Unit 14

Approximation methods
in quantum mechanics

Perturbation theory:

TISE: ˆ ψ n = Enψ n
H

ˆ (0)ψ n(0) = En(0)ψ n(0)

H
(closely related; simplified; exact solution)
perturbation: δ H ˆ =H ˆ −H ˆ (0)

ψ n(0) ⇔ ψ n

perturbation can
shift unperturbed
levels, split
degenerate levels

SM355 – 2005 1 22 September/Tut7

iterative process: approximation can be fed back in to get
better approximation

δH
ˆ =H
ˆ −H
ˆ (0) = kH
ˆ (1) leads to perturbation expansions:

En = En(0) + kEn(1) + k 2 En(2) + …

ψ n = ψ n(0) + kψ n(1) + k 2ψ n(2) + …

equating terms of same order give a series of

relationships, the most important being the first-order
relationship:

kEn(1) = (ψ n(0) , δ H
ˆ ψ n(0) )

i.e., the first-order energy correction is equal to the

expectation value of the perturbation evaluated in the
zero-order eigenstate
SM355 – 2005 2 22 September/Tut7
different sets of degenerate zero-order eigenvectors may
give different corrections (shifts or splittings)
2
(δ H ) pn ψ (0)
(δ H ) pn
kψ =∑ =∑
(1) p 2 (2)
k E
−E −
n (0) (0) n (0) (0)
p≠n En p E
p≠n n E p

diagonal matrix elements = first-order energy corrections:

kEn(1) = (ψ n(0) , δ H
ˆ ψ (0) ) = (δ H )
n nn

terms of perturbation expansion decrease rapidly if small

perturbation: (δ H ) pn En(0) − E p(0) p≠n

problems when the perturbation removes the degeneracy of

a set of degenerate zero-order states: combine states

variational method:

estimate energy eigenvalues, especially ground state

energy

use trial wavefunction ψ t ( x)

E =
( ˆψ )
ψ ,H
t t

(ψ t ,ψ t )
uses adjustable parameters: minimize E

SM355 – 2005 3 22 September/Tut7

 Unit 15
Identical particles and atomic structure

Symmetric function: f ( x2 , x1 ) = f ( x1 , x2 )

Antisymmetric function: f ( x2 , x1 ) = − f ( x1 , x2 )

Pˆ12 Ψ ( r1 , r2 , t ) = Ψ ( r2 , r1 , t ) exchange operator

Schrödinger’s equation for 1-D system of two non-

interacting particles:

⎛ 2
∂2 2
∂2 ⎞ ∂Ψ
− −
⎜ 2m ∂x 2 2m ∂x 2 1 1+ V ( x ) + V ( x2 ⎟
) Ψ ( x , x , t ) = i ( x1 , x2 , t )
∂
2 1 2
⎝ 1 1 2 2 ⎠ t

Probability: Ψ * ( x1 , x2 , t ) Ψ ( x1 , x2 , t ) ∆x1∆x2

Solutions: Ψ ( x1 , x2 , t ) = Ψ A ( x1 ) Ψ B ( x2 )e −i ( EA + EB ) t /
with
2
d 2ψ A
− 2
+ V1 ( x1 )ψ A = E Aψ A
2m1 dx1
d 2ψ B
2
− 2
+ V2 ( x2 )ψ B = E Aψ B
2m2 dx2
E = E A + EB
SM355 – 2005 4 22 September/Tut7
Identical particles: cannot be distinguished by means of
any inherent property such as mass, charge, or spin

Wave function for a system of identical particles must be

either symmetric or antisymmetric under the interchange
of the coordinates of any pair of particles:
1
ψ s ( x1 , x2 ) = [ψ A ( x1 )ψ b ( x2 ) + ψ A ( x2 )ψ B ( x1 )]
2
1
ψ a ( x1 , x2 ) = [ψ A ( x1 )ψ b ( x2 ) −ψ A ( x2 )ψ B ( x1 )]
2
E = E A + EB

half-integer spin: fermions antisymmetric total Ψ

integer spin: bosons symmetric total Ψ

ψ s (r1 , r2 ) = ψ A (r1 )ψ A ( r2 )

two identical spin-half particles:

1
[α (1)β (2) − α (2) β (1)] singlet
2
1
α (1)α (2) [α (1)β (2) + α (2)β (1)] β (1) β (2)
2
(triplet: S = 1 ms = 1,0, −1)

⎧ sym × sym
Ψ S = spatial × spin = ⎨
⎩ antisym × antisym
Ψ A = oneA × otherS
SM355 – 2005 5 22 September/Tut7
Pauli exclusion principle: no two identical fermions in a
system can be in the same state (have all the quantum
numbers the same) ⇒ antisymmetric total wavefunction
⇒ periodic table

• conduction electrons have small contribution to

specific heat
• superfluidity of 4He at low temperature: bosons
• Mott scattering: takes into account symmetry of
Ψ (note Rutherford does not take care of identical
particles)

symmetry is important when there’s significant overlap

Helium atom:

semi-classical Bohr model, modified to use

Coulomb electron-electron repulsion
electronic screening

can use first-order perturbation theory

one-particle hydrogen-like wave functions
perturbation: electron-electron interaction
split singlet and triplet states
good agreement
ground state energy level: variational theory, 2%
energy levels: specified by n, L, S, J
SM355 – 2005 6 22 September/Tut7
Many electrons:

Hartree self-consistent field method

“aufbau” method (one-particle hydrogen-like electron

states, Pauli exclusion principle) ⇒ periodic table, etc.

energy levels have large gaps: shells between gaps

SM355 – 2005 7 22 September/Tut7

 Unit 16
Applications: the fine structure of
the hydrogen atom, and the binding of
the hydrogen molecular ion

spin-orbit

1 ⎛ e2 ⎞1 ˆ ˆ
δH
ˆ spin-orbit =
⎜ 4πε m 2 c 2 ⎟ r 3 L ⋅ S
2 ⎝ 0 ⎠
Thomas precession
relativistic

relativistic perturbation

expand classical relativistic KE as a Taylor series in

( p / mc) 2 , p → pˆ = −i ∇
( )
2
p
ˆ ⋅ p
ˆ
δHˆ rel = −
8m3c 2

e2 2
δH
ˆ Darwin = δ ( x)δ ( y )δ ( z )
8ε 0 m 2 c 2
Darwin term 2 2

( ψ,δ Hˆ Darwin ψ ) = 8ε m2c 2 ψ (0) 2

e
0
only for s-states of hydrogen atom (l = 0) (see Q1.9 1997)

SM355 – 2005 8 22 September/Tut7

calculate energy shifts due to perturbations:

l>0
1⎛ e2 ⎞ 2
δE (1)spin-orbit
= ⎜
n ,l ,l + 12
2 ⎝ 4πε 0 m 2 c 2 ⎟⎠ 2a03 ( l + 12 ) (l + 1) n3
1⎛ e2 ⎞ 2
δ En(1)spin-orbit =− ⎜
,l ,l −
2 ⎝ 4πε 0 m 2 c 2 ⎟⎠ 2a03 ( l + 12 ) n3
1
2

ER2 ⎧ 3 4 ⎫
δE (1)rel
= ⎨ − ⎬
2mc 2 ⎩ n 4 ( l + 12 ) n3 ⎭
n ,l , j

E ⎡ α2 ⎛ 1 3 ⎞⎤
(1) total
= − 2R ⎢ + − ⎥
n ⎝⎜ j + 12 4n ⎠⎟ ⎦
E n, j 1
n ⎣
e2 1
α ≡ fine structure constant = ≈
4πε 0 c 137

l = 0, no spin-orbit interaction, L ⋅ S = 0 for spherically

symmetric spatial wave function; still have relativistic
1⎛ e2 ⎞ 2
δ En,0, 1
(1)Darwin
= ⎜
2 ⎝ 4πε 0 m 2c 2 ⎟⎠ ( na0 )3
term
2

exactly the same as above for l = 0

others: positronium: electron and positron

quarkonium: quark and antiquark (QCD)
SM355 – 2005 9 22 September/Tut7
H +2 :

3-body Schrödinger equation: 6 independent coordinates

(not separable – not easy)

stationary nucleus model: Born-Oppenheimer model

(exact solutions exist)

variational method: 2 1s wave H wavefunctions

(binds, but dissociation energy too small)

H2 follows He – more tightly bound than H +2

SM355 – 2005 10 22 September/Tut7