Normal Modes of Vibration

C734b 2008

C734b 2008 Normal Modes of Vibration

Internal vibrational modes of a molecule containing N atoms is made up of the superposition of 3N-(5 or 6) simple harmonic vibrations called normal modes -5 for linear molecules (3 translations + 2 rotations) -6 for nonlinear molecules (3 translations + 3 rotations) Normal coordinates , Qk, are linear combinations of atomic displacements xi, yi, zi from the equilibrium positions of the atoms. {Qk} are properties of the molecules and are determined by molecular symmetry each transforms according to one or other IR of the molecular point group.

C734b 2008 Normal Modes of Vibration

To find the normal modes study the transformation of the atomic displacements {xi yi zi) by setting up a local basis set (ei1 ei2 eis) on each atom.

Example: H2O (C2v)

3N = 3x3 = 9 vectors
x2 z2

x1 z1

O
y1

y2 x3 z3

y3

Molecule lies in the yz plane

C2v: {E, C2, v(xz), v (xz)

( R) will be a 9x9 matrix

C734b 2008 Normal Modes of Vibration 3

1 0 0 0 (E ) = 0 0 0 0 0

0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 1

atom 1

atom 2

atom 3

(E ) = 9
C734b 2008 Normal Modes of Vibration 4

(C2): x1 -x3 y1 -y3 z1 z3

x2 -x2 y2 -y2 z2 z2

x3 -x1 y3 -y1 z3 z3

0 0 0 0 0 0 0 0 (C2 ) = 0 0 0 0 1 0 0 1 0 0

0 0 0 0 0 0 0 0 1

0 1 0 0 0 0 1 0 0 0 0 1 1 0 0 0 0 0 0 1 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

atom 3

atom 2

atom 1

(C2 ) = 1
C734b 2008 Normal Modes of Vibration 5

[v(xz)]:

x1 x3 y1 -y3 z1 z3

x2 x2 y2 -y2 z2 z2

x3 x1 y3 -y1 z3 z1 atom 3

0 0 0 0 0 0 0 0 ( v ( xz ) ) = 0 0 0 0 1 0 0 1 0 0

0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0

1 0

0 1 0 0 0 0 1 0 0 0 0 1 0 0 0 0 0 1 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

atom 2

atom 1

[ v (xz )] = +1
C734b 2008 Normal Modes of Vibration 6

[v(yz)]:

x1 -x1 y1 y1 z1 z1

x2 -x2 y2 y2 z2 z2

x3 -x3 y3 y3 z3 z3

1 0 0 0 ( v ' ( yz ) ) = 0 0 0 0 0

0 0 1 0 0 1 0 0 0 0 0

0 0 0

0 0 0 0 0 0 0 1 0 0 0 0 0 1 0 0

0 1 0 0 0 0 0 0 0 0 0
'

0 0

0 0

[ v ( yz )] = +3

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 1 0 0 0 1 0 0 0

atom 1

atom 2

atom 3

C734b 2008 Normal Modes of Vibration

Reducible character set is: = {9, -1, +1, +3} Don Dont want to do this for large molecules! Shortcut: recognize that (R) contribution = 0 from atoms which move because they contribute only to off-diagonal matrix elements. Let NR = # atoms which do not move for a given symmetry operation, R.

(R ) = x , y ,z N R

x , y ,z

= character representation for (x,y,z)

This may require doing a direct sum

x , y , z (C2 v ) = A1 B1 B2

Can read this off the character table

x , y ,z = {3,1,+1,+1}

x , y ,z N R = {3 3,11,+11,+1 3}

={9,-1,1,3} same reducible representation as before.

C734b 2008 Normal Modes of Vibration 8

Do reduction in C2v
1 [(9)(1)(1) + (1)( 1)(1) + (1)(1)(1) + (3)(1)(1)] = 3 4 1 a2 = [(9 )(1)(1) + (1)( 1)(1) + (1)( 1)(1) + (3)(1)( 1)] = 1 4 1 b1 = [(9 )(1)(1) + (1)( 1)( 1) + (1)(1)(1) + (3)(1)( 1)] = 2 4 a1 = b2 = 1 [(9)(1)(1) + (1)( 1)( 1) + (1)( 1)(1) + (3)(1)(1)] = 3 4

total = 3 A1 A2 2 B1 3B2

From character table:

translation transforms as x y z = B1 B2 A1

rotation transforms as Rx R y Rz = B2 B1 A2

C734b 2008 Normal Modes of Vibration

Subtract from total = vib = total translation - rotation

vib = 2 A1 B2
Allowed transitions

Note: 3N-6 = 3 for H2O # modes deduced!

It can be shown that the transformation of atomic displacements {xi, yi, zi} to a set of normal coordinates {Qk} results in a Hamiltonian which is a sum of one-dimensional harmonic oscillators. Therefore the wave function is a product of 1D harmonic oscillator wave functions:

n nk = N k H n ( k Qk )e
k k

2 2 k Qk

where k =

k
h

and nk vibrational quantum number of the kth mode.

C734b 2008 Normal Modes of Vibration

10

 n1 ,n2 ,L (Q1 , Q2 , L) = nk (Qk )

k =1

5 3 N 6

or

n1 , n2 ,L = n1 n2 L = nk
k

Typically, most molecules are in their ground vibrational ground state where nk = 0 for k =1, , 3N-6 or 3N-5
= e
k
2 2 k Qk

Note: H0 constant

which is invariant under any point symmetry operation; that is, its totally symmetric. Ground states of all normal modes transform as the totally symmetric IR of the point group of the molecule Excited vibrational state symmetry is determined by the symmetry products of the particular Hermite polynomials of the normal mode(s) involved.
C734b 2008 Normal Modes of Vibration 11

Most common transitions are fundamental transition where only a single vibrational mode is excited.

ni = 0; ni nk

nk = 1

0,0,L ,0, L ,0 0,0, L,1, L ,0

Note: H1(x) = 2x which means the ground state transforms like 1 and the excited state transforms like Qk. Transitions are induced by infrared radiation. The operator responsible is the electric dipole moment operator, D.

r = er D
A transition is allowed if the matrix element
0,0,L,0,L,0 0 0,0, L1,L,0 | D

C734b 2008 Normal Modes of Vibration

12

Thus: A fundamental transition is allowed only if the normal coordinate Qk for that mode forms a basis for the same IR as x, y, and/or, z.

For water in C2v, A1 transforms as z, B1 transforms as x, and B2 transforms as y.

Q vib = 2 A1 B2 all 3 vibrations are allowed.

Note: only light polarized along the z-axis and the y axis will excite water. Not an issue in gases or liquids since i) the light sources are often incoherent sources (random polarizations), and ii) the molecules tumble about. Such polarization effects could arise using lasers and exciting solid samples whose orientation have been fixed. It can also have a bearing on samples adsorbed onto surfaces.
C734b 2008 Normal Modes of Vibration 13

Raman Scattering
Raman scattering is an inelastic scattering process. Photon looses (or gains) one quantum of vibrational energy to (or from) the molecule. Here, the electric field of the light indices an electric dipole in the molecule, a process that depends on the polarizability of the molecule, .

r r D = E
xx zx

is a tensor which has the form: yx

xy xz yy yz zy zz

ij = ji

The components of the polarizability transform like the binary products of coordinates, x2, y2, xz, etc.

C734b 2008 Normal Modes of Vibration

14

Thus: A fundamental transition is Raman active if a normal mode forms a basis for one or more components of the polarizability

For H2O A1, A2, B1, and B2 are all Raman active. This means there are 3 Raman bands and therefore 3 coincidences with the infrared absorption spectrum. Here coincidence implies the same frequency. Some general points: 1.) If the symmetry of the molecule is lowered by a perturbation, this may remove degeneracies and/or permit transitions that were forbidden in the more symmetric molecule. 2.) The number of Raman and infrared bands can sometimes be used to distinguish between various structures. 3.) Molecules having an inversion center will have Raman and infrared bands but no coincidences.
C734b 2008 Normal Modes of Vibration 15

4.) Stretching modes (for example C=O bonds) can often be analyzed separately because they come in a characteristic region of the infrared spectrum. This means a full vibrational analysis is unnecessary. Instead, study the transformation of the unit vectors directed along the appropriate ligands. For example: ML3(CO)3

L L M C=O L C=O C=O

It is only necessary to study the 3 vectors in C2v symmetry to determine the symmetry of the CO stretching modes.

C734b 2008 Normal Modes of Vibration

16

Example: Consider the case of Fe(CO)5 Raman and IR spectra of the molecule in the region of the CO stretches.

2 IR bands

3 Raman bands

The molecule can have two geometries. Do these spectra help to distinguish them?

C734b 2008 Normal Modes of Vibration

17

CO

C4v
CO CO

OC OC

Fe

E 2C4 CO 5
B1 E

C2 1

2 v 3

2 d 1
Raman active? Yes Yes Yes

CO = 2 A1

IR active? Yes No

Predict 3 IR bands and 5 Raman bands

Yes

C734b 2008 Normal Modes of Vibration

18

CO

OC

Fe CO

CO
CO

D3h

CO

E 5

2C3 2

3C2 h 1 3
IR active? No Yes

2S3 0

3 v 3
Raman active? Yes Yes

CO = 2 A1' E'
" A2

Expect 2 IR bands and 3 Raman bands

Yes

No

C734b 2008 Normal Modes of Vibration

19

The spectra is most consistent with Fe(CO)5 having a D3h geometry. This was ultimately confirmed to be the case by X-ray crystallography.

C734b 2008 Normal Modes of Vibration

20

10