Approximate Solutions to the Quantum Anharmonic Oscillator

Using Time-Independent Perturbation Theory

1

Robert Ringstad1
Department of Physics, Northeastern Illinois University, Chicago, Ill 60625
Dated: December 21, 2016
Abstract

In the modeling of the interactions between particles, a potential energy function which depends only
on the square of the position is commonly chosen. However, this hamonic potential fails to accurately
describe the real interactions that occur within many physical systems. By adding in anharmonicity to
the potential, more realistic solutions can be obtained. In the realm of quantum systems, modifying the
potential energy by adding a small change (or perturbation) can be studied through Time-Independent
Perturbation Theory. It is the goal of this work to explore perturbations of the harmonic potential, a
model system which in one dimension does not require the use of degenerate perturbation theory.

Contents

Independant Schrodinger Equation

h2 d2
(x) + V (x)(x) = E(x)
2m dx2

1 Introduction to the Quantum Harmonic

Oscillator
1
1.1 Analytic Approach . . . . . . . . . . .
1
1.2 Algebraic Approach . . . . . . . . . .
3

(1)

for the potential energy function

V (x) =

1
m 2 x2 .
2

2 Overview of Time Independent PerturIn operator form, with

bation Theory
3
1 2
H =
(
p + m2 2 x
2 ),
2m
3 Perturbing the Quantum Harmonic Os-

(2)

(3)

4 we wish to find solutions of H n = En n .

5
Substituting the potential energy into the
6 Schrodinger Equation and solving for the second
derivative of (x), we find the governing equation of
4 Conclusion
7 state for the quantum harmonic oscillator,
 2 2

d2
m 2 2m
=
x 2 E .
(4)
5 Important Equations &
dx2
h2
h
Results
7
From here, there are two possible routes one may
proceed down. The first is a more straightforward
of Ordinary Differential Equations tech1 Introduction to the Quantum application
niques, dubbed the Analytic Approach. Second is a
Harmonic Oscillator
more algebraic approach; beginning with considering
a factorization of the Hamiltonian, constructing opBefore the analysis of various perturbations on the erators based on those factors allows solutions to be
harmonic potential, a brief overview of the unpert- obtained without explicitly solving the ODE at hand,
erbed quantum harmonic oscillator is appropriate [1]. eq. (4).
Most importantly, the operator approach used to
solve the system algebraically enables the final anal1.1 Analytic Approach
ysis to be undertaken in a much more natural way.
In addition, the contrast between analytic and algeIn order to proceed with an analytic solution to
bratic approachs shows how powerful a more operato the Quantum Harmonic Oscillator, it is beneficial to
based approach is.
first nondimensionalize (4) to make our work easier.
To begin, we start with some boilerplate. The If we substitute x = x0 x , where x0 is our new
nonp m
task at hand is to solve the one dimensional Time- dimensionalized variable, we find that x0
h
x.
cillator
3.1 Linear Perturbation . . . . . . . . . .
3.2 Cubic Perturbation . . . . . . . . . . .

The use of a non-dimensionalized variable transforms which can be substituted into (9).
(4) into the following form:
After judicious manipulation, and carefully redefin

ing
sums to all start at the same initial index, (9) be2
d
2E
= x02 +
.
(5) comes [UP TO HERE WITH EQN REFERENCES]
02
dx
h

X
With our non-dimensionalized differential equation
[(j + 1)(j + 2)aj+2 + ( 2j 1)aj ] x0j = 0.
in hand, an analytic solution can be developed by first
j=0
considering the asymptotic behavior of the problem.
(13)
In particular, when the value of |x| increases without
0j
bound, the first term on the RHS of (5) dominates Because the x s form a linearly independant set, we
0j
strongly over the second term on the RHS. Consid- can equate the coefficient of x to zero. This yields a
ering this dominating feature, the Schr
odinger Equa- recursion relation for the coefficients aj , namely that
tion reads:
2j + 1
d2
aj .
(14)
aj+2 =
02

x
.
(6)
(j
+ 1)(j + 2)
dx02
This is a common differential equation with a well
In order for (x0 ) to be an admissible factor of our
known solution, solvable through many methods (in- wavefunction, we suppose that there must be some
cluding power series expansion in terms of x0 ). Solu- highest n where an = 0. In other words, the infinite
tions of (6) are
series in (11) is in fact, a finite series.
02

(x0 ) Aex

/2

+ Bex

02

/2

= 2n + 1



1
For this solution to be an admissible wavefunction, it
En = n +
h
(15)
2
must go to zero as the independant variable goes to
. This requires us to set B = 0, so our solution By supposing the series must truncate, we are forcing
now reads
a quantization condition on the energy. Substituing
02
(x0 ) Aex /2
(7) back into (15), we find that
If we suppose that the solution to the original, un2(n j)
aj+2 =
(16)
simplified differential equation is a product of the
(j + 1)(j + 2)
form in (7) with a function depending on x0 , we can
where n is the energy level of the solution that is
substitute the following ansatz into (5).
being
sought.
02
(x0 ) = (x0 )ex /2
(8)
(18) can be recognized as the recursion relation for
Hermite
Polynomials, denoted Hn . Recalling that
After substitution into (5) and some algebraic maour
wavefunction
is
nipulation, the following differential equation in results, where

2E
h
.

n (x0 ) = (x0 )ex

d2
d
2x0 0 +
dx02
dx

(x0 ) =

aj x0j .

/2

(9) after normalization and writing in terms of Hn , the

solution to the quantum harmonic oscillator is

The solution of (9) is outlined here as a power series

solution in x0 . Suppose that

02

n (x0 ) =

(10)

 m 1/4
h

02
1
Hn (x0 )ex /2 .
n
2 n!

(17)

In (19), we have an even family of solutions when

n is even, and an odd family of solutions when n is
We need to find the first and second derivatives of odd. That is to say,
(10) with respect to x0 . They read
hm | n i = mn
(18)

X
d
=
jaj x0j1
(11) A generating formula for the terms in Hermite polydx0
nomials, the Rodrigues Formula,
j=1

2
X
 n
d
2
d
=
j(j 1)aj x0j2
(12)
n x2
02
Hn (x) = (1) e
ex
(19)
dx
j=2
dx
j=0

Then the product of these operators is

can be used to find the terms of (19).


We can tabulate a few of the solutions to the quan1
1
2
2
a

=
p

+
(m
x
)
+
tum harmonic oscillator, and
a graph can be ob +
p m
2hm
2
1, so x0 = x,
tained. For simplicity, let
h

1
1
to make graphing easier.
H +
a
a
+ =
h
2
n

n (x)


m 1/4 x2 /2
e

h


2
m 1/4
(2x) ex /2
4
h




2
m 1/4
2x2 1 ex /2
4
h




2
m 1/4
2x3 3x ex /2
9
h

1/4


2
m
4x4 12x2 + 3 ex /2
576
h

(23)

Similarly,

En

1
1
H .
(24)
h
2
3
By presupposing that a
+ n and a
n are eigenh
1
2
values
of
H
,
we
find
that
the
action
of a
+ is to raise
5
2
h
the solution an energy level, corresponding to the en2
7
ergy being raised by a unit of h
. The action of a
is
h
3
2
to lower the energy level of the solution, correspond9
4
h
ing to the energy being lowered by a unit of h
. In
2
this manner, a
+ is called the raising operator, while
a
is called the lowering operator. Through another
Table 1: Wavefunctions and energies for n = 0 means, we have recovered that
through n = 4.


1
En = n +
h.
(25)
2
0

a
+ a
=

1
h
2

If we apply a
to the ground state of the system,
0 , we should hit a wall. That is,
a
0 = 0.

(26)

Using this fact, we can solve for 0 explicitly, which

is
 m 1/4 m 02
e 2h x .
0 (x) =
(27)
h
Then, armed with 0 , the application of the raising
operator will yield any desired n . In symbols,
n

n (x) = An (
a+ ) 0 (x)

(28)

where An is a constant of normalization.

Figure 1: Plot of wavefunctions for n = 0 through
n = 4.

1.2

Algebraic Approach

Overview of Time Independent Perturbation Theory

Suppose we have an exactly solvable Hamiltonian,

If we consider defining a pair of operators based on denoted H (0) , giving
factoring the Hamiltonian,
H (0) n(0) = En(0) n(0)
(29)
1 2
2 2 2
H =
(
p +m x
),
(20) and we wish to find the new energies and wavefunc2m
tions when we add some small, time-independant perturbation H 0 to the original Hamiltonian. If we dewe define
note
1
H = H (0) + H 0 ,
(30)
(ip + m
x)
(21)
a
+ =
2hm
then we are looking for solutions to the equation
1
a
=
(ip + m
x).
(22)
2hm
H n = En n .
(31)
3

Time-Independent Perturbation Theory gets its By taking the inner product in the same manner as
before, the second order energy correction is
start by supposing that we can write
H = H (0) + H 0

(32)
En(2) =


2
 (0)
(0) 
X hm |H 0 | n i

.
(38)
(0)
(0)
En Em
where 0 < 1. is effectively a placeholder to
m6=n
aid in algebraic manipulation, and will be set to one.
Using the second order energy correction, we can
Now, we expand n and En in terms of a power series
find the first order correction to the wavefunction.
in .
To do so, we use the fact that we can express our

X
j (j)
n =
n
(33) first order correction to the wavefunction as a linear
combination of the uncorrected wavefunction.
j=0
X
(1)
(0)

=
c(1)
(39)
n
mn m
En =
j En(j)
(34)
m6=n
j=0

The first order wavefunction correction is found to be

Substituting (34), (35), and (35) into (33), and (after an analagous process to the energy corrections:
equating the coefficients of corresponding powers of substitution and taking inner products)
, we find that to first order,
(0)
(0)
X hm
|H 0 | n i (0)
(1)
m .

=
(40)
n
(0)
(0)
H (0) n(1) + H 0 n(0) = En(0) n(1) + En(1) n(0) . (35)
En Em
m6=n
(0)

We can exploit the orthonormality of the n s by

Higher order corrections to the energy and suc(0)
cessively the wavefunction can be found through retaking the inner product of (37) with n .
peated algebraic manipulation of the original equa

(0) 
(0)  (1)
(0)
0
(0)
tion (33), solving for corresponding powers of , and
hn H n i + hn |H | n i =
taking
inner products.




(0)  (0)  (1)
(0)  (1)  (0)
hn En  n i + hn En  n i
(0)

(1)

Pulling out the En and En from the terms on the

right...




hn(0) H (0) n(1) i + hn(0) |H 0 | n(0) i =

Perturbing the Quantum

Harmonic Oscillator
The form of the perturbations used will be

En(0) hn(0) | n(1) i + En(1) hn(0) | n(0) i.

H 0 =
x

(41)

H = x

(42)

It can be recognized that the first term on the left

cancels with the first term on the right;

where and are small, real numbers to be thought

of as the strength of the perturbation. Prior to work
 
ing out the linear and cubic perturbations to the
 (1)
(0) 
(0)

h
H
 n i + hn(0) |H 0 | n(0) i =
n 
quantum harmonic oscillator, the development of a

(
(
key relationship, based on the raising and lowering
(0) ((
(0)((
(1)
(1)
(0)
(0)
En(hn | n i + En hn | n i.
(
operators a
+ and a
, is needed.
If
the
sum
of
these
two operators is considered, we
Thus we have found the first-order energy correction
find
that
for time independant perturbation theory, namely
1
that
(i
p + m
x + i
p + m
x)
a
+ + a
=
(1)
(0)
0
(0)
2hm
En = hn |H | n i.
(36)
r
h
x
=
(
a+ + a
)
(43)
In a similar fashion, to second order in , it is found
2m
that
which will be indespensible in the development of
H (0) n(2) +H 0 n(1) =
(37) the energy and wavefunction corrections in the sub(0) (2)
(1) (1)
(2) (0)
sequent sections.
En n + En n + En n .
4

3.1

Linear Perturbation

From here, we expand the bra-ket in terms of its

integral definition.
Given the unperturbed Hamiltonian and the linear
Z
(0)
(0)
(0)
perturbation
(
a+ + a
)n(0) dx
hm |(
a+ + a
)| n i = m
Z
1

(0)
(0)
(0)
x2
H (0) = m
= m
( n + 1n+1 + nn1 )dx
2
Z
Z
H 0 =
x,
(44)

(0) (0)
(0) (0)
n1 dx (52)
= n + 1 m n+1 + n m
the full Hamiltonian reads
If m 6= n + 1, the first term in (55) vanishes, while if
1
m 6= n 1, the second term vanishes. This says that
H = m
x2 +
x.
(45)
m = n 1 are the only terms which appear in (52).
2
The term where m = n + 1 is
The first order energy level correction is

2


 (0)
(0) 
a+ + a
)| n i
 n + 12
hn+1 |(
(1)
(0)
0
(0)
En = hn |H | n i
=
n (n + 1)
nn1
(0)
(0)
= hn |
x| n i
= (n + 1),
(53)
En(1) = hn(0) |
x| n(0) i
(46)
while the term with m = n 1 is
2

 (0)
which is just the expectation value of position for the
(0) 
2
a+ + a
)| n i
hn1 |(
| n|
harmonic oscillator (times )! Since we know this to
=
n (n 1)
nn+1
be zero, we find that
= n.
(54)
En(1) = 0
(47)
Plugging into (52) yields our second correction to the
energy,
Now, we move on to the second order corrections.
2
First, the energy correction is given by
En(2) =
(55)
2m 2
2


 (0)
(0)
X hm |H 0 | n i
Interestingly, this expression for the energy correcEn(2) =
(0)
(0)
tion does not depend on the energy level. Rather, it
En Em
m6=n
is a constant for all energy levels.
2

 (0)
(0) 
x| n i
Using the expression for the first correction to the
hm |
X




=
wavefunction,
with direct parallels to the calculations
n + 12
h m + 21
h
m6=n
yielding the second correction to the energy, one finds
2

that
 (0)
(0) 
x
|

i
2 X hm |

n

(2)

En =
(48)

2  (0)
(0)
h

nm
n(1) =
n

n
+
1
(56)
n1
n+1
m6=n
2m 2
which we substitute expression (46) into. This gives
2

En(2) =

2m 2


2
 (0)
(0) 
a+ + a
)| n i
X hm |(
m6=n

nm

It should be noted that the expression in (59) is an

exact eigenfunction of the full Hamiltonian, (48). We
have managed to solve a perturbation problem exactly, using approximation methods! In fact, if one
performs a shift of (x a) to the linear perturbation
case, it reduces to the original quantum harmonic oscillator with corresponding shifts in its energy levels.
One can also obtain the same result by performing
variational methods on the ground state of the perturbed problem with a Gaussian trial wavefunction,
verifying that the found wavefunction is an eigenfunction of the perturbed Hamiltonian. Applying a raising operator an arbitrary number of times gives any
succesive energy levels wavefunction.

(49)

To expand (52), we must first tackle the expres(0)

(0)
sion inside the norm, hm |(
a+ + a
)| n i. First,
however, we must recall the action of the raising and
lowering operators. Symbolically, we write

a
+ n = n + 1n+1
(50)

a
n = nn1 .
(51)
5

3.2

Cubic Perturbation

For the second correction in the energies, we have


2
 (0)
(0) 
X hm |H 0 | n i
En(2) =
(0)
(0)
En Em
m6=n


 (0)  3  (0) 2
n i
hm x
X




=
n + 12 h m + 21 h
m6=n


 (0)  3  (0) 2

i
2 X hm x

n

=
h
nm
m6=n

2

 (0) 
3  (0) 
a
+
a

i
2 2 X hm (

n
+

h
(62)
En(2) =
3
4
8m
nm

Moving to the cubic case, the unperturbed Hamiltonian and the linear perturbation are
1
m
x2
2
H 0 = x
3 ,

H (0) =

(57)

and the full Hamiltonian reads

H =

1
m
x2 + x
3 .
2

(58)

m6=n

Before we can proceed, H 0 must be represented in

terms of the raising and lowering operators, a
+ and Evaluating (65) requires finding


a
.
(0) 
hm
(
a+ + a
)3  n(0) i.
Plugging in for x
,

This expectation value has 8 terms in it. Referring

to (62) and working term by term, as well as considering the conditions on m such that the inner product
does not vanish we find the following... This information is easier to digest if tabulated, so tabulating by
terms and sorting by the requirement on m.

#3

"r

(
a+ + a
)
2m

3/2
h

=
(
a+ + a
)3 .
2m

x
3 =

Expanding, using extreme caution not to invert the

order of multiplication of operators yields

x
=

h
2m

3/2

(
a3+

a
+ a
2

a
2+ a

a
a
2+

a
2 a
+

+a
+ a
a
+ +
+a
a
+ a
+

(59)

a
3 ).

The first order energy level correction is

En(1) = hn(0) |H 0 | n(0) i
 3  (0)
= hn(0)  x
 n i


En(1) = hn(0) x
3  n(0) i

Term

hm | n i = 0

m 6= n + 3

m 6= n + 1

m 6= n + 1

m 6= n + 1

m 6= n 1

m 6= n 1

m 6= n 1

m 6= n 3

Expectation Value

n+3 n+2 n+1

n n+1

3

n+1

(n + 2) n + 1

(n 1) n
3
( n)

(n + 1) n

n n1 n2

It follows that there will be four different contributions

in our sum for the second order energy correc(60)
tion, when m = n 1 and m = n 3.
For m = n + 3, the contribution is
If we refer to the expression for x
3 , we see that in
none of the 8 terms which appear do we have the
(n + 1)(n + 2)(n + 3)

.
(63)
same number
of
raising
and
lowering
operators.
To
3

3  (0)
compute x
n i, we can notice that after the action
When m = n + 1, the contribution is
(0)
3
of x
, an even | n i will become odd, and visa versa.


2
Therefore, because of the orthonormality of the even
(64)
 n + 1 n + 3 n + 2 + 2n + 3  .
and odd solutions,
When m = n 1 gives
En(1) = 0

9n3 ,

(61)
6

(65)

while m = n 3 contributes
(n)(n 1)(n 2)
.
3

mechanics and practice of operator manipulation are

exemplified.
In this work, only the second correction to the energy for two different perturbations are given, because of the desire to perform all manipulations manually, without the aid of a computer algebra system.
A continuation of this work would find (for the cubic, and perhaps a quartic potential) the energy corrections through fourth order, and the wavefunction
corrections through third order.
This paper was completed as part of a final project
for Quantum Mechanics II during Fall 2016 at Northeastern Illinois University, Chicago, Ill.

(66)

Therefore, the second order energy correction to

the perturbed (cubic) quantum harmonic oscillator
is given by the following formula...
En(2) =

2
h2
(27n3 + n(n 1)(n 2)
24m3 4

(67)
3(n + 1)( n + 3 n + 2 + 2n + 3)2
(n + 1)(n + 2)(n + 3))

Conclusion

Through the use of non-degenerate TimeIndependant Perturbation Theory as applied to the

Quantum Harmonic Oscillator in one dimension, the

Important Equations &

Results
impt eqn here

References
[1] David J. Griffiths, Introduction to Quantum Mechanics, (Addison-Wesley, San Francisco, 2nd. Ed., 2002),
p. 40-59
[2] David J. Griffiths, Introduction to Quantum Mechanics, (Addison-Wesley, San Francisco, 2nd. Ed., 2002),
p. 249-257