Vibrational Spectroscopy

Vibrational states and energies Vibrational spectroscopy Infrared Raman Normal Mode Analysis

Vibrational States and Energies

Quantum approach to vibration

Solution is Gaussian Energy is quantized 2 2 h 2 k Q = E 2 + 2 2 Q

1 E = v + h 2
Q
v is the quantum number Allowed transitions v -> v + 1, v -> v - 1

The bonding electronic state gives rise to a potential energy surface for the nuclear motion

Harmonic approximation
2 1 V Q = kQ 2 1/4 Q 2 0 Q = e 1/4 Q 2 1 Q = 2Qe

... E v = v + 1 h 2

There is a potential energy surface that corresponds to each electronic state of the molecule
The shift in the nuclear displacement arises from the fact that the bond length increases in the * state compared to the state. The overlap of the vibrational wave functions is key to understanding the shape of absorption bands.

There are 3N-6 vibrational degrees of freedom in a molecule with N atoms

Three degrees of freedom are required for translation. Three degrees of freedom are required for rotation. For example, in H2O there are 9 total degrees of freedom and 3 vibrational degrees of freedom. In C6H6 there are 36 degrees of freedom and 30 Vibrational degrees of freedom. Exception: In linear molecules there are only 2 rotational degrees of freedom and therefore the number of vibrations is 3N - 5.

The vibrational degrees of freedom can be expressed as normal modes.

All normal modes have the same form for the harmonic oscillator wavefunction and differ only in the force constant k and reduced mass . The total wavefunction is a product of normal modes. The total nuclear wavefunction for water is 123. The normal mode wavefunctions of water correspond to the symmetric stretch, bend, and asymmetric stretch. These are linear combinations of the stretching and bending internal coordinates of H2O.

Normal modes of water

In water vapor 1 3, but symmetries are different, 1 3. ( is the symmetry) However, the third overtone of 1 has the same symmetry 2 bend 1654 cm-1 as the combination band 1 1 1 = 1 3 3 . Strong anharmonic coupling leads to strong overtones at 11,032 and 10,613 cm-1. 3 asymmetric stretch 3935 cm-1

1 symmetric stretch 3825 cm-1

Comparison of harmonic and anharmonic potentials

Frequency shift due to molecular interactions

Hydrogen bonding lowers O-H force constant and H-O-H bending force constant.

vapor liquid 1 3825 3657 2 1654 1595 3 3935 3756

The intermolecular hydrogen bonding stretching mode is difficult to observe.

Vibrational Transitions

Transition dipoles
In order for infrared light to be absorbed the polarization must be aligned with the direction of the transition moment. For a vibrational mode this is determined by the directional change in the dipole moment. This is shown below for the bending mode of H2O.

O H H H

O H

Transition dipoles
The change in ground state dipole moment during vibration interacts with light.
g = g + Q+ Q

The first term is static and does not contribute to the transition. Calling the vibrational wavefunctions i the transition moment is:

g 10 = Q

1Q 0dQ,

Dipole derivatives
The vibrational wavefunctions i are Gaussians, thus the transition moment for transition from vibrational state 0 to vibrational state 1 is:

g 10 = Q

Q 2/2

Qe

2 Q 2/2

g 1 dQ = 2 Q

The transition dipole moment is proportional to the dipole derivative. This is true for any normal mode of vibration (i.e. harmonic).

Absorption of infrared radiation leads to vibrational transitions

v=0

Absorption of infrared radiation leads to vibrational transitions

v=1 v=0

The selection rule for vibrational transitions is v = 1

v=2 v=1 v=0

Two methods for calculating FC

The overlap of nuclear wavefunctions in the ground and excited state known as the FC factor can be expressed in a sum-over-states 2

FC =

v = 0 v = 0
0

v|v

or time correlator formalism.

1 FC =

i|i(t) e (i + 0)te tdt

The sum-over-states method

The absorption lineshape is determined by the displacement of the excited state potential energy surface. The FC factors can be calculated analytically in the linear coupling approx-imation (no frequency shift).

FC =

v=0

S ve S vh v!

The Franck-Condon factor determines the envelop of the absorption lineshape

S = 2/2
S is electron-phonon coupling is nuclear displacement

Resonance Raman spectrum is obtained by a laser light scattering experiment

Detector Lens Sample UV Laser Spectrograph

Inelastic light scattering produces a frequency shift. There is exchange of energy between the vibrations of the molecule and the incident photon.

Raman scattering
Raman scattering is an inelastic light scattering process. In the resonant picture it involves evolution in the excited state so it also depends on the FC factor and the transition dipole moment. On the left a sum-over-states picture is shown.

Kramer-Heisenberg-Dirac
Raman scattering depends on the molecular polarizability. The electric field drives the system into excited state |n> and then from |n> it returns to the final state |f>.
<i| |n><n| |f > <i| |n><n| |f > 1 = n = 1 0 + nf + i n 0 nf i n h

if

Two electric field interactions are required. In the above expression and are any two of the Cartesian coordinates x, y, or z. The energy differences nf include both electronic and vibrational contributions e.g. nf = eg - nvib. We can consider both non-resonant and resonant cases for KHD.

Analysis of isotope effects

Vibrational spectra are analyzed within the harmonic approximation. Reduced mass m 1m 2 k = k = m1 + m2 m m
1 2

For a diatomic we can see the effect directly m 1m 2 k = = = m1 + m2

The same principle applies to polyatomics But first we must analyze the normal modes.

Normal Modes of Vibration

Polyatomic molecules can be considered as a set of coupled harmonic oscillators. Although this is a classical model we shall see that it can used to interpret spectra using the quantum-mechanical harmonic oscillator wave functions. The collective motions of the atoms in a molecule are decomposed into normal modes of vibration within the harmonic approximation. The normal modes are mutually orthogonal. That is they represent linearly independent motions of the nuclei about the center-of-mass of the molecule.

Cartesian equations of motion

N 1 T = m i x i 2 + y i 2 + zi 2 2i = 1

V = V0 + +

i=1

V x + V y + V z x i i y i i zi i

i=1

2V x 2 + 2 V y 2 + 2 V z 2 x i2 i y i2 i zi2 i V x y + V y z + V z x x iy j i j y iz j i j zix j i j

i, j = 1

T is the kinetic energy and V is the potential energy expressed as a Taylors series in x, y and z.

Mass-weighted coordinates
3N 1 T = 2 2i = 1 i 3N 1 V = a ij i j 2 i, j = 1

1 = m 1 x 1 , 2 = m 1 y 1 , 3 = m 1 z1 , ... 3N = m N zN a ij = V i j

The equations of motion are:

i + a ij j = 0
j=1

3N

Solutions
Trial solutions have the form:

i = isin
0 0 0

t + t + t +

i = icos i = isin
i +
0

These give a linear system of coupled equations:

a ij 0j = 0 j=1

3N

Which is equivalent to the matrix equation:

A I 0 = 0
A is the matrix of coefficients. I is the identity matrix. are the eigevalues.

Diagonalization of the matrix

The general form of the matrix equations is

a 11 a 12 a 13... a 21 a 22 a 23... a 31 a 32 a 33... ...

1 0 0... 0 2 0... 0 0 3... ...

0 1 0 2 =0 0 3 ..

There is a trivial solution in which all of the terms in the 0 column vector are zero. The interesting solution, however, is the solution for which the determinant of the matrix |A - I| is equal to zero.
V = 1 TA 2

a 11 a 12 a 13... a 21 a 22 a 23... 1 V = 1 2 3 ... a a a ... 2 31 32 33 ...

1 2 3 ..

Definition of normal coordinates

In fact, the procedure of finding det |A - I| is a matrix diagonalization of A. To perform this diagonalization we transform to normal coordinates Qi where:

Qi =

In matrix form Q = LT, which can also be written:

l ki k k=1

3N

Q1 l 11 l 21 l 31... l 12 l 22 l 32... Q2 = l 13 l 23 l 33... Q3 ... .

1 2 3 ..

The Q are normal coordinates

L is a unitary matrix; its inverse is equal to its transpose L-1 = LT. The matrix L will diagonalize A.
L TAL = = 1 0 0... 0 2 0... 0 0 3... ...

Diagonalization of the matrix

The eigenvalues are The kinetic energy is:
3N 2 T T T 1 1 1 T = Q L LQ = Q Q = Qi 2 2 2i = 1
3N T T T 1 1 1 V = Q L ALQ = Q Q = iQi2 2 2 2i = 1

i = i = 2 i

The uncoupled equations of motion are now represented by

Qi = Qi sin
0

i t +

These solutions represent collective motions of the nuclei. Each Q contains simultaneous displacements of many nuclei.

Internal Coordinates
Cartesian coordinates are less convenient than a coordinate system defined in terms of the bonds, angles, etc. of the molecule. Such a coordinate system is called an internal coordinate system. Only motions relative to the center-of-mass are included and thus there are 3N - 6 internal coordinates for a non-linear polyatomic with N atoms. For linear polyatomic molecules there are 3N - 5 internal coordinates. The internal coordinates are Stretch r Bend Torsion 4 Wag

Example: CO2
For example, for CO2 we have the following internal coordinates. r 1 r 2 R= 1 2

1 r 1 r2

Example: CO2
For example, for CO2 we have the following internal coordinates.
2 2 2 V = 1 k r r 1 + k r r 2 + k 2 + k + 1 2 + k r r 1 1 2

1 k r + k r + k r + k r r + ... r 2 2 r 1 2 rr 1 2 2 r 2 1

2T = = R BB
T

T 1

R=R G R

det FG I = 0

Normal modes - CO2

Asymmetric stretch Asymmetricstretch stretch Symmetricstretch stretch Asymmetric Symmetric -1 -1 -1 2349 cm 1 2289inactive) cm-1 (infrared 2349 cm 2349 cm 3 33 (IRactive) active) (Raman active) (IR

Bends Bends -1 -1 667 cm 2 2 667 cm

(infrared active) (IR active)

There are 4 normal modes (3N - 5). Three of them are infrared active since they show a dipole moment change in their motion.