Quantum mechanics course Stationary Ptexamples | Perturbation Theory (Quantum Mechanics) | Scientific Theories

# Lecture 20.

Perturbation Theory: Examples
* The tilted potential well
 The quantum-confined Stark effect
* Degenerate perturbation theory
 Two-dimensional quantum well
• Previously we discussed an APPROXIMATE approach to determine the energy eigenvalues
and eigenfunctions of a PERTURBED system in terms of those of an EXACT system
* In these equations 
n
and 
n
are the energy eigenvalues and eigenfunctions of the
exact system while E
n
and 
n
are those of the perturbed system
* Today we discuss some illustrative APPLICATIONS of this PERTURBATION THEORY
We begin by considering the case of an electron that moves in a TILTED potential
well that results when a uniform electric field is applied to the system
The Tilted Potential Well
) 23 . 19 (
,
*
¯
=
+
÷
+ + =
n k k
k n
nk nk
nn n n
V V
V E 
 

) 24 . 19 (
,
*
¯
=
+
÷
+ =
n k k
k
k n
nk
n n
V
 
 
 
• The UNPERTURBED system that here is taken to be an INFINITE potential well centered on
the origin x = 0
* The energy EIGENVALUES for this system were computed previously
* With the well centered on the origin it is easy to show that the EIGENFUNCTIONS of
the Hamiltonian exhibit either EVEN or ODD symmetry and take the form
The Tilted Potential Well

, 3 , 2 , 1 ,
2
2
2 2
2
= = n
mL
n
n

) 1 . 20 ( , 5 , 3 , 1 , cos
2
) (  =

= n x
L
n
L
x
even
n

) 2 . 20 ( , 6 , 4 , 2 , sin
2
) (  =

= n x
L
n
L
x
odd
n

V

-L/2 +L/2
• For the PERTURBED system we wish to consider how the GROUND-STATE energy is
modified by the application of the electric field
* The perturbation to the exact Hamiltonian due to the application of the electric field is
* The FIRST-ORDER correction to the ground-state energy depends on the matrix
element V
11
and VANISHES due to the antisymmetry of the integrand
This result is true for ALL eigenvalues of the potential well whose first-order
corrections all vanish due to antisymmetry
This is REASSURING since the correction to the energy should NOT depend on
the direction of the electric field
The Tilted Potential Well
) 3 . 20 ( eEx V =
) 4 . 20 ( 0 cos
2
2 /
2 /
2
11
) 1 (
1
=
1
J
(

= =
÷
dx x
L
x eE
L
V E
L
L

• The SECOND-ORDER correction to the energy depends on matrix elements of the form
* Here we have exploited the fact that the function x is antisymmetric while cos[x/L] is
symmetric so that the only matrix elements that do not vanish are those involving
EVEN values of k whose wavefunctions are ANTISYMMETRIC
The second-order energy correction to the ground-state eigenvalue is therefore
As discussed previously we see that the energy is LOWERED due to the presence
of the perturbation
The Tilted Potential Well
) 5 . 20 ( , 6 , 4 , 2 , cos sin
2
2 /
2 /
1
 =
1
J
(

=
÷
k dx x
L
x x
L
k
eE
L
V
L
L
k
 
) 6 . 20 ( 3 , 2 , 1 ,
1 1 2
1 , 2
*
1 , 2 ) 2 (
1
 =
÷
÷ =
¯
·
=
k
V V
E
k k
k k
 
• For a LOWER-BOUND on the second-order energy correction E
1
(2)
we consider the FIRST
term of Eq. 20.6 alone (V
21
)
* Substituting this result into Eq. 20.6 we may therefore write
Note here that we have exploited the fact that for the infinite well 
2
= 4
1
In order for this result to be valid we require the energy shift E
1
(2)
be SMALLER
than the inter-level separation ~
1
The Tilted Potential Well
) 7 . 20 (
9
16
cos
2
sin
2
2
2 /
2 /
21
eEL dx x
L
x x
L
eE
L
V
L
L

 
=
1
J
(

=
÷
) 8 . 20 (
243
256
3
1
2 2 2
4
1
21
*
21
1 2
21
*
21 ) 2 (
1
    
L E e V V V V
E ÷ = ÷ =
÷
÷ =
• While we have only considered the LOWEST matrix element V
21
in our calculation of E
1
(2)
the calculation CAN be extended to higher order elements V
2k,1
* An analytical solution is actually possible in this case but yields a result that differs by
only 0.1%from Eq. 20.8
* An important result of our analysis is that in a quantum well formed between different
semiconductors an electric field REDUCES the energy gap for electron-hole pair
creation
This is referred to as the QUANTUM-CONFINED STARK EFFECT
The Tilted Potential Well
• SHOWN LEFT IS THE POTENTIAL WELL IN
THE ABSENCE OF THE ELECTRIC FIELD WHILE
THE WELL IN THE APPLIED FIELD IS SHOWN
RIGHT
• NOTE HOW THE ENERGY GAP FOR ELECTRON
EXCITATION TO THE CONDUCTION BAND IS
REDUCED IN THE PRESENCE OF THE ELECTRIC
FIELD
• THIS SHIFTS THE ABSORPTION THRESHOLD OF
THE QUANTUM WELL TO LOWER FREQUENCIES
• * A particle of mass m is confined in an infinite potential well of length L. If this potential
is now subject to a -function perturbation of the form V(x) = L
o
(x-L/2) estimate the
resulting modifications to the energy levels of the well
The ODD energy levels are all RAISED by the SAME amount 2
o
The EVEN energy levels are UNAFFECTED by the perturbation to first order
however since their wavefunctions all VANISH at the position where the delta-
function perturbation is located
Example
 , 3 , 2 , 1 , sin
2
) ( =

= n x
L
n
L
x
n

¦
¹
¦
´
¦
= ÷
1
J
(
=
even n
odd n
dx L x L
L
x n
L
E
o
o
L
n
, 0
, 2
) 2 / ( sin
2
0
2 ) 1 (

 

• The perturbation theory that we have developed thus far can FAIL if two or more levels of
the system under study are degenerate since the perturbation expansion then DIVERGES
* A NEWapproach is needed here and to develop this we note that since the degenerate
levels lead to divergence this suggests that we FOCUS on the effects of these levels
* To develop this degenerate perturbation theory we consider the specific problem of a
TWO-DIMENSIONAL infinite square well of side length a in the x-y plane
It is relatively straightforward to show that the quantized energies of such a well
are given by
) 23 . 19 (
,
*
¯
=
+
÷
+ + =
n k k k n
nk nk
nn n n
V V
V E 
 

Degenerate Perturbation Theory
) 9 . 20 ( , 3 , 2 , 1 , , ) (
2
2 2
2
2 2
,

= + = q p q p
ma
q p

• The GROUND-STATE of the well is found by taking p = q = 1 and is therefore NON-
DEGENERATE
* The next energy level is DOUBLY DEGENERATE however
* It is straightforward to show that the wavefunctions associated with these two
degenerate levels are
Degenerate Perturbation Theory
) 11 . 20 (
2
sin cos
2
2 , 1
a
y
a
x
a
A
 
  = ÷
) 12 . 20 ( sin
2
cos
2
1 , 2
a
y
a
x
a
B
 
  = ÷
) 10 . 20 ( ) 1 2 (
2
) 2 1 (
2
2 2
2
2 2
2 2
2
2 2
2 , 1
+ = + = ÷
ma ma
   
 
• We now consider what happens if we add a PERTURBATION to the potential in the well
* The idea in degenerate perturbation theory is to solve the Schrödinger equation
EXACTLY but only for the degenerate states
* For the doubly-degenerate level of interest here we therefore need to recast the
Hamiltonian as a 2 x 2 matrix
* The first matrix element is easily evaluated
Degenerate Perturbation Theory
) 14 . 20 ( 0 , ) , ( > ÷ = K Kxy y x V
) 15 . 20 (
| | | |
| | | |
H

> < > <
> < > <
=
B H B B H A
A H B A H A
) 16 . 20 ( 0 | | | | | |   = + = > < + > < = > < A V A A H A A H A
o
REMEMBER THAT 
A
IS AN EIGENSTATE OF
H
o
WITH ENERGY 
THIS INTEGRAL
VANISHES BECAUSE
OF THE SYMMETRY
OF V (Eq. 20.14)
• The next matrix element is similarly evaluated
* The last term on the RHS of Eq. 20.17 is just the integral
* The matrix Schrödinger equation therefore reduces to
Degenerate Perturbation Theory
) 17 . 20 ( | | | | | | | > < ÷ = > < ÷ > < = > < B Kxy A B Kxy A B A B H A 
) 18 . 20 (
9
16
sin
2
cos
2
sin cos
4
2
2
2 /
2 /
2
A ÷ ÷ ÷ =
1
J
(
÷
+
÷
Ka dxdy
a
y
a
x
xy
a
y
a
x
a
K
a
a

   
) 19 . 20 ( a a E =

A ÷
A ÷

• The condition for solution to Eq, 20.19 is
* Solution of Eq. 20.20 now yields TWO distinct energy solutions
Thus we see that the effect of the perturbation is to LIFT the degeneracy yielding
TWO non-degenerate solutions
The degeneracy is lifted since the perturbation to the Hamiltonian BREAKS the
symmetry of the potential well
We will discuss some examples of degenerate perturbation theory in the
following classes
Degenerate Perturbation Theory
) 20 . 20 ( 0 ) (
2 2
= A ÷ ÷ =
÷ A
A ÷

E
E
E
) 21 . 20 ( A ± =  E
Homework
P20.1 Assuming hydrogen nucleus (proton) is a uniformly charged sphere with a radius of 10
-15
m, instead of a point as we have assumed in lecture 17. Using perturbation theory,
calculate the corresponding correction in the ground state energy. Hint: The potential
energy inside the sphere is changed to
P20.2 A particle of mass m is in an infinite potential well perturbed as shown in the figure
below. (a) Calculate the first-order energy shift of the n
th
eigenvalue due to the
perturbation. (b) Write out the first three nonvanishing terms for the perturbation
expansion of the ground state in terms of the unperturbed eigenfunctions of the
infinite well. (c) Calculate the second-order energy shift for the ground state.
P20.3 Consider the perturbed 2-D oscillator Hamiltonian
Use perturbation theory to calculate the energy shift of the degenerate first excited state
to first order due to the perturbation ìxy. What are the first order wave functions?
a
e
0
4
1

÷
0
a/2
a
h
2
/(40ma
2
)
xy y x k p p
m
H
y x
 + + + + = ) (
2
1
) (
2
1
2 2 2 2