Spectra of Diatomic Molecule: Vibrational, ……

Electron in the e.m. field

WKB Approximation

B. Aryal
CDP, TU, KIrtipur
B. Aryal
CDP, TU, KIrtipur
2/7/2018 Second Semester Orientation 3
 Describe the nature of the potential of vibrating diatomic
molecule. Explain Morse potential and hence anharmonic
oscillator. Use stationary perturbation theory to find energy
eigenvalue of vibrating diatomic molecule.

Discuss vibrational and rotational energy levels and energy gaps.

Describe the selection rule for vibrational-rotational spectra and
explain P- and R-branches in the vibrational-rotational band
Spectra of Hydrogen atom
Theoretical Spectra of HCl

Experimental
 n = 5 to n = 4

2500 A
5A 50 A rotational

vibrational vibrational
rough, bristly, scratchy, prickly, hairy, shaggy, wiry
The vi ration transition produ e coarse structure and rotational
transitions a fine structure on the ele troni spe tra.
For a diatomic molecule with reduced mass m and mean bond
length ro, the harmonic oscillator potential has the form
m2
m1 r
CM

r1 r2 m
r

For undisturbed molecule, V(ro) = 0. In this situation energy

levels are described by,
2
This equation gives equally spaced
energy levels, with characteristic
frequency no = w/2p.

In realistic situation, temperature do not remain constant.

In the laboratory, following facts are realized:
(a) As temperature increases, molecules vibrate more
vigorously, gives rise to larger number of successfully
closer energy levels. The higher excited energy levels are
closely spaced.
(b) Molecules are found to be dissociate finally, at very high
temperatures!
Therefore the nature of molecular
vibrations is not exactly the same
 
as that of the harmonic oscillator.
This suggests that the quadratic
potential of equation (1) must be
modified to include at least a few
higher order terms,

3
Asymmetry of PE Reduces the
energy gap

The shape of PE curve should deviates from parabolic to

asymmetric. The resulting oscillator is named as anharmonic
oscillator.
 Dissociation Energy
n=8
Energy

n=2

SHO Energy Levels Vibrational Energy Levels

The anharmonic molecular vibrations are best described by
Morse Potential,
4
Here, the exponential function can be expanded into terms
containing quadratic, cubic and higher powers in (r-ro) as (3).
Let us discuss equation (4) at first,
4

Differentiating (4) w. r. t. r,

5
The Potential Energy V(r) will be minimum at
Therefore equation (5) gives,

≠0 =0
 6
Therefore, the minimum PE occurs at r = ro, which is the
mean bond length of the molecule.
Similarly at r , V(r) = De, the dissociation energy, energy
required to stretch the bond from ro to infinity.
The parameter b contains the force constant k of the bond.
Substituting r – ro = x in equation (4),
7

8
This is similar (analogous) to equation (3), i.e.,
9

The exponential term of (8) can be expanded by using,

The exponential term of (8) can be expanded by using,

10
Therefore,

11

Similarly,

12

Substituting (11) and (12) in (8),

Substituting (11) and (12) in (8),

We get,

Simplifying,
13
Now we equate the coefficients of x2 and x3 with (9),

14

15
Similarly, when equating the coefficient for x4, we get the
values of b, [HomeWork],

Finally, we get anharmonic potential as,

16
asymmetric
This is our required potential for vibrating diatomic molecule.
This potential is asymmetric, suggesting that it is harder to
compress bond than to stretch it!
The negative coefficient of second term indicates that the
energy eigenvalue due to this term lowers the energy levels
whereas the last term reduces the spacing between the
energy levels.
 Describe the nature of the potential of vibrating
diatomic molecule. Explain Morse potential and
hence anharmonic oscillator. Use stationary
perturbation theory to find energy eigenvalue of
vibrating diatomic molecule.
The potential for a vibrating diatomic molecule is,

We know that the Hamiltonian of one-dimensional

anharmonic oscillator is,
2

Harmonic Oscillator anharmonic Oscillator

(Unperturbed Hamiltonian) (Perturbed Hamiltonian)
Here,
and 3

Therefore,
Now we introduce a switching parameter l as,
4
When l=0 we have unperturbed system and for l = 1, the
perturbation is fully turned on. The time-independent
Schrodinger equation is,
5
The perturbation expansion of wave function and energy
eigenvalues are,

And,

Substituting in (5), we get,

Re-arranging like powers of l we have

Equating lo both sides, we get,

Zeroth order
wavefunction of
Harmonic oscillator!

Equating l1 both sides, we get,

You get,