Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

Chapter Three
Approximation Methods: Correction Theories

The systems that have an exact solution of S.E. are in general virtual
systems, such as potential step, potential well, ..etc. real systems are
almost more complicated, for example;
i. Usually oscillators are not a simple harmonics.
ii. The presence of external forces, such as the electromagnetic fields, will
change the energy levels of an atom.
iii. The mutual interaction between the particles in the more than one
particle system will make S.E. cannot be solved.
iv. S.E. cannot have an exact solution when spin is taken into
consideration.
Therefore, we need the correction methods.

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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

3-1 Time Independent None Degenerate Perturbation Theory

3-1-1 Rough Treatment
i. Assume that we have a quantum mechanical system described by S.E.

H n = E n n
But this equation cannot be solved exactly as before, thus we assume that
there is a small (rough) perturbation such that;

H H o

H = Ho+ H

H o Exact part

H Perturbed part

H o U n = EonU n

Remember that

ii. The effect of the perturbation is;

Eon Eo

U o o

E1n E1

U 1 1

E 2 n E2

U 2 2

iii. To calculate roughly the first order correction to Eon, we have to solve
the S.E.;

H n = ( H o + H ) n = En n

We know;

H U n = EonU n and

U n d = mn

*
m

For small perturbation;

En Eon + E1n and n U n

Then;

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Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

H o U n + H U n EonU n + E1nU n

H U n E1nU n

Multiply from the left by U*n and integrate

E 1n U *n H U n d = ( H ) nn

Therefore, the first order correction to En is roughly the expectation value

of the perturbed energy ( H ) when the system in state Un.

3-1-2 Formal Treatment

H = Ho+ H

Assume;

0 1

Where is the perturbation factor.

Such that;

= 0 Unperturbed
= 1 Full perturbed
Let;

n = on + 1n + 2 2 n + ...........
En = Eon + E1n + 2 E2 n + ...........

H n = En n

( H o + H )( on + 1 n + 2 2 n + ......) = ( Eon + E1 n + 2 E 2 n + ......)

( on + 1 n + 2 2 n + .....)

( H o on Eon on ) + ( H on + H o on E1n on Eon 1n ) +

2 ( H 1n + o 2 n E 2 n on E1n 1n Eon 2 n ) + 3 (........) + ....... = 0

Zero- order correction:

( H o on Eon on ) = 0

H o on = Eon on
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Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

But;

H oU n = EonU n
on = U n

First- order correction:

H on + H o 1n = E1n on + Eon 1n
Assume;

1n = a nkU k
k

H U n + H o ankU k = E1nU n + Eon ankU k

k

Multiply from the left by U m* and integrate over all the system space;

*
m

H U n d + ank Eok U m* U k d = E1n U m* U n d + Eon ank U m* U k d

k

( H )mn + a nk Eok mk = E1n mn + Eon a nk mk

k

( H )mn + anm Eom = E1n mn + Eon anm

( H )mn + anm ( Eom Eon ) = E1n mn
Case i. m = n

E1n = ( H )mn

Case ii. m n anm = ( H )mn /( Eon Eom )

1n = anmU m
m

= a nmU m + a nnU n
mn

H.W: using the relation = on + 1n , prove that ann = 0 ? And then

give the physical meaning.
The matrix of H called Matrix of Perturbation;

( H )mn = U m* H U n d
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Department of Physics/College of Education

( H )oo
( H )
1o

.....

( H )no

( H )o 1
( H )11
.....
( H )n 1

2014-2015

Quantum Mechanics/M.Sc. Course

..... ( H )on
..... ( H )1n

.....
.....

..... ( H )nn

For the first order correction;

En = Eon + ( H )nn

Where E1n = ( H )nn

( H )mn
Um
m n E on E om

n = Un +

( H )mn
Um
m n E on E om

Where 1m =

Notes:
1. First order correction to energy comes from diagonal elements of
the perturbation matrix.
2. First order correction to wave function comes from the offdiagonal elements of perturbation matrix.
3. Depending on the denominator, states which contribute most to

n will be those for which Eom is closes to Eon.

Second- order correction:

H 1n + H o 2 n = E2 n on + E1n 1n + Eon 2 n
Recall that 1n = a nkU k and assume that; 2 n = bnjU j then;
k

nk

H U k + bnj H oU j = E 2 nU n + E 1 n a nkU k + E on bnjU j

j

Multiply from the left by U m* and integrate over all space;

nk

( H )mk + bnj E oj mj = E 2 n mn + E 1 n a nk mk + E on bnj mj

j

nk

( H )mk + bnm Eom = E 2 n mn + E1n anm + Eon bnm

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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

Case (i): m = n
E2 n = ank ( H )nk E1 n ann
k

( H )kn
.( H )nk + ann ( H )nn E1n ann
k n E on E ok

( H )nk
=
k n E on E ok

Case (ii): m n

nk

( H )mk = bnm ( Eon Eom ) + E1n anm

bnm = ank
k

( H )mk
E1n
anm
Eon Eom
Eon Eom

Q ann = 0 and E1n = ( H )nn

( H )kn .( H )mk
( H )mn .( H )nn

( Eon Eom )2
k n ( E on E ok ).( E on E om )

bnm =

H.W: Show that;

bnn =
=

1
ank
2 k n

1
2
anm

2 m n
2

( H )mn
1
=
2 m n ( Eon E om ) 2

2 n = bnjU j = bnjU j + bnnU n

j

jn

= bnmU m + bnnU n
mn

( H )kn .( H )mk
( H )mn .( H )nn
1 ( H )mn
=

U m
n
( E on Eom )
2 ( Eon Eom )2
m n k n ( E on E ok )( E on E om )

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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

Therefore, the energy and the wave function corrected up to the secondorder are;
2

( H )nk
E n = E on + ( H )nn +
k n ( E on E ok )

n = U on + anmU m + bnmU m + bnnU n

mn

mn

Solution:

d = 1
*

+ 1 + 2 2 )* .( o + 1 + 2 2 )d = 1

o* o + o* 1 + 2 o* 2 + 1* o + 2 1* 1 + 3 1* 2 + 2 2* o +
d = 1
3 * + 4 *

2
1
2
2
U on* U on +

2
U on* a nmU m + 2U on* bnjU j + a*nmU m* U on + 2 a nm U m* U m + 2 bnj* U *jU on d = 1

m
j
m
m
j

1 + anm nm + 2 bnj nj + a*nm mn + 2 anm nm + 2 bnj* jn = 1

2

1 + ann + 2 bnn + a*nn + 2 anm + 2 bnn* = 1

2

Q ann = a*nn = 0
1 + 2 bnn + 2 anm + 2 bnn* = 1
2

Q bnn = bnn*
1 + 2 ( 2bnn + anm ) = 1
2

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Department of Physics/College of Education

bnn =

1
2
anm

2 mn

2014-2015

Quantum Mechanics/M.Sc. Course

,ann = 0

Notes:
1. Second order correction to energy involves first order correction to
wave function.
2. Second order correction to energy is smaller by ( H )nk /( Eon Eok )
than the first order.
3. Perturbation wave function rapidly get very complicated.
4. In principle we have a method to proceed to higher order correction
as needed.

3-2 Stark Effect on S.H.O.

b

V = E cos dx = Ex
a

energy = eV = eEx
2

H=

px 1
+ m 2 x 2 eEx
2m 2
2

Ho =

px 1
+ m 2 x 2
2m 2

and H = eEx

First order correction to energy: E1n = ( H ) nn = (eEx)nn = ?

Second order correction:
2

( H )nk
E2n =
k m E on E ok
+

( H )nk = eE U n* xU k dx

x = (2 )

+
2 (a + a )

, = m / h

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Department of Physics/College of Education

( H ) nk =

eE
2

2014-2015

Quantum Mechanics/M.Sc. Course

*
U n (a + a )U k dx

eE
2

{ k

n ,k 1

+ k + 1 n ,k + 1

Thus the only non- zero matrix elements of ( H )nk are those in which

k = n + 1 and k = n 1 , so;
0
1
eE
( H )nk =
2 0

0
2

2
0

..... .....
..... .....

3 .....

0 .....

( H )nk
E2n =
k m E on E ok
=

e2 E 2
2

n +1
n
+

( h ) h

e2 E 2
E2 n =
2m 2
1
e2 E 2
En = ( n + )h
2
2m 2

e 2 E 2 / 2 m 2

h
h

Hence, the effect of the perturbation is to shift each energy level by a

mount e 2 E 2 / 2m 2 .

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Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

3-3 Anharmonic Oscillator

Oscillators are the basis of many important models in physics, for
examples (photons, phonons, magnons,..). In real system, it is often
necessary to employ an anharmonic oscillator with cubic and / or
quadratic terms in the potential energy.
2
2
3
4
px 1
+ m 2 x + c x + D x
2m 2
Let H = cx3 only.

H=

p x2 1
H=
+ m 2 x 2 + cx 3
2m 2

E1n = ( H )nn = U n* cx3U n dx = zero

Off diagonal:

( H )nk = U n* H U k dx = cn \ x 3 \ k

x 3 = ( 2 ) 2 ( a+ a )3
3

+ +

+3

= ( 2 ) ( a + 3 a a a+ 3 a a a + a )
2

( H ) nk = c(2 )

3
2 n | a

n | a a a | k = k n | a a | k 1

= k k 1 n | a | k 2
= k k 1 k 2 n | k 3

= k ( k 1 )( k 2 ) n ,k 3
Second term:
+

+3

| k + 3 n | a a a | k + 3 n | a a a | k + n | a

First term:

+ +

3 n | a a a | k = 3 k n | a a | k 1

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| k

Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

= 3 k k n | a | k
= 3 k k k n | k 1

= 3k k n ,k 1
Third term:
+ +

3 n | a a a | k = 3 k + 1 n | a a | k + 1
+

= 3 k + 1 k + 1 n | a | k
= 3 k + 1 k + 1 k + 1 n | k + 1

= 3( k + 1 ) k + 1 n ,k +1
Forth term:
+ + +

+ +

n | a a a | k = k + 1 n | a a | k + 1
+

= k + 1 k + 2 n | a | k + 2
= k + 1 k + 2 k + 3 n | k + 3

= ( k + 1 )( k + 2 )( k + 3 ) n ,k + 3
( H ) nk = c(2 )

k (k 1)(k 2) n,k 3 + 3k k n,k 1 + 3(k + 1) k + 1 n,k +1 +

(k + 1)(k + 2)(k + 3) n,k +3

0
3

0
3
3 0
6 2
= c(2 ) 2
0
6
0 2 6

..... .....

.....

6 2
0
2 6
0
.....
0
9 3
0
2 15 .....

9 3
0
24
0
.....
0
24
0 15 5 .....

..... ..... .....

0
.....
0

Note that all the diagonal matrix element are equal to zero as will be
found before.
Perturbed Energies:
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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

En = Eon + E1n + E2 n
2

( H )nk
= E on + ( H )nn +
k m E on E ok

For ground state (n=0):

2

( H )ok
E o = E oo + ( H )oo +
k o E oo E ok

The only non- zero elements are; ( H )o1 and ( H )o 3 which equal to
3c( 2 )

6 c( 2 )

and

respectively.

2
2

1
c
3
( 6)
+
Eo = h + 0 + 3

2
8 1 h 3 h 1 h 7 h
2
2
2
2
2

1
11 c 2
= h
2
8 h 3
Perturbed wave functions:

n = on + 1n + .......
Ground state (n=0):
( H )ko
Uk
k o Eoo E ok

o = Uo +
= Uo

2
3U 1 + U 3

3
( 2 ) 2 h
c

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Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

3-4 Time- Independent Degenerate Perturbation Theory

1. Degenerate quantum system: two or more wave function has the
same energy.
2. first order correction are found as in the form: E1n = ( H )nn .
3. If the first order corrections are non- zero, they may lift the
degeneracy. For example, application of uniform magnetic field to
hydrogen atom (Zeeman Effect) gives different values of the
magnetic quantum number (m). While application of the electric
field (Stark Effect) does not lift the degeneracy in first order
because E1n=0.
4. We cannot use the second order perturbation theory because of the
denominator term, like Eon-Eok which can be zero.
So, one have to revised scheme to allow for degeneracy.
Suppose the S.E. for the perturbed system is;
( H o + H ) | p = E p | p

And the solution is;

| p = c pj | j
j

Substitute in S.E. and multiply by

k |

c pj k | H o | j + c pj k | H | j = E p c pj k | j
j

pj

Eoj kj + c pj ( H )kj = E p c pj kj

c pk Eok + c pj ( H ) kj = E p c pk
j

c pk ( E p E ok ) = c pj ( H )kj

..........( )

For simplest, assume that we have only two degenerate eigen functions
| r

and

| s

where;
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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

Eor = Eos
The effect of the perturbation is to mix the two eigen functions together.
| p = c pj | j
j

So, the perturbed wave functions | r and | s are;

| r = c rr | r + crs | s
| s = c sr | r + c ss | s

, Er E s

Equation (*) can be written as;

c pk ( E p E ok ) = c pr ( H )kr + c ps ( H )ks

Consider the perturbed state | r

c rk ( E r Eok ) = c rr ( H ) kr + c rs ( H ) ks

Which gives for;

k =r

crr {( H )rr + Eor Er } + crs ( H )rs = 0

k=s

crr ( H )sr + crs {( H )ss + Eos Er } = 0

These two equations have a solution if and only if there Wronksen is

zero; i.e.
( H )rr + E or E r
( H )sr

( H )rs
( H )ss + E os E r

=0

So, we can get;

E r2 E r {( H )rr + Eor + ( H )ss + Eos } + {( H )rr + Eor }{( H )ss + Eos }
( H )rs ( H )sr = 0

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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

The solution of this quadratic equation is;

E r = Eor +

( H )rr + ( H )ss 1
m [( H )rr ( H )ss ] 2 + 4 ( H )rs
2
2

You should remember that Eor = Eos .

In the same procedure we can get E s .

3-5 Stark Effect of Hydrogen Atom (Sihff p252)

For n=2 energy level, there are 4 degenerate wave function;
| nl m | 200 , | 210 , | 21 + 1 , | 21 1

Suppose that the electric field is applied in z- direction thus;

H = eEz = eEr cos

The matrix of perturbation is;

2lm | eEr cos | 2lm = eE 2*lm r cos 2lm d

Which consist of sixteen elements. By looking at the parity and the

symmetry, we can see that, the only non- zero elements;
( H ) 210, 200 = ( H ) 200, 210 = 200 | eEr cos | 210

2
eE 4
r / a
=
r ( z r / a o )e
dr . sin .cos d . d
32ao4 0
0
0
o

= 3eEao
Hence, the matrix of perturbation is;

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Department of Physics/College of Education

2014-2015

0
3eEa
o

3eEa o
0
0
0

Quantum Mechanics/M.Sc. Course

0 0
0 0

0 0

0 0

Consider that;
| r =| 200

and | s =| 210 such that

E or = E os = E( n = 2 )

( H )rr = ( H )ss = 0

Thus;

and

( H )rs = ( H )sr = 3eEao

Therefore,

E r = E( n = 2 ) m ( H )rs

E r = E( n = 2 ) + 3eEa o
E s = E( n = 2 ) 3eEa o

\ r

\ r

2 fold
E( n = 2 )

deg .state

4 fold
deg .states

\ s

\ s

Before perturbation

H.W:

| s = 2

2 (

200

2 (

200 210 )

Es = E( n =0 ) 3eEao

After perturbation

It can be easily seen that; crr / crs = 1. therefore;

| r = 2

Er = E( n = 2 ) + 3eEao

+ 210 )

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Department of Physics/College of Education

eE z
200 | eEr cos | 210 =
.
16( 2 ) ao

I = 2 r e

2
r / a
e
dr . cos 2 sin . d
0
0

r / ao

( x ) = e t t x 1 dt

dr

Let

Quantum Mechanics/M.Sc. Course

2
zr / ao
e
dr. cos 2 sin d . d

0
0

zr
4
r 2 ao
0

eE 4
r
. r 2
4
32a o 0
ao

2014-2015

r
= t r = ao t dr = ao dt
ao

I = 2 ao4 .t 4 e t .ao dt = 2 ao5 t 4 e t dt = ao5 ( 5 ) = 2 ao5 .4 !

II =
=

1 5 r / a
r e
dr
ao 0
o

1 5 5 t
5
5 t
5
5
!
a
t
e
a
dt
=
a
o
o
o t e dt = a o ( 6 ) = a o 5

ao 0
0

III = cos 2 sin d =

0

1
(( 1 )3 13 ) = 2
3
3

IIII = d = 2
0

200 | eEr cos | 210 =

2
5
5
.
2
a
.
24

a
.
120
.
.2
o
o
3
32ao4
eE

eE
2
( 48 120 )ao5 . .2
4
32a o
3

eE
2
.( 72 )ao5 . .2
4
32ao
3

eE
4
.(72)ao . = 3eEao
32
3

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Department of Physics/College of Education

2014-2015

Quantum Mechanics/M.Sc. Course

3-6 The Variation Method

Occasions for use this method are;
1. When there is no similar problem capable of exact solution, so
perturbation theory cannot used.
2. When there is a similar exact problem but perturbation term is too
large.
3. When the S.E. is non- separable and a large numerical solution
would be required.
The principle aim for using this method is; to calculate quickly an
upper bound for each of the two or three lowest energy level of the
system.

Energy Expectation Value:

Assume that the system have the following energy levels;

Eo E1 E2 ....., with the corresponding eigen functions

| 0 , | 1 , | 2 ,....,

such

as; H | n = En | n. According to the principle of linear superposition, any

arbitrary wave function can be written in terms of the functions | n as
follows;
| = cn | n
n

Thus;

| H |
H =
|

But;

*
| H | = cm
cn E n mn = cn E n
2

n m

*
| = c m
c n mn = c n
n m

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Department of Physics/College of Education

H = c n En / c n
2

2014-2015

Quantum Mechanics/M.Sc. Course

If we replaced each value En by Eo we get;

H Eo .

2
n

2
n

H Eo

| H |
Eo
|

Notes:
1. This provide an upper bound on Eo. Thus, it would be useful if the
right- hand side can be minimized.
2. In this method we choose a trial wave function with an adjustable
parameter and then we minimized the upper bound with respect to
this parameter.
3. The choice of the wave function is determined by the physics of
the system.

Minimization:
Choose the trial wave function to be real for simplicity, and;

H d
H =
2
d

2 d = H d

Vary implicitly with respect to the adjustable parameter and find the
variation of as follows;

( ) 2 d + 2 . d = ( H + H )d

Since H is Hermitical and is real, thus;

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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

H d = H d

2 d = ( H )d
2

The minimization condition is = 0

Case (i): if is infinitely an adjustable, then can take any value.
Thus we must have;

H =
And hence;

= Eo

And

=| 0

Case (ii): when is not infinitely an adjustable the minimization H is

used as an over estimate for Eo.

h2 2
H =
+V
2m

h2
2d + Vd

H = 2m
2
d

d = {.( ) ( ).( )}d

2

= ( )ds ( )2 d
s

= ( )2 d
2
h2
2
d + V d

H = 2m
2
d

So, the minimization of H with respect to the parameter ( ) i.e.

H / can be found from this equation.

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Department of Physics/College of Education

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Quantum Mechanics/M.Sc. Course

Example: Using the variatonal method find the energy and wave function
of ground state in the H- like atoms.
To choose the trial wave function we must note;
a) must be spherically symmetrical.
b) 0 as r
c) has no nodes.
Thus; suggest that

( r ) = A exp( r / 2 )
3
A 2 e r 4r 2 dr = 1 A =

0
8

1
r

1
= Ae 2
r
2

r
h 2 2 r

e
2
2
H = A
e
4

r
dr

Zk
4

r
dr

r
2m 0 4

h 2 2 Zk

8m
2

H h 2 Zk
=

=0

4m
2

E min =
E min =

ground

2mZk
h2

h 2 4m 2 Z 2 k 2 Zk 2mZk
.
. 2
8m
2 h
h4

mZ 2 k 2
2h 2

E min =

mZ 2 k 2

h2

mZ 2 k 2
2h 2

Z
=
ao

exp(Zr / ao )

Where k = e 2 / 4 o and ao = 4 o h 2 / me 2

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