Harmonic Oscillator

The diatomic molecule can be modeled as harmonic oscillator oscillates around

center of mass

The potential energy of the harmonic oscillator is

Stretching
Compression

The Schrdinger equation is

(

This type of equation has known solutions

The wave function will be

Where
called the Hermit polynomial
And the energy will be
(

Where

Compare it with
Plank assumption

 At n=0

The energy level diagram will be

ZPE =

Comments
1- As n increase E increase
2- Energy levels are equally spaced by
3- Minimum possible energy =
called the Zero-Point Energy (ZPE)
4- Wave functions extend beyond separations allowed by classical mechanics
The Probability Density
I- Classical Harmonic Oscillator
For the classical harmonic oscillator, the speed of motion will be low at the
compression and stretching positions (reach to zero) due to changing direction,
so the probability of finding the oscillator in these positions are high while at the
equilibrium region the speed of motion reaches the maximum value so the
probability of finding the oscillator in this position is very low.
Pr

Change direction
Maximum Speed
Minimum Speed
Low Pr
High Pr

Comp

Eq

Str

II- Quantum Harmonic Oscillator

For the Quantum harmonic oscillator, the probability is the square of the wave
function

Pr
Comments
1- At n=0 is maximum probability at equilibrium position (opposite to classical)
2- There is a probability of oscillation in non-classical region (beyond classical
vibration range)
3- Classical properties observed at high quantum numbers

Limitations of S.H.O.
Simple Harmonic Oscillator does not predict bond dissociation

Harmonic

At r = , diatomic molecule
dissociates into 2 atoms
Actual
Anharmonic

re = bond length
Due to equal spacing of energy all transitions occur at the same frequency
i.e. single line spectrum! BUT Experimentally many lines (overtones)
The actual potential is called the Morse potential, when it is used in the
Schrdinger equation, the energy will be

Overtones

Fundamental
vibrations

Where

Compare it with
Plank assumption

is the Anharmonicity constant

Comments
1- As n increase the spacing decrease
2- The spacing reach zero at high r
values
3- S.H.O. Fits well at low excitation
BUT Fits poorly at high excitation

Prediction of Dissociation energy (D0)

The following figure shows the relation between
the dissociation energy, D0, and the minimum energy,
De, of a molecular potential energy curve.
So

Simple Harmonic Oscillator Approximation (Polyatomic Molecules)

( )

The Force constant

Using this approximation the wave number of the normal modes can be calculated
Normal modes = 3*N-6
The wave numbers

 Example the water molecule

Mode Experimental
Calculated
-1
cm
cm-1
3652
3806

3756
3928
1595
1600
3
The lower excitation energy has low difference

Difference
cm-1
154
172
5

Examples:
A 1H35Cl molecule has a force constant of 516 Nm1. Calculate the vibrational
stretching frequency

Hydrogen bromide (1H81Br) absorbs infrared radiation of wavenumber 2649.7

cm-1. Calculate the force constant of the 1H81Br bond. (The molar masses of 1H
and 81Br are 1.008 g mol-1, and 80.916 g mol-1, respectively.)

 The infrared absorption spectrum of 1H35Cl has its strongest band at

8.651013 Hz.
(1) Calculate the force constant
(2) Calculate the zero-point vibrational energy
(3) What happens to the strongest absorption band in IR spectrum if we deuterate
the molecule?
(4) What happens to the force constant if we deuterate the molecule?