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12 Harmonic Oscillator

The document summarizes the harmonic oscillator model used to describe diatomic molecular vibrations. It discusses: 1) The harmonic oscillator potential energy and Schrodinger equation for vibrational states. Energy levels are equally spaced and increase with quantum number n. 2) The harmonic oscillator model is a good approximation for low vibrational states but breaks down at higher energies and dissociation. The anharmonic Morse potential better describes actual molecular potentials. 3) Normal mode vibrations in polyatomic molecules can also be modeled as harmonic oscillators to calculate vibrational frequencies from force constants.

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BRENDA ANDREA ROCHA VILLEGAS
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39 views6 pages

12 Harmonic Oscillator

The document summarizes the harmonic oscillator model used to describe diatomic molecular vibrations. It discusses: 1) The harmonic oscillator potential energy and Schrodinger equation for vibrational states. Energy levels are equally spaced and increase with quantum number n. 2) The harmonic oscillator model is a good approximation for low vibrational states but breaks down at higher energies and dissociation. The anharmonic Morse potential better describes actual molecular potentials. 3) Normal mode vibrations in polyatomic molecules can also be modeled as harmonic oscillators to calculate vibrational frequencies from force constants.

Uploaded by

BRENDA ANDREA ROCHA VILLEGAS
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Harmonic Oscillator

 The diatomic molecule can be modeled as harmonic oscillator oscillates around


center of mass μ

 The potential energy of the harmonic oscillator is

Stretching

Compression
𝑉 𝑘𝑥

 The Schrödinger equation is

( )

( )

 This type of equation has known solutions


 The wave function will be

Where called the Hermit polynomial


 And the energy will be
Compare it with
Plank assumption
( )
Where

√
 At n=0

 The energy level diagram will be

𝜈
5
𝜈
𝜈 3
𝜈
𝜈
𝜈
ZPE = 𝜈

 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
Schrödinger equation, the energy will be
( ) ( ) Compare it with
Overtones Plank assumption
Fundamental
vibrations

Where 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 Difference
-1
cm cm-1 cm-1
̅ 3652 3806 154
̅ 3756 3928 172
̅3 1595 1600 5
 The lower excitation energy has low difference

 Examples:
 A 1H35Cl molecule has a force constant of 516 Nm−1. 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
8.65×1013 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?

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