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,
 Use stationary perturbation theory to find
Vibrational energy of diatomic molecule.

Discuss vibrational and rotational energy levels and

energy gaps. Describe the selection rule for
vibrational rotation spectra and explain P- and R-
branch in the vibration-rotation spectra.
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
6 Harmonic oscillator!

Equating l1 both sides, we get,

7

Equating l2 both sides, we get,

8
Let us find first order correction to energy. For this we
multiply equation (7) by from the left by putting n-
indices for E and y and integrate over all space, we get,
Solving for En(1) , we get,

one zero
Replacing the indices, i.e., for m = n, we get,
9

Therefore, first order correction to energy is simply the

average of the perturbation over the unperturbed
wavefunction! The perturbation is, 10

We know that the wavefunction of the ground state

harmonic oscillator (unperturbed wavefunction) is,

11
Therefore, first order correction to energy is,

12
Solve this integration!
(even and odd function)
The even function can be solved using,

13
Therefore,
Finally, we get,

13
Therefore, energy eigenvalue of anharmonic oscillator is,

14

Introducing anharmonicity constant,

15

The vibrational energy levels are described by,

16
 17

For lower energy levels,

this term is negligible!
Energy gap between any two successive level is,

Using (17), we get,

The second term provides the correction for anharmonicity. 18

The observed dissociation energy for the H2 molecule is 4.5

eV. If the molecule vibrates with frequency 1.32 x 1014 Hz
behaves like a Morse Oscillator, calculate the energy gap
between the levels n = 7 to n = 8. Compare the result with the
harmonic oscillator potential.

19
 Discuss vibrational and rotational energy levels and
energy gaps. Describe the selection rule for vibration-
rotation spectra and explain P- and R- branch in the
vibration-rotation spectra.
The vibrational energy levels are given by,
19

The rotational energy levels are given by,

Wave number
20

Here the spacing between the levels are gradually increased

B, B, 6B, B, B, …. .
For lower energy levels, the second term of equation (19) can
be neglected.
Let us check whether the values of and for a diatomic
molecule (say for CO) are comparable or not.
For CO, and . Therefore,
rotational energy levels are 100 to 1000 times less than that
of the vibrational energy levels. The relative spacing of the
levels are as follows:

n=2
Vibrational Energy Levels
n=1
n=2
n=0

n=2
n=1
n=0
Electronic Energy Level, n = 1
The selection rule,

restricts vibrational transitions to adjacent energy levels.

The selection rule,

restricts rotational transitions to adjacent energy levels.

Considering only lower transition levels, the initial
vibrational-rotational state is,
21

Transition to a new vibration-rotation state (n’, l ’), involves

the energy difference,
22
For vibration, equation (22) 22

=1

23

Gives two sets of frequencies

This gives two sets of frequencies.
For the quantum number l’,
(1) l’ = l+ ) >> frequencies are nR
(2) l’ = l-1) >> frequencies are nP
Therefore, we obtain,
Therefore, we obtain,

Here, l = , , , , ……..
Similarly, when putting l’= l - 1
Here, l = , , , ……..
These two sets of frequencies can be re-written as,
Here, l = , , , ……..24
Here, l = , , , ……..25
Thus the vibrational-rotational band consists of two sets of
lines, the P-branch and the R-branch. In both the case, l = 0 is
not allowed.
 D J = -1 DJ=0 DJ=+1
P-branch Q-branch R-branch
l=6

l=5
l=4
l=3 l=2
n=1
l=6
l=5
l=4
l=3 l=2
n=0
 l = 0 is not allowed!

Spectral lines in vibrational-rotational band for 0  1

vibrational transition in a typical diatomic molecule.
Electronic
Discuss the effects of nuclear motion during electronic
transition. Explain rotation and vibration of diatomic
molecule assuming adiabatic approximation.
 In the last class we have seen how rotational
transitions, coupled to a vibrational transition, lead
to a vibration-rotation band in the molecule.

Vibrational energy levels are associated with each

electronic energy level, indicating the transition
of an electron may be coupled with the changes
in the vibrational levels!

Vibronic
Ro-vibration
 During electronic
transition, electrons
move very much faster
than nuclei, so nuclei
remain stationary. Excited Electronic States

(classical idea).

This is due in fact that

nuclei are much more
massive than electrons and
Ground Electronic State
the electronic transition
takes place faster than the
nuclei can respond.
 Each electronic state has its own set of vibrational states.

Each electronic state

has its own set of
vibrational parameters. we’ De’

- mean bond length, ro

- dissociation energy, De
- vibrational frequency, we De”

we”

ro” ro’
Note: single prime (’) = upper state
double prime ” = lower state
Considering lower vibrational energy levels
If electronic excitation
is much faster than 2
nuclei move, then 1
wavefunction cannot
v’ = 0
change.

The most likely

transition is the one
that has most overlap
with the excited state
wavefunction.
v” = 0
Look at this more closely…

Negative overlap in middle

Positive overlap at edges
very small overlap

Negative overlap to left, postive

overlap to right
overall zero overlap

Excellent overlap everywhere

 1

2
0 3
4

Wave number
 Immediately after the
electronic transition,
nuclei re-adjust
themselves v=10
s…l….o….w…..l…y
with thenew electronic
very poor overlap at n=0
configuration.
Because of this, the
molecules must
undergo a vibration,
called vibronic
transition
Adiabatic Approximation
Here we improve our model for a diatomic molecule by
considering kinetic energy of nuclei in the rotational-vibrational
spectra.
Because of the larger mass, the nuclei in a molecule move much
slower than the electrons. This means electrons can immediately
adjust their positions to the new nuclear configuration when the
nuclei move.
The electronic wavefunction y (r,R) depends on the internuclear
distance R because they are barely affected by the velocity of
moving nuclei.
The kinetic energy by the nuclear motion (ENUC = ½ Mv2)
is small compared to that of the electrons. We therefore
write total Hamiltonian as,
1
 1
Here Ho represents Hamiltonian for rigid molecule and
TK is the kinetic energy of nuclei.
Since TK is small compared to Ho, we regard TK as small
perturbation of H. In this situation, total wavefunction,
2

Molecular Electronic wavefunction of

wavefunction the rigid molecule at fixed
nuclear positions RK, where
electronic coordinates ri are
variable!

This implies that the electronic and nuclear motion are

independent and coupling between them is neglected.
The total energy is the sum of the energy of rigid
molecule in the nth electronic state and kinetic energy of
nuclei (Evib + Erot).

E Binding
Energy of rigid
molecule
E = Enel + Evib + Erot

Dissociation
Energy De of
non-rigid
molecule

Re R
Inserting (2) in Schrodinger Equation, we get,
3
This equation describes electronic wave function F of
the rigid molecule in the electronic state and En(0) is the
total electronic energy of this state without considering
KE of the nuclei.
The second equation,
4

determines the motion of the nuclei in the potential,

5

Time average of kinetic Total potential energy

energy of electron of electrons and nuclei.
The second term of equation (5) represents total PE of
electrons and nuclei. The total energy of non-rigid
molecule is the sum of the KE of nuclei and total energy
of rigid molecule.
6

Therefore, equation (4)

can be expressed as,

Here m is the reduced mass of the two nuclei. The index

m gives the m quantum state of the nuclear movement
(vibrational-rotational) state.
The potential energy of the nuclear motion depends only
on the nuclear distance, not on the orientation of
molecule in space (q, f). Therefore,
8
can be separated as,
9
The radial part of the Schrodinger equation is,

10

describes vibration of the diatomic molecules.

The angular part,
11

Determines its rotation.

1. Describe the nature of the potential of vibrating diatomic molecules.
Explain Morse potential and hence anharmonic oscillator. Find the
expression for potential of a vibrating diatomic molecule in terms
of dissociation energy.

2. Use stationary perturbation theory to find energy eigenvalue of vibrating

diatomic molecule. [Note: You need to go to second order correction to
energy, this was HW, I hope you all have solve this!]

3. Discuss vibrational and rotational energy levels and energy gaps. Describe
the selection rule for vibrational-rotation spectra and hence explain P- and
R-branch in the vibration-rotation spectra.

4. Discuss the effects of nuclear motion during electronic transition. Explain

rotation and vibration of diatomic molecule assuming adiabatic
approximation. [Note: Today I will discuss.]
(a)The observed dissociation energy of the H-molecule is 4.5 eV.
(a) If the molecule vibrates with frequency n0 = 1.32 x 1014 Hz
behaves like a Morse oscillator, calculate the energy gap
between the levels n = 7 to n = 8. (b) Compare the result with
that of the Harmonic oscillator potential.
[Ans: 0.41 eV, 0.54 eV]

(a)For the carbon monoxide it is given that the rotational

constant B = 1.93 cm-1 and vibrational constant is 2160 cm-1.
What are the frequencies of the first three lines of the R- and
P-branches in the vibration-rotation spectrum of CO?
[Ans: 2163.9 cm-1, 2167.7 cm-1, 2171.6 cm-1 for R-
branch and 2156.1 cm-1, 2152.3 cm-1, 2148.4 cm-1 in
P-branch]
State and explain Franck Condon principle.
Considering lower vibrational energy levels

2
1
If electronic excitation
is much faster than v’ = 0
nuclei move, then
wavefunction cannot
change.

v” = 0
Look at this more closely…

Negative overlap in middle

Positive overlap at edges
overall very small overlap

Negative overlap to left, postive

overlap to right
overall zero overlap

Excellent overlap everywhere

 1

2
0 3
4

Wave number
 Immediately after the
electronic transition,
nuclei re-adjust
themselves v=10
s…l….o….w…..l…y
with thenew electronic
very poor overlap at n=0
configuration.
Because of this, the
molecules must
undergo a vibration,
called vibronic
transition
.
Consider an electrical
dipole transition from
the initial vibrational
state (n”) of the ground
electronic level (n’’), to
some vibrational state
(n ’) of an excited
electronic state (n’),
The
.
molecular dipole moment operator μ is determined by the
charge (−e) and locations (ri) of the electrons as well as the
charges (+Zje) and locations (Rj) of the nuclei:

1
The probability amplitude P for the transition between these two
states is given by

2
where ψ and ψ ′ are overall wavefunctions of the initial and
final states. The overall wavefunctions are the product of the
individual vibrational (depending on spatial coordinates of
the nuclei) and electronic space and spin wavefunctions:
3
This separation of the electronic and vibrational
wavefunctions is an expression of the Born–Oppenheimer
approximation and is the fundamental assumption of the
Franck–Condon principle.
Combining these equations leads to an expression for the
probability amplitude in terms of separate electronic space,
spin and vibrational contributions:

4
 4
This integral is equal to zero because electronic wavefunction
of different states are orthogonal.

Remaining is the product of three integrals.

The first integral is the vibrational overlap

integral, also called the Franck–Condon factor.
The remaining two integrals contributing to the
probability amplitude determine the electronic spatial
and spin selection rules.
The spin-independent part of the initial integral is here
approximated as a product of two integrals:

This factorization would be exact if the integral 5

over the spatial coordinates of the electrons would not

depend on the nuclear coordinates.
However, in the Born-Oppenheimer approximation ye
and ye’ do depend on the nuclear coordinates, so that
the integral is a function of nuclear coordinates. Condon
approximated that the transition dipole surface is
independent of nuclear coordinates.
There are no vibrational selection
rules, so any Dv is possible.

Relative vibrational intensities

come from the FC factor

μ21 = constant × FC factor

Summary
The Franck-Condon Principle describes the
intensities of vibronic transitions.
It states that when a molecule is undergoing an electronic
transition, the nuclear configuration of the molecule
experiences no significant change.
It is because nuclei are much more massive than electrons
and the electronic transition takes place faster than the nuclei
can respond.
When the nucleus realigns itself with the new electronic
configuration, the theory states that it must undergo a
vibration.
What about equation of continuity for
relativistic particle?
 What about equation of continuity for relativistic particle?
In non-relativistic quantum mechanics, equation of
continuity is,
1

What will happen to this equation in relativistic case?

In relativistic physics the current density and charge density can not be
distinct (or completely separable entities). Because a static charge
distribution in one inertial frame will appear as current distribution in
the other moving inertial frame.

Therefore, by looking equation of continuity, one can think

about four vector of current density,

2
 E uation of continuity in elativistic QM…..
Consider a volume element dV = dx1 dx2 dx3 . The charge
distribution in this small volume element is,
dq = r dx1 dx2 dx3 3
Now, we multiply this equation by a four vector dxm we get,
dq dxm = r dx1 dx2 dx3 dxm

4
Invariant under Lorentz
transformation

This means four dimensional volume element is invariant

under Lorentz transformation!
A charge is invariant, thus LHS of equation (4) remain
invariant. Therefore the RHS of equation (4) must be
expressed in terms of four vector to make it invariant!

Lorentz must be Lorentz invariant >>

invariant must be a four vector

5
 Therefore, the current four vector is represented as,
6
jm must transform from one inertial frame to the other (say S
and S’), moving with velocity v relative to S along x1-axis
under Lorentz transformation as,

Where,

So that,
And,

Similarly,
Therefore we get,

These are required transformation equation for current

and charge densities.
The inverse transformations for current and charge
densities are obtained by replacing v by –v and
interchanging primed and unprimed quantities.
Now the equation of continuity can be written as,

Therefore, four
divergence of the
current four vector
vanishes!

Four dimensional divergence operator

Discuss WKB approximation and find its turning point
solution. Discuss importance of this approximation
over variational method.
 The WKB method
I already studied is good for highly
variational excited states.
method….. why
WKB now?

The variational
method is good for
ground state and
other low energy
states
 Idea behind the WKB approximation
If the energy is large, the wave function will be
quickly oscillating (?). The potential will then look
like it’s slo ly arying

The WKB approximation, named after Wentzel,

Kramers, and Brillouin, is a method for obtaining an
approximate solution to a time-independent one-
dimensional Schrödinger equation.
 Wentzel- Kramers - Brillouin
Gregor Leon Brillouin
Hendrik Kramers
Wentzel

Dutch
German 1894- 1952
1898- 1978 French
1889- 1969
WKB assumed that V(x) should be varying function of x,
 WKB assumed that V(x) should be varying function of x,

Since V(x) varies slowly with xo, i.e., 1

Equation (1) takes this form:

2

V>E
E E
V<E V=E
V(x) V(x)

xo
x xo x
 The general solution of the
Region I V>E
SWE for the Region I
E
V<E V=E
V(x) Region II
along x-direction is,
xo x
Therefore the general solution here,
for Region I can be expressed
as, and we know,
3
Therefore, the general
Now the SWE for the Region II is solution can be written as,

which is non-oscillatory! f(x)

Now the SWE for the Region II is

which is non-oscillatory!
Substituting general solution for Region I to the SWE for
Region II (WKB assumed semi-classical approach!),
 4

Now the power series expansion of f(x) in around x0 is given

by,

Substituting (5) in (4), we get,

We neglect higher order of ,

6
 6
Since is a real parameter, therefore the coefficients of each
power of must vanish to satisfy (6), i.e.,
For

For

Integrating this,
 9

Using (5), [taking up to the first order of ]

Substituting from (8) and (9),

Substituting this in the general solution of SWE for Region I,

 10

Substituting this in the general solution of SWE for Region I,

p  x   2m  E  V  x  

Therefore the general solution of SWE for Region I is,

At the turning point, i.e., E = V, p = 0 and hence

In other words, diverges at the turning point!
Similarly in the Region II (exponential solution because E<V
here), the solution will be,

This is classically forbidden region! At the turning point this

also diverges. [Classically the particle stops at xo and then
turns back to resume in the opposite direction!]
As both the wavefunctions

At turning points, E = V

Now we need to discuss turning point solutions considering

slowly varying potential.
Turning point solution
Since both WKB functions yI and yII are found to be NOT
expectable at turning point (x = xo), we co side slowly
varying potential as a fu ctio of x (V(x)) that approximate it
with a straight line in a very small region near xo, i.e.,

1
Since V(x) varies slowly with xo, i.e.,

Equation (1) takes this form:

2

11
The Schrodinger Equation

Substituting (11),
12

Let us introduce

Equation (12) takes this form:

13
It is one of the standard differential equation. Its solution is
named as Airy Function. This equation can be expressed into
standard Bessel Equation!
Let us introduce
Let us introduce
14
Differentiating

Again differentiating

15

Substituting (14) and (15) in Schrodinger Equation (eq. 13),

 16

Let us consider,
 17

Now,

Again differentiating,
 18
Again differentiating,

19
Substituting (18) and (19) in (16), you get,

On Simplifying, you get,

The form of this e uatio is si ila to the Standard Bessel

Differential Equation, i.e.,
You know its solution! Right?
 In the WKB approximation, what can we say
about the solution for the wave function ? (HW)

A. The amplitude and the wavelength are fixed

B. The amplitude is fixed but the wavelength varies
C. The wavelength varies but the amplitude is fixed
D. Both the wavelength and the amplitude vary
E. There are multiple wavelengths for a given position
 The WKB approximation

The WKB approximation is based on the idea that

for any given potential, the particle can be locally
seen as a free particle with a sinusoidal wave
function, but whose wavelength varies very
s…l…..o….w…..l…..y in space.
 Set up Standard Bessel Differential Equation from
Schrodinger equation using WKB approximation and
find its general solution for E>V and E<V. Deduce
connection formula for WKB approximation. Discuss
the validity of this approximation
 Region I V>E
E
V<E V=E
V(x) Region II

xo x
 Equating real parameter:

Airy Function
Airy Function
The general solution is,

We have,

1
This is the solution for region I with x < xo, near xo.
Similarly for region II, with x > xo, the differential equation is,

y20 - +

We have,

Here we need to introduce,

The solution for region II will be,

The Fourier expansion of Bessel function is,

The modified Bessel function is,

For x → xo (called small argument, i.e., s = 0), we have,

For x → xo (called small argument, i.e., x → 0), we have,

Therefore, near the turning point,

We know,
Substituting this in (3) >>
 4

Similarly for region II, the general solution,

At the turning point, waves must be continuous, so here we

apply boundary value conditions,
For large argument, i.e., x → Exercise!

Exercise!

Therefore, the solution in the region I VERY FAR from the

turning point is,

Similarly, the solution in the region II VERY FAR from the

turning point is,
Similarly, the solution in the region II VERY FAR from the
turning point is, 7

The solution in the region I VERY FAR from the turning point
is, 6

Connection Formula: Need to connect at the turning point!

Since WKB approximation breaks down near the turning point
xo (i.e., on both sides of x = xo), we need to find out a scheme
for determining the wave function near x = xo.
Let us set,
Here we are assuming that the
incident beam have equal amplitude!
Using (6),

8
Similarly,
9
 8
Similarly,
9
Therefore the connection formula that connects the WKB
solution on the right of the turning point is, Exponentially
decreasing!

10

To get the analytic extension of Here we have assumed that the

exponentially increasing solution incident beam have equal but
we need to set AI = -BI = (p/2)1/2. opposite amplitude!
Then, you will have,

11

Similarly,
12
Therefore the connection formula that connects the WKB
solution on the left of the turning point is, Exponentially
increasing!

13
 When the potential
barrier is located to the
left of the turning
point, region I and II
get reversed!

Connection formula
are actually the bridge
formula when passing
through the turning
point.
Let us begin with
14

Comparing the coefficients of h0,

This is called zeroth order approximation. When equating the

coefficient of h1 (called first order approximation), we get,

This approximation is valid only when,

Since 15
For a small change, we can write
16

The WKB approximation is valid if the change in the reduced

de Broglie’s a elength ( ) within a region is much smaller
than the change in the size of the region that produces the
former change.
Again,

17
Since,

Or,
19

To satisfy this condition, potential should vary slowly with x!

Should be large enough!

Varying Potential

V(x)

Turning points

Classical region (E>V)

Varying Potential

V(x)

varying very slowly

In respect to wavelength


Classical region (E>V)

 In the WKB approximation, what can we say
about the solution for the wave function ? (HW)

A. The amplitude and the wavelength are fixed

B. The amplitude is fixed but the wavelength varies
C. The wavelength is fixed but the amplitude varies
D. Both the wavelength and the amplitude vary
E. There are multiple wavelengths for a given position
Show that WKB quantization rule for a linear
harmonic oscillator is
 Use WKB connection formula to find transmission
coefficient of one dimensional barrier.

Discuss the bound states quantization condition using

WKB connection formula.

Use WKB method to estimate the energy levels of a

one-dimensional harmonic oscillator.
 Potential Barrier >> Alpha Decay
V(x)

E(a) < V(x)

X
a 0 b
We know that the transmission coefficient for the alpha particle having energy E in the barrier
potential V of width 2a, satisfying E<V, is given by,
4 E (V  E )
T
4 E (V  E )  V 2 sinh 2 (2 Ka)
If KL>>1, then the transmission coefficient
16 E (V  E ) 2 KL 16 E  E  2 KL
T e  1  e
V 2
V  V
Taking log both sides
16 E (V  E ) 
ln T  ln    ln e 2 KL
 or ln T  C  2KL
 V2 
One Dimensional Barrier
V(x)
RI RII RIII

Quantum mechanically,
the particles tunneling
through the barrier and
E
emerging to the right of
the barrier is non-zero.

Here we find expression

for transmission E>V E<V E>V
coefficient using WKB a b
approximation.
In region I and III,
1

In region II,
2

The turning points a and b are well separated and potential

can be approximated as straight line,
The solution of Schrodinger equation in region III is
oscillatory,
where 3
 4

Applying connection formula for the left of the turning point

at x = b, we get,

5
Substituting this in (5),

Applying connection formula for the right of the turning point

at x = a, we get,
Now, for above equation reduces to,

Therefore the incident wave is,

8
and the reflected wave is,

and the reflection coefficient is given by,

10

This is our required expression for reflection coefficient.

The transmission coefficient is given by,
The transmission coefficient is given by,

11

This is our required expression for transmission coefficient.

To make the WKB approximation valid, momentum (p) should
be very high. i.e., k2 should large enough.
To make the WKB approximation valid, momentum (p) should
be very high. i.e., k2 should large enough.

For larger value of k2, a becomes large and the second term
of equation (11) can be neglected!

The decay of parent nuclei into alpha particles & daughter

nuclei can be viewed as tunneling of a-particles through the
coulomb potential barrier.
Barrier Potential: a-decay
V(x)

E(a) < V(x)

X
-a 0 a
We know that the transmission coefficient for the alpha particle having energy E in the barrier
potential V of width 2a, satisfying E<V, is given by,
4 E (V  E )
T
4 E (V  E )  V 2 sinh 2 (2 Ka)
If KL>>1, then the transmission coefficient
16 E (V  E ) 2 KL 16 E  E  2 KL
T e  1  e
V 2
V  V
Taking log both sides
16 E (V  E ) 
ln T  ln    ln e 2 KL
 or ln T  C  2KL
 V2 
 ALPHA DECAY
We have,

ln T  C  2KL V(x)
For a system of potential
barrier of width x, this
expression can be written as,

ln T  C  2 Kx
ln T  2 Kx
If a system of potential barrier is
smooth, then, we can write,

ln T  2 Kdx X

Thus, x
2m(V  E )
ln T  2 dx
2

This equation is valid for infinitely narrow (i.e., smoothly curved) barrier.
 ALPHA DECAY
In our case,
m: mass of the a-particle
E: Energy of the a-particle
V: Coulomb potential of the atom
V(r)
Thus,

2m(V  E )
ln T  2 dx
2

can be written as, E

r1 2ma [V (r )  E ]
ln T  2 dx
r0  2

Here,

2 Ze2
E
r1
2 r0 r1 r
2 Ze
V radius of radius of
r the nuclei the atom
 ALPHA DECAY
r1 2ma [V (r )  E ]
ln T  2 dr
r0  2
As Z increases, T increases.
becomes,
As E increases, T increases.
2ma r1 1 1 
 2Ze   dr As r0 increases, T increases.
ln T  2 2

2 r0
 r r1 
substituting
r r
 cos 2  dr  2r1 cos  sin d  1 sin 2 
r1 r1
and solving, we get,
B
ln Ta  A Z  called Geiger Nutall Law .
E
A  2.79 r0
B  3.97
 V(x)
RI RII RIII
Consider a potential
well that has two rigid
walls, at x = a & x = b, as
shown in the left. E

The WKB wave function

will be oscillatory in the
E<V E>V E<V
region II (a<x<b), where
as it will be non- a b
oscillatory otherwise.
Using WKB connection
formula, WKB solution 1
to the left of the
turning point a, i.e., in
the region I,

Using WKB connection

formula, WKB solution 2
for the barrier, in the
region II, to the right of
the turning point a,
Using WKB connection
3
formula, WKB solution
for the barrier, in the
region III, to the right
of the turning point b,

Using WKB connection

formula, WKB solution
for the barrier, in the
region III, to the left of
the turning point b,

4
Since, particle is bounded, yII should not depend on turning
point! Therefore, we can write,

5
 5

Thus, in general,

Since ,

This equation provides the proper prescription for specifying

the energy level for the potential well. For the larger value of
n, above quantization rule becomes semi-classical.
Use WKB quantization rule to find the energy levels of
a one dimensional linear harmonic oscillator
The energy of a linear harmonic oscillator is,

1
Using WKB quantization rule,

2
Where x = ±a are turning points.

Since, at the turning point k(x) = 0 = P(x), therefore (3) gives,

4
Therefore the turning points are,

Substituting (3) and (4) in the WKB quantization condition,

Let us introduce,
 This expression is
identical to that of
the previous one!
Use WKB approximations or WKB turning points solutions to
find the energy eigenvalue of H-atom.

Use WKB method to find the difference between the odd and
even eigenvalues of a double well.
 I already studied The WKB method
WKB connection is good for highly
formula…. Let me excited states.
think what I
understood??

The WKB approximation is based on

the idea that for any given
potential, the particle can be locally
seen as a free particle with a
sinusoidal wave function, but whose
wavelength varies very
s…l..o…w..l.y in space.
 Discuss Fortrat diagram and its importance.

Explain the features of vibrational Raman spectra.

The vibrational energy levels are given by,
1

The rotational energy levels are given by,

Wave number
2

Here the spacing between the levels are gradually increased

B, B, 6B, B, B, …. .
For lower energy levels, the second term of equation (19) can
be neglected.
The selection rule,

restricts vibrational transitions to adjacent energy levels.

The selection rule,

restricts rotational transitions to adjacent energy levels.

Considering only lower transition levels, the initial
vibrational-rotational state is,
There will be 2 sets of frequencies:
Here, l = , , , …….. 3
Here, l = , , , …….. 4
Thus the vibrational-rotational band consists of two sets of
lines, the P-branch and the R-branch. In both the case, l = 0 is
not allowed.
 D J = -1 DJ=0 DJ=+1
P-branch Q-branch R-branch
l=6

l=5
l=4
l=3 l=2
n=1
l=6
l=5
l=4
l=3 l=2
n=0
 l = 0 is not allowed!

Spectral lines in vibrational-rotational band for 0  1

vibrational transition in a typical diatomic molecule.
 Here the rotational quantum You know the rotational quantum
number are different! The wave number of each lines! You also
numbers are not equally spaced! know the wave number associated
with each lines!
 Rotational quantum number
It is found that the wavenumber
is quadratic in rotational R
quantum number! P

wavenumber
 It is found that the
wavenumber is quadratic in
rotational quantum number!

Here a and b corresponds to

spectroscopic notation!

The vertex of a Fortrat

parabola, with the value of J
such that

This value is
Fortrat diagram explains
multivariate nature of
rotational transitions.

m
The Fortrat diagram gives information regarding the rotational
structure of molecular spectra. This information is extremely
important for rotational chemistry. In general, the line of P-branch
are densely distributed between the rotational quantum number 0
to certain value (say 16 in above figure), and the P branch turns
back, thus more transition lines form closer to the vertex of the
parabola.
Isotopic Effect
The Fortrat diagram gives information regarding
the rotational structure of molecular spectra.
Symmetric and di-symmetric properties of
molecules can be studied through Fortrat
diagram. This information is extremely
important for rotational chemistry.
Discuss Raman Vibrational spectra.
When a beam of monochromatic radiation passes through a
liquid or gaseous substance, it might get scattered. Either the
frequency of the radiation is unchanged (Rayleigh scattering)
or the scattered radiation has lower frequency (Stokes lines)
or higher frequency (anti-Stokes lines).
The important molecular property is the
polarizability which must change during
the vibration, in the Raman Vibrational
spectra.
The polarizability of ellipsoid should either change in shape or
size during a vibration for it to be Raman active.
Summary

>> The molecular property that must change during a

vibration for it to be Raman active is its polarizability.

·>> Thus, Raman spectroscopy is complementary to

microwave and infrared spectroscopy, where the property
that must vary is the dipole moment.

>> Anti-Stokes lines are much weaker than Stokes lines.

>> The polarization of Raman lines gives information about

the symmetry of a vibration.
 Raman spectroscopy is a spectroscopic technique
used to observe vibrational, rotational, and other low-
frequency modes in a system. Raman spectroscopy is
extensively used in chemistry to provide a structural
fingerprint by which molecules can be identified.