Contents

Time-independent nondegenerate perturbation theory

Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Perturbation theory
Quantum mechanics 2 - Lecture 2
Igor Lukacevic
UJJS, Dept. of Physics, Osijek
17. listopada 2012.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
1
Time-independent nondegenerate perturbation theory
General formulation
First-order theory
Second-order theory
2
Time-independent degenerate perturbation theory
General formulation
Example: Two-dimensional harmonic oscilator
3
Time-dependent perturbation theory
4
Literature
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Contents
1
Time-independent nondegenerate perturbation theory
General formulation
First-order theory
Second-order theory
2
Time-independent degenerate perturbation theory
General formulation
Example: Two-dimensional harmonic oscilator
3
Time-dependent perturbation theory
4
Literature
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Do you remember this?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Do you remember this?
H
0

0
n
= E
0
n

0
n

0
n
|
0
m
=
nm
complete set
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Now, let us kick the potential bottom a little...

Igor Lukacevic Perturbation theory

Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Now, let us kick the potential bottom a little...

What wed like to solve now is...

H
n
= E
n

n
A question
Does anyone have an idea how?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H = H
0
+H

Igor Lukacevic Perturbation theory

Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H = H
0
+H

unperturbed Hamiltonian
perturbation Hamiltonian
small parameter
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H = H
0
+H

unperturbed Hamiltonian
perturbation Hamiltonian
small parameter
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H = H
0
+H

unperturbed Hamiltonian
perturbation Hamiltonian
small parameter
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Name Description Hamiltonian
L-S coupling Coupling between orbital and H = H
0
+ f (r )

L

S
spin angular momentum in a H

= f (r )

L

S
one-electron atom H
0
= p
2
/2m Ze
2
/r
Stark eect One-electron atom in a constant H = H
0
+ eE
0
z
uniform electric eld

E = e
z
E
0
H

= eE
0
z
H
0
= p
2
/2m Ze
2
/r
Zeeman eect One-electron atom in a constant H = H
0
+ (e/2mc)

J

B
uniform magnetic eld

B H

= (e/2mc)

J

B
H
0
= p
2
/2m Ze
2
/r
Anharmonic Spring with nonlinear restoring H = H
0
+ K

x
4
oscilator force H

= K

x
4
H
0
= p
2
/2m + 1/2Kx
2
Nearly free Electron in a periodic lattice H = H
0
+ V(x)
electron V(x) =

n
V
n
exp[i (2nx/a)]
model H
0
= p
2
/2m
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H is small compared to H
0
eigenstates and eigenvalues of H do not dier much from those of H
0
eigenstates and eigenvalues of H
0
are known
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H is small compared to H
0
eigenstates and eigenvalues of H do not dier much from those of H
0
eigenstates and eigenvalues of H
0
are known
expand

n
=
0
n
+
1
n
+
2

2
n
+. . . ,
E
n
= E
0
n
+E
1
n
+
2
E
2
n
+. . .
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Assume
H is small compared to H
0
eigenstates and eigenvalues of H do not dier much from those of H
0
eigenstates and eigenvalues of H
0
are known
expand

n
=
0
n
+
1
n
+
2

2
n
+. . . ,
E
n
= E
0
n
+E
1
n
+
2
E
2
n
+. . .
and sort
(
0
) . . . H
0

0
n
= E
0
n

0
n
,
(
1
) . . . H
0

1
n
+ H

0
n
= E
0
n

1
n
+ E
1
n

0
n
,
(
2
) . . . H
0

2
n
+ H

1
n
= E
0
n

2
n
+ E
1
n

1
n
+ E
2
n

0
n
,
.
.
.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Making
0
n
|
_
(
1
) and using the normalization property of
0
n
, we get
First-order correction to the energy
E
1
n
=
0
n
|H

|
0
n

For calculation
details, see Refs
[2], [3] and [4].
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
First-order correction to the energy
E
1
n
=
0
n
|H

|
0
n

Example 1
Find the rst-order corrections to the energy of
a particle in a innite square well if the oor
of the well is raised by an constant value V
0
.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
First-order correction to the energy
E
1
n
=
0
n
|H

|
0
n

Example 1
Find the rst-order corrections to the energy of
a particle in a innite square well if the oor
of the well is raised by an constant value V
0
.
Unperturbed w.f.:
0
n
(x) =
_
2
a
sin
_
n
a
x
_
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
First-order correction to the energy
E
1
n
=
0
n
|H

|
0
n

Example 1
Find the rst-order corrections to the energy of
a particle in a innite square well if the oor
of the well is raised by an constant value V
0
.
Unperturbed w.f.:
0
n
(x) =
_
2
a
sin
_
n
a
x
_
Perturbation Hamiltonian: H

= V
0
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
First-order correction to the energy
E
1
n
=
0
n
|H

|
0
n

Example 1
Find the rst-order corrections to the energy of
a particle in a innite square well if the oor
of the well is raised by an constant value V
0
.
Unperturbed w.f.:
0
n
(x) =
_
2
a
sin
_
n
a
x
_
Perturbation Hamiltonian: H

= V
0
First-order correction:
E
1
n
=
0
n
|V
0
|
0
n
= V
0

0
n
|
0
n
= V
0
corrected energy levels: E
n
E
0
n
+ V
0
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 1
Find the rst-order corrections to the energy of
a particle in a innite square well if the oor
of the well is raised by an constant value V
0
.
Unperturbed w.f.:
0
n
(x) =
_
2
a
sin
_
n
a
x
_
Perturbation Hamiltonian: H

= V
0
First-order correction:
E
1
n
=
0
n
|V
0
|
0
n
= V
0

0
n
|
0
n
= V
0
corrected energy levels: E
n
E
0
n
+ V
0
Compare this result with an exact solution
for a constant perturbation all the
higher corrections vanish
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 1
Find the rst-order corrections to the energy of
a particle in a innite square well if the oor
of the well is raised by an constant value V
0
.
Unperturbed w.f.:
0
n
(x) =
_
2
a
sin
_
n
a
x
_
Perturbation Hamiltonian: H

= V
0
First-order correction:
E
1
n
=
0
n
|V
0
|
0
n
= V
0

0
n
|
0
n
= V
0
corrected energy levels: E
n
E
0
n
+ V
0
Compare this result with an exact solution
for a constant perturbation all the
higher corrections vanish
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 1 (cont.)
Now, cut the perturbation to only a half-way
across the well
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 1 (cont.)
Now, cut the perturbation to only a half-way
across the well
E
1
n
=
2V
0
a
_
a/2
0
sin
2
_
n
a
x
_
dx =
V
0
2
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 1 (cont.)
Now, cut the perturbation to only a half-way
across the well
E
1
n
=
2V
0
a
_
a/2
0
sin
2
_
n
a
x
_
dx =
V
0
2
HW. Compare this result with an exact one.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Now we seek the rst-order correction to the wave function.
(
1
) and
1
n
=

m=n
c
mn

0
m
give
First-order correction to the wave
function

1
n
=

m=n

0
m
|H

|
0
n

(E
0
n
E
0
m
)

0
m
For calculation
details, see Refs
[2], [3] and [4].
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
First-order correction to the wave
function

1
n
=

m=n

0
m
|H

|
0
n

(E
0
n
E
0
m
)

0
m
For calculation
details, see Refs
[2], [3] and [4].
In conclusion
First-order perturbation theory gives:
often accurate energies
poor wave functions
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
H
0
eigenenergies: E
0
n
=
_
n +
1
2
_

Igor Lukacevic Perturbation theory

Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
H
0
eigenenergies: E
0
n
=
_
n +
1
2
_

H
0
eigenfunctions:

0
n
(x) =
_
1
2
n
n!
_

x
2
2
H
n
(x

)
Dont forget...
n H
n
()
0 1
1 2
2 4
2
2
3 8
3
12
4 16
4
48
2
+ 12
5 32
5
160
3
+ 120
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
H
0
eigenenergies: E
0
n
=
_
n +
1
2
_

H
0
eigenfunctions:

0
n
(x) =
_
1
2
n
n!
_

x
2
2
H
n
(x

)
E
1
n
=
0
n
|ax
3
|
0
n
= 0
Dont forget...
n H
n
()
0 1
1 2
2 4
2
2
3 8
3
12
4 16
4
48
2
+ 12
5 32
5
160
3
+ 120
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
H
0
eigenenergies: E
0
n
=
_
n +
1
2
_

H
0
eigenfunctions:

0
n
(x) =
_
1
2
n
n!
_

x
2
2
H
n
(x

)
E
1
n
=
0
n
|ax
3
|
0
n
= 0
For
1
n
we need expressions
0
m
|H

|
0
n

Dont forget...
n H
n
()
0 1
1 2
2 4
2
2
3 8
3
12
4 16
4
48
2
+ 12
5 32
5
160
3
+ 120
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
H
0
eigenenergies: E
0
n
=
_
n +
1
2
_

H
0
eigenfunctions:

0
n
(x) =
_
1
2
n
n!
_

x
2
2
H
n
(x

)
E
1
n
=
0
n
|ax
3
|
0
n
= 0
For
1
n
we need expressions
0
m
|H

|
0
n

for m = n 2k , k Z these are zero

Dont forget...
n H
n
()
0 1
1 2
2 4
2
2
3 8
3
12
4 16
4
48
2
+ 12
5 32
5
160
3
+ 120
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
Hamiltonian: H =

2
2m
d
2
dx
+
1
2
kx
2
+ ax
3
H
0
eigenenergies: E
0
n
=
_
n +
1
2
_

H
0
eigenfunctions:

0
n
(x) =
_
1
2
n
n!
_

x
2
2
H
n
(x

)
E
1
n
=
0
n
|ax
3
|
0
n
= 0
For
1
n
we need expressions
0
m
|H

|
0
n

for m = n 2k , k Z these are zero

so, well, for example, take only these:
m = n + 3, n + 1, n 1, n 3
Dont forget...
n H
n
()
0 1
1 2
2 4
2
2
3 8
3
12
4 16
4
48
2
+ 12
5 32
5
160
3
+ 120
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
n|ax
3
|n + 3 = a
_
(n + 1)(n + 2)(n + 3)
(2)
3
n|ax
3
|n + 1 = 3a
_
(n + 1)
3
(2)
3
n|ax
3
|n 1 = 3a
_
n
3
(2)
3
n|ax
3
|n 3 = a
_
n(n 1)(n 2)
(2)
3
Dont forget...
n H
n
()
0 1
1 2
2 4
2
2
3 8
3
12
4 16
4
48
2
+ 12
5 32
5
160
3
+ 120
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a
harmonic oscilator with applied small
perturbation W = ax
3
.
n|ax
3
|n + 3 = a
_
(n + 1)(n + 2)(n + 3)
(2)
3
n|ax
3
|n + 1 = 3a
_
(n + 1)
3
(2)
3
n|ax
3
|n 1 = 3a
_
n
3
(2)
3
n|ax
3
|n 3 = a
_
n(n 1)(n 2)
(2)
3
Energy dierences
m E
n
E
m
n+3 3
n+1
n-1
n-3 3
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Example 2
Compute the rst-order corrections for a harmonic oscilator
with applied small perturbation W = ax
3
.
n|ax
3
|n + 3 = a

(n + 1)(n + 2)(n + 3)
(2)
3
n|ax
3
|n + 1 = 3a

(n + 1)
3
(2)
3
n|ax
3
|n 1 = 3a

n
3
(2)
3
n|ax
3
|n 3 = a

n(n 1)(n 2)
(2)
3
Energy dierences
m E
n
E
m
n+3 3
n+1
n-1
n-3 3

1
n
=
a
2
_
1
3
_
n(n 1)(n 2)
2

0
n3
+ 3n
_
n
2

0
n1
3(n + 1)
_
n + 1
2

0
n+1

1
3
_
(n + 1)(n + 2)(n + 3)
2

0
n+3
_
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Making
0
n
|
_
(
2
), using the normalization property of
0
n
and orthogonality
between
0
n
and
1
n
, we get
Second-order correction to the
energy
E
2
n
=

m=n
|
0
m
|H

|
0
n
|
2
E
0
n
E
0
m
For calculation
details, see Refs
[2], [3] and [4].
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
First-order theory
Second-order theory
Now we seek the second-order correction to the wave function.
(
2
) and
1
n
=

m=n
c
mn

0
m
give
Second-order correction to the wave function

2
n
=

m=n
_

0
n
|H

|
0
n

0
m
|H

|
0
n

(E
0
n
E
0
m
)
2
+

k=n

0
m
|H

|
0
k

0
k
|H

|
0
n

(E
0
n
E
0
m
)(E
0
n
E
0
k
)
_

0
m
For calculation
details, see Refs
[2], [3] and [4].
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Contents
1
Time-independent nondegenerate perturbation theory
General formulation
First-order theory
Second-order theory
2
Time-independent degenerate perturbation theory
General formulation
Example: Two-dimensional harmonic oscilator
3
Time-dependent perturbation theory
4
Literature
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Symmetry Degeneracy
Perturbation
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Symmetry Degeneracy
Perturbation
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
A question
Whats wrong with
E
2
n
=

m=n
|
0
m
|H

|
0
n
|
2
E
0
n
E
0
m
, m, n q
if unperturbed eigenstates are degenerate E
0
1
= E
0
2
= = E
0
q
?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Matrix H

in basis B
H

=
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
H

11
H

1,q+1
. . .
.
.
.
0
H

q/2,q/2
0
.
.
.
H

qq
H

q+1,1
.
.
.
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
_
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
For n = 1,
q

m=1
(H

pm
E

pm
)a
nm
= 0 appear as
_
_
_
_
_
H

11
E

1
H

12
H

13
. . . H

1q
H

21
H

22
E

1
H

23
. . . H

2q
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
H

q1
_
_
_
_
_
_
_
_
_
_
a
11
a
12
.
.
.
a
1q
_
_
_
_
_
= 0
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
The q roots of secular equation det

n
I

= 0 are the diagonal elements of

the submatrix of H

.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
H = H
0
+ H

H
0

0
n
= E
0
n

0
n
E
0
1
q-fold degenerate
m
1
E
Construct

n
=
q

i =1
a
nm

0
m
which diagonalizes submatrix
of H

n
|H

|
k
= E

nk
m
2

%
Nondegenerate
perturbation theory
with basis B
q

(H

)a = 0
m
3
E
det

n
I

= 0
m
8
m
6 m
5
m
4
T
c

y
c
{
n
}
Gives new basis B
m
7
'
{a
ni
} E

1
, E

2
, . . . , E

q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator

n
=
n
+
1
n
+
2

2
n
+. . . n q

n
=
0
n
+
1
n
+
2

2
n
+. . . n > q
E
n
= E
0
n
+E
1
n
+
2
E
2
n
+. . . n q (E
0
1
= = E
0
q
)
E
n
= E
0
n
+E
1
n
+
2
E
2
n
+. . . n > q
E

n
=
n
|H

|
n
n q
E
1
n
=
0
n
|H

|
0
n
n > q
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator

n
=
n
+
1
n
+
2

2
n
+. . . n q

n
=
0
n
+
1
n
+
2

2
n
+. . . n > q
E
n
= E
0
n
+E
1
n
+
2
E
2
n
+. . . n q (E
0
1
= = E
0
q
)
E
n
= E
0
n
+E
1
n
+
2
E
2
n
+. . . n > q
E

n
=
n
|H

|
n
n q
E
1
n
=
0
n
|H

|
0
n
n > q
So, what do we get from degenerate perturbation theory:
1st-order energy corrections
corrected w.f. (with nondegenerate states they serve as a basis for
higher-order calculations)
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Two-dimensional harmonic oscilator Hamiltonian:
H
0
=
p
2
x
+ p
2
y
2m
+
K
2
(x
2
+ y
2
)

np
=
n
(x)
p
(y) |np
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Two-dimensional harmonic
oscilator Hamiltonian:
H
0
=
p
2
x
+ p
2
y
2m
+
K
2
(x
2
+ y
2
)

np
=
n
(x)
p
(y) |np
E
np
= (n + p + 1) is
(n + p + 1)-fold degenerate.
Whats the degeneracy of |01
state?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Two-dimensional harmonic
oscilator Hamiltonian:
H
0
=
p
2
x
+ p
2
y
2m
+
K
2
(x
2
+ y
2
)

np
=
n
(x)
p
(y) |np
E
np
= (n + p + 1) is
(n + p + 1)-fold degenerate.
Whats the degeneracy of |01
state?
E
10
= E
01
= 2
0
.
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Now, turn on the perturbation: H

= K

xy
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Now, turn on the perturbation: H

= K

xy
nd w.f. which diagonalize H

1
= a
10
+ b
01

2
= a

10
+ b

01
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Now, turn on the perturbation: H

= K

xy
nd w.f. which diagonalize H

1
= a
10
+ b
01

2
= a

10
+ b

01
calculate the elements of submatrix of H

in the basis {
10
,
01
}
H

= K

_
10|xy|10 10|xy|01
01|xy|10 01|xy|01
_
= E
_
0 1
1 0
_
E =
K

2
2
,
2
=
m
0

Igor Lukacevic Perturbation theory

Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
Now, turn on the perturbation: H

= K

xy
nd w.f. which diagonalize H

1
= a
10
+ b
01

2
= a

10
+ b

01
calculate the elements of submatrix of H

in the basis {
10
,
01
}
H

= K

_
10|xy|10 10|xy|01
01|xy|10 01|xy|01
_
= E
_
0 1
1 0
_
E =
K

2
2
,
2
=
m
0

solve the secular equation

E
E E

= 0 E

= E
E
10
E
+
= E
10
+E
E

= E
10
E

d
d
d
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
obtain the new w.f. from
_
E

E
E E

__
a
b
_
= 0
=
E

= +E
1
=
1

2
(
10
+
01
)
E

= E
2
=
1

2
(
10

01
)
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
General formulation
Example: Two-dimensional harmonic oscilator
obtain the new w.f. from
_
E

E
E E

__
a
b
_
= 0
=
E

= +E
1
=
1

2
(
10
+
01
)
E

= E
2
=
1

2
(
10

01
)
HW
How does the threefold-degenerate energy
E = 3
0
of the two-dimensional harmonic oscilator separate due to the perturbation
H

= K

xy ?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Contents
1
Time-independent nondegenerate perturbation theory
General formulation
First-order theory
Second-order theory
2
Time-independent degenerate perturbation theory
General formulation
Example: Two-dimensional harmonic oscilator
3
Time-dependent perturbation theory
4
Literature
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Problem
If the system is initially in H
0
, what is the probability that, after time t,
transition to another state (of H
0
) occurs?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Problem
If the system is initially in H
0
, what is the probability that, after time t,
transition to another state (of H
0
) occurs?
Let us assume:
H(r , t) = H
0
(r ) +H

(r , t)

n
(r , t) =
n
(r )e
i t
H
0

n
= E
0
n

n
(r , t) =

n
c
n
(t)
n
(r , t) , t > 0
i

t
= (H
0
+H

)
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Problem
If the system is initially in H
0
, what is the probability that, after time t,
transition to another state (of H
0
) occurs?
Let us assume:
H(r , t) = H
0
(r ) +H(r , t)

n
(r , t) =
n
(r )e
i t
H
0

n
= E
0
n

n
(r , t) =

n
c
n
(t)
n
(r , t) , t > 0
i

t
= (H
0
+H

)
Can you remember the meaning of these coecients?
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Inserting (r , t) and c
n
(t) = c
0
n
+c
1
n
(t) +
2
c
2
n
(t) +. . . into time-dependent
S.E. and factorizing the perturbation Hamiltonian as H

(r , t) = H

(r )f (t) gives
Probability that the system has undergone a transition from state
l
to state

k
at time t
P
l k
= P
lk
= |c
n
|
2
=

kl

_
t

e
i
kl
t

f (t

)dt

2
For calculation details, see Refs [2] and [3].
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Contents
1
Time-independent nondegenerate perturbation theory
General formulation
First-order theory
Second-order theory
2
Time-independent degenerate perturbation theory
General formulation
Example: Two-dimensional harmonic oscilator
3
Time-dependent perturbation theory
4
Literature
Igor Lukacevic Perturbation theory
Contents
Time-independent nondegenerate perturbation theory
Time-independent degenerate perturbation theory
Time-dependent perturbation theory
Literature
Literature
1
I. Supek, Teorijska zika i struktura materije, II. dio,

Skolska knjiga,
Zagreb, 1989.
2
D. J. Griths, Introduction to Quantum Mechanics, 2nd ed., Pearson
Education, Inc., Upper Saddle River, NJ, 2005.
3
R. L. Libo, Introductory Quantum Mechanics, Addison Wesley, San
Francisco, 2003.
4
A. Szabo, N. Ostlund, Modern Quantum Chemistry, Introduction to
Advanced Electronic Structure theory, Dover Publications, New York,
1996.
5
Y. Peleg, R. Pnini, E. Zaarur, Shaums Outline of Theory and Problems of
Quantum Mechanics, McGraw-Hill, 1998.
Igor Lukacevic Perturbation theory