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Physical Chem Lec 5

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Indian Institute of Technology, Guwahati

Guwahati, INDIA 781 039

Department of Chemistry Date: 05-06 December 2022


CH101
Class 5; Physical Chemistry

Vibrational Motion:
Consider the following restoring force that acts on a stretched spring (Hook’s Law)
F = −k ( X 0 − x) ; where k is the force constant
X0
and x is the displacement of the spring from the
equilibrium position.
1
The potential energy is, V = k ( X 0 − x) 2 .
2
This is the potential energy associated with a
harmonic oscillator.
X0 + x
X0 is the equilibrium position of the spring.

Now, consider molecules where real chemical bonds exist. For simplicity and
convenience one can assume that the vibrational motion of the chemical bonds to be
harmonic and thus want to find the energy associated with the vibrational motion of the
molecular bonds. Consider, for example, a carbon-carbon bond. The bond stretched and
compressed between an equilibrium distance of R0 to R0 ± r, where r is the extent of
stretching (compression).

C C C C C C

X0 X0 + x X0 - x
One can simplify the equations by setting X0 = 0 (origin of coordinates).
1 2
Then V = kx
2

1
One can write the Schrödinger wave equation for the system:

 2 d 2 1 2
− + kx  = E
2m dx 2 2
The solution of the above equation is not simple, but well known in mathematics.
The details of the solutions appear like

y2 1
− 2 4
v ( x) = N v H v ( y )e 2 ; where y = x ; and  ={ }
 mk
H v ( y ) is a Hermite polynomial. The values for different v are

H 0 ( y) = 1
H1 ( y ) = 2 y
H 2 ( y) = 4 y 2 − 2
H 3 ( y ) = 8 y 3 − 12 y
H 4 ( y ) = 16 y 4 − 48 y 2 + 12
H 5 ( y ) = 32 y 5 − 160 y 3 + 120 y
H 6 ( y ) = 64 y 6 − 480 y 4 + 720 y 2 − 120

Also, the Hermite polynomials are the solutions of the differential equation

H "v − 2 yH 'v + 2vH v = 0 ; where the primes denote differentiation.

They Hermite polynomials satisfy the following recursion relation

H v +1 − 2 yH v + 2vH v −1 = 0

An important integral related to this is

if ; v'  v


− v' v
H H e − y2
dy = { 0

 2 v v! if ; v' = v

2
x2
y2 −
− 2
Thus the wavefunction for the ground state is: 0 ( x) = N 0 e 2 = N 0 e 2

The wavefunction for the first excited state is

y2 x2
− −
x 2 2
1 ( x) = N1 2 ye 2 = N1 2( )e

In the figures below assume n = v

3
The energy expression for the
harmonic oscillator is
1
Ev = (v + )
2
v is the quantum number and
takes the values of v = 0, 1, 2,
3,……

k
=
m
When v = 0, the minimum
1
energy is  .
2
This is called zero point energy
Explanation for zero point energy. Just like the particle in a box, the oscillator here is
confined in a potential well. Hence its position is not completely uncertain (that is its
position uncertainty is not infinity). Hence its momentum is not zero. Thus its kinetic
energy is not zero. Hence the zero point energy.

y2

Normalization of the wavefunction v ( x) = N v H v ( y )e 2

Nv is not known. The function needs to be normalized.


   1
1=  v*v dx =   v*v dy =   N v2 H v2 ( y )e− y dy = N v2 2 2v v!
2

− − −
1
  2

 Nv = 
1 

1 
  2 2v v! 

4
One can show that for a harmonic oscillator

x =0

 1 
x2 =  v + 
 2 (mk )
Thus 1 2 1  1  1 1
V = kx = k  v +  =  v + 
2 2  2 (mk ) 2  2 

Since the total energy is E= T + V

1
V = Ev
2
and
1
T = Ev
2

 
x =  v* xv dx = N v2   H v e − y / 2  x H v e − y / 2 dx
2 2

− −    

= N v2 2   H v e − y / 2  y H v e − y / 2 dy
2 2

−    

= N v2 2  (H v ) y (H v )e − y dy
2

−
u sin g , recursion − relation
1
yH v = vH v −1 + H v +1
2
get

(H v ) y(H v )e − y
2
 dy
−
 1 
= v  (H v −1 )(H v )e − y dy +  (H v +1 )(H v )e
2 − y2
dy = 0 + 0
− 2 −
 x =0

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