Anharmonic

Oscillator
Perturbation Method
Anharmonic Oscillator
is defined as
the deviation
of a system
from harmonic
oscillation, or
an oscillator
not oscillating
in simple
harmonic
motion.
Picture 1
Perturbation Theory
It is the a systematic
procedure for
obtaining
approximation
solutions to the
perturbed problem,
by building on the
known exact solution
to the unperturbed
case. Picture 2
Perturbation Theory
Wed like to solve for the new eigenfunctions and
eigenvalues:

Eq. 1

When a pertubation is applied to a system the new

Hamiltonian is given as:

Eq. 2
where H is the unperturbed Hamiltonian and H is
the pertubed Hamiltonian.
Perturbation Theory
Writing wave function as power series in , we
have

Eq. 3

and the eigenvalues are given as

Eq. 4
Perturbation Theory
To first order

To second order
Perturbation Theory
Plugging Eqs.3, 4 and 2 into Eq. 1 we have

Collecting like power of

First Order
Evaluating

But H is Hermitian, so

and this cancels the first term on the right.

First Order
Evaluating

Moreover, , so

It says that the first-order correction to the energy

is
the expectation value of the perturbation in the
unperturbed state !
Second Order
Evaluating

Again, we exploit the Hermiticity of H:

Second Order
Evaluating

Moreover,
Second Order
but

so
Second Order
Finally

This is the fundamental result of second-order

perturbation theory.
Sample Problem
Adding
to the Hamiltonian of a
harmonic oscillator with
frequency a perturbation of
the form .

(a) Find the energy of the

ground state up to the second
order using the perturbation
theory.
Algorithm
1) Write the new hamiltonian of the system.
2) Use the perturbation theory formula
3) Use the lowering and raising operator to solve
4) Substitute as n=0 , 1, 2
5) Add all answer
6) Print sum
Solution
(a) The new Hamiltonian of the system will be:

| are the unperturbated eigenstates of Harmonic

Oscillator. The energy of the ground state expended
to a series will be:
Solution
Using the perturbation theory formulas

where
Solution
and
by using the lowering and raising operators a
and a and their properties:

As we expect the mean value of x at the ground

state will be zero therefore:

To find we will first calculate the terms :

Solution
After some algebra one can see that :

Therefore:

Substituting into (2) we get:

Solution
Therefore the energy of the ground state up to
second order in will be:

We can see that the ground state shifts down when

this perturbation is present. The other conclusion is
that this perturbation couples only the nearest
neighbor states.
References
Griffiths, D.J. (1995) Introduction to Quantum
Mechanics, Upper Saddle River New Jersey, Person
Prentice Hall Inc.

Kroemer, H. (1994) Quantum Mechanics, Englewood

Cliffs, New Jersey, Person Prentice Hall Inc.

(2017) 123 zero energy

Retrieved from https
://solaralberta.ca/business-profile/123-zeroenergy
References
Ionut Catalin Parvu (2013) PERTURBED stamp sign
Retrieved from
https://www.shutterstock.com/image-illustration/perturbed-
stamp-sign-text-word-logo-540890584?src=wy-ocNoPtzlPCdG1sC
fiKg-1-19

Shay, H.T., Holmes, A. ,(10 Dec 2016) Vibrational Overtones

Retrieved from
https://chem.libretexts.org/Textbook_Maps/Physical_and_The
oretical_Chemistry_Textbook_Maps/Map%3A_Physical_Chemistry
_(McQuarrie_and_Simon)/13%3A_Molecular_Spectroscopy/13-05.
_Overtones_Are_Observed_in_Vibrational_Spectra
Thank You