. matrix elements v1 =1,v 2 =0 H v1 =0,v2 = 2 can be nonzero. The eigenstates
of the coupled modes are mixed vibrational wave functions i ' = ci1 v1 =1, v2 =0 + ci 2 v1 =0,v2 = 2 .
The effect is denoted as Fermi resonance and leads to an intensity borrowing of the weak
combination band or overtone from the fundamental as well as to a repulsion between both
states (compare section 5.6).
(7.7 Example: Fermi resonance in CO2).

7.8 Symmetry of vibrational wavefunctions: arbitrary excited states

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 11 According to sections 7.5 to 7.8 the symmetry of an arbitrary vibrational state with the
vibrational quantum numbers v1, v2, v3,... corresponding to the normal modes of symmetry 1,
2, 3,... is:
vib = (1 ) 1 (2 ) 2 (3 ) 3 ...
v

Note: We have discussed the symmetry of vibrational wavefunctions in terms of the harmonic
approximation. However, the results are not affected, if we take anharmonicities into account,
as the different parts of the Taylor expansion of the Hamiltonian (section 7.4) must be totally
symmetric (A1) within the group of the molecule. If we thus express the anharmonic wave
function as a sum over harmonic functions anh = ai i , only those functions contribute,
i

which have the same symmetry.

7.9 Selection Rules

Electrical dipole transitions are described by matrix elements if the type

f i i where i are the components of the vector of the dipole operator (with i=x,y,z).

We have seen that the integrand must be totally symmetric (A1) for the integral to be non
zero. This immediately leads to the dipole selection rule:
A1 vib, f i vib,i

Note:
We consider the components of the dipole moment operator

x = qi xi ; y = qi y i ; z = qi zi
i

(1) A symmetry operation exchanges equivalent atoms with identical charge.

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 12 (2) The operator contains the sums

x ; y ; z
i

only, which remain unaffected by a

change of indices.
Therefore, it is sufficient to investigate the transformation properties of the functions x, y, z,
which span the same representation as the components of the dipole operator. Typically, these
are tabulated in the character table.

Remark concerning IR reflection absorption spectroscopy (IRAS) at metallic surfaces: For

metallic surfaces the parallel component of the electric field is efficiently screened by the
conduction electron. Thus the electric field vector must be nearly perpendicular to the surface,
and only the electric field component perpendicular to the surface contributes to the field
strength at the surface. Similarly, dipole fields of the oscillating molecules are screened by the
conduction electrons. This resulting field is normally constructed by assuming an (imaginary)
image charge inside the metal. The image charge leads to the effect that perpendicular dipole
moments are amplified, whereas parallel dipoles are extinguished. Thus the relevant matrix
element for IR absorption at metallic surfaces is:
f z i .

If we assume excitation from the ground state ( i = A1 ) and take into account that z or z is
symmetric with respect to any possible symmetry operation of a surface, i.e. = A1 , we
z

obtain the so called metal surface selection rule (MSSR) as:

f = A1 .

Raman transitions are described by matrix elements if the type

f ij i where ij are the components of the tensor of the dielectric polarizability (with

i,j=x,y,z). Analogous to the previous case, we obtain the selection rule:

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 13 A1 vib, f i vib,i

As we will discuss in the next section, the polarizability is a symmetric tensor of rank 2
connecting the electric field and the induced dipole moment:
11 12 13
v
r
= 12 22 23 E

13 23 33

We will see that upon a symmetry operation described by the transformation matrix Rij this
type of tensor transforms according to

aij ' = Rik R jl kl .

kl

e.g.
a xx ' = R xx2 xx + R xy2 yy + R xz2 zz + 2 R xx R xy xy + 2 R xx R xz xz + 2 R xy R xz yz

Transformation of function x2 for comparison:

(x' )2 = (Rxx x + Rxy y + Rxz z )2 = Rxx2 xx + Rxy2 yy + Rxz2 zz + 2 Rxx Rxy xy + 2Rxx Rxz xz + 2 Rxy Rxz yz
Thus, the components of the tensor show the same transformation behaviour as the quadratic
forms x2, y2, z2, xy, xz, yz.

Typically, these functions are tabulated in the character table. But how are they determined?
In principle there are two methods:

(1) Application of the symmetry operation to the basis (x2, y2, z2, xy, xz, yz),
determination of the representation matrices and of their characters, analysis in terms
of the irreps of the symmetry group.

(2) Analogous to the method applied in the symmetry analysis of overtones (section 7.7)

Chapter 7 Symmetry and Spectroscopy Molecular Vibrations p. 14 wavefunctions of 1st overtone of 3fold deg. mode: Qa2, Qb2, Qc2, Qa Qb, Qa Qc, Qb Qc
quadratic functions of three coordinates: x2, y2, z2, xy, xz, yz

Example:
Symmetry of the quadratic forms in Td:
xyz=T2
R

8C3

3C2

6S4

6d

R2

C3

C2

(R)

-1

-1

(R2) 3

-1

(E)

Recursion formula for triply degenate modes (see section 7.7):

1
1

2
2 (R ) = 2 (R ) (R ) + (R 2 ) [ (R )] 0 (R ) + (R 2 )
3
2

1
2
= ( (R )) + (R 2 )
2

2(R) 6

A1 + E + T2

(7.8 Exercise: CO32-: Symmetry of normal modes, IR / Raman activity of fundamentals and 1st overtones).

Note: from the IR and Raman selection rules it is immediately evident that if the inversion i is
element of the symmetry group of the molecule, a IR active transition is Raman inactive and
vice versa (exclusion principle). Moreover all 1st overtones of centrosymmetric molecules are
IR inactive.