CHAPTER 6: AN APPLICATION OF PERTURBATION THEORY
THE FINE AND HYPERFINE STRUCTURE OF THE HYDROGEN ATOM
(From Cohen-Tannoudji, Chapter XII)
We will now incorporate a weak relativistic effects as perturbation of the non-relativistic
Hamiltonian
Ĥ = Ĥ0 + W
ˆ2
~ ˆ4
~
2 P P 1 1 dV(R) ~ˆ ~ˆ ~2
= mec + + V(R) − 3 + 2 L · S + 2 ∆V(R) + . . .(6.1)
2m 2 2m c 2 R dR 8m c2
| e {z } | 8m e c
{z } | e {z }| e {z }
Ĥ0 Ŵmv ŴS O ŴD
Ŵmv - variation of mass with velocity
ŴS O - spin-orbit coupling
ŴD - Darwin term
The energies relevant to the relativistic effects are weak compared to the energy
associated with Ĥ0
!2
Ŵmv ŴS O ŴD Ŵmv 1
' ' ' ' α2 ' (6.2)
Ĥ0 Ĥ0 Ĥ0 Ĥ0 137
In addition we will consider hyperfine structure which comes from the interaction of
the electron and nuclear magnetic momenta
µ0
(
q ~ˆ ~ˆ 1 ~ˆ
~ˆ I · n̂ − M
~ˆ S · M
~ˆ I
Ŵh f = − L · M I + 3 M S · n̂ M (6.3)
4π meR3 R3
)
8π ~ˆ ˆ
~
~
ŴS O
+ MS · M I δ R ' (6.4)
3 2000
ˆ
ˆ~ gPµn~I q ~
MI = , µn = P (6.5)
~ 2MP
Fine structure of the n = 2 level
2s (n = 2, l = 0) and 2p (n = 2, l = 1)
EI 1 2 2
E = − = − µc α (6.6)
4 8
Orbital angular momentum L̂z: l = 0, m = 0 and l = 1, m = +1, 0, −1
Electron spin Ŝ z: m = ±1/2
Nuclear spin Iˆz: m = ±1/2
The perturbation Hamiltonian
Ŵ f = Ŵmv + ŴS O + ŴD (6.7)
Ŵ = Ŵ f + Ŵh f (6.8)
Matrix representation of Ŵ f
16 × 16 matrix
– Ŵ f does not act on ths spin variables of the proton
– Ŵ f does not connect the 2s and 2p subshells
– L̂2 commutes with Ŵ f
1. 2s subshell
m s = ±1/2 ⇒ 2 dimensional
ˆ
Ŵmv and ŴD do not depend on S~
⇒ they are proportional to a unit matrix and are given as
ˆ4
~
D E P
Ŵmv = hn = 2; l = 0, mL = 0| − |n = 2; l = 0, mL = 0i
2s 8m3e c2
13
= − mec2α4 (6.9)
128
D E ~2
ŴD = hn = 2; l = 0, mL = 0| ∆V(R)|n = 2; l = 0, mL = 0i
2s 8m2e c2
1
= m e c2 α4 (6.10)
16
and since l = 0
D E
ŴS O = 0 (6.11)
Thus the fine structure terms lead to shifting the 2s subshell as a whole by an
amount
D E D E D E 5mec2α4
Ŵmv + ŴD + ŴS O = − (6.12)
128
2. 2p subshell
(a) Ŵmv and ŴD terms
ˆ ˆ
– commute with ~L and do not act on spin S~ variables
⇓
a multiple of a unit matrix
D E 7
Ŵmv = − m e c2 α4 (6.13)
D E2p 384
ŴD = 0 (6.14)
2p
(See Complement BXII)
(b) ŴS O
various elements:
1 0 0 ˆ ~ˆ
~ 1
hn = 2; l = 1; s = ; mL; mS |ξ(R)L · S |n = 2; l = 1; s = ; mL; mS i
2 2
e2 1
ξ(R) = 2 3
(6.15)
2
2me c R
In {|~ri} representation, we can separate the radial part of the matrix elements
from the angular and spin parts:
1 ˆ ˆ 1
ξ2phl = 1; s = ; m0L; m0S |~L · S~ |l = 1; s = ; mL; mS i (6.16)
2 2
e2
Z ∞ 1 1
ξ2p = |R (r)| 2 r 2 dr = m c2 α4 (6.17)
21 e
2m2e c2 0 r3 48~2
ˆ ˆ
Problem: the diagonalization of the ξ2p ~
L · S~ operator
ˆ ˆ
Problem: the diagonalization of the ξ2p ~
L · S~ operator
Basis {|l = 1; s = 1/2; mL; mS i}
– common eigenstates of L̂2, Ŝ 2, L̂z, Ŝ z
Introducing the total angular momentum
ˆ ˆ ˆ
J~ = ~L + S~ (6.18)
( )
1
|l = 1; s = ; J, m J i (6.19)
2
Addition of angular momentum: J = 1 + 1/2 = 3/2 and J = 1 − 1/2 = 1/2
2
ˆ ˆ ˆ ˆ
Jˆ2 = ~L + S~ = L̂2 + Ŝ 2 + 2~L · S~ (6.20)
then
ˆ~ ~ˆ 1
2 2 2
ξ2p L · S = ξ2p Jˆ − L̂ − Ŝ (6.21)
2
ˆ ˆ 1
ξ2p ~L · S~ |l = 1; s = ; J, m J i
" 2 #
1 3 1
= ξ2p~2 J(J + 1) − 2 − |l = 1; s = ; J, m J i (6.22)
2 4 2
ˆ ˆ
The eigenvalues of ξ2p ~
L · S~ depend only on J and not on m J , and are equal
to
" #
1 1 3 3 1
J= : ξ2p − 2 − ~2 = −ξ2p~2 = − mec2α4 (6.23)
2 2 4 4 48
" #
3 1 15 3 1 1
J= : ξ2p − 2 − ~2 = + ξ2p~2 = mec2α4 (6.24)
2 2 4 4 2 96
The six-fold degeneracy of the 2p level is therefore partially removed by ŴS O
The fine structure of the n = 2 level: energies
2s1/2
5
− mec2α4 (6.25)
128
2p1/2
!
7 1 2 4 5
− − me c α = − mec2α4 (6.26)
384 48 128
2p3/2
!
7 1 2 4 1
− + me c α = − mec2α4 (6.27)
384 96 128
The fine structure of the n = 2 level
The hyperfine structure of the n = 1 level
a) The degeneracy of the 1s level
– no orbital degeneracy (l = 0)
– Ŝ z, Iˆz: each 2 value ±1/2
( )
1 1
|n = 1; l = 0; mL = 0; mS = ± ; mI = ± i (6.28)
2 2
b) The 1s level has no fine structure
Ŵ f does not remove the degeneracy of the 1s state
D E 5
Ŵmv = − mec2α4 (6.29)
1s 8
D E 1
ŴD = mec2α4 (6.30)
D E1s 2
ŴS O = 0 (6.31)
1s
Ŵ f shifts the levels by − 18 mec2α4
Since l = 0 and s = 1/2, J = 1/2 ⇒ only one fine structure level, 1s1/2
Matrix representation of Ŵh f in the 1s level
µ0
q ~ˆ ~ˆ 1
ˆ~ ˆ~ ˆ~ ˆ~
Ŵh f = − L · MI + 3
3
3 M S · n̂ M I · n̂ − M S · M I (6.32)
4π
meR{z } R
| | {z }
=0 due to spherical symmetry of 1s state
=0 as l=0
8π ~ˆ
ˆ~ ~
+ MS · M I δ R
(6.33)
|3 {z }
,0
ˆ
~
g µ I
~ˆ I = P n , qP~
M µn = (6.34)
~ 2MP
The matrix elements are
0 0 2µ0 ~ˆ ˆ~ ~
hn = 1; l = 0; mL = 0; m s; mI | − M S · M I δ R |n = 1; l = 0; mL = 0; m s; mI i
3
In coordinate representation, we separate the orbital and spin parts of the matrix
elements
ˆ ˆ
Ahm0S , m0I |~I · S~ |mS , mI i (6.35)
where
q2 gP ~ |n = 1; l = 0; mL = 0i
A = hn = 1; l = 0; m L = 0|δ R (6.36)
30c2 me MP
2 !−3
q gP 1 2 4 me 2 α4 1 + me 1
= R 10 (0) = g p m e c (6.37)
30c2 me MP 4π 3 MP MP ~2
The orbital variables have thus disappeared, and we are left with the problem of two
spin 1/2’s, coupled by an interaction
ˆ ˆ
A~I · S~ (6.38)
where A is a constant.
Eigenstates and eigenvalues
Initial basis {|s = 1/2; I = 1/2; m s; mI i}
– common eigenvectors of Ŝ 2, Iˆ2, Ŝ z, Iˆz
New basis
– introducing total angular momentum F ~ˆ = S~ˆ + ~Iˆ : {|s = 1/2; I = 1/2; F; mF i}
– common eigenvectors of Ŝ 2, Iˆ2, F̂ 2, F̂z
ˆ
F~ : F = 0, mF = 0 and F = 1, mF = 1, 0, −1
ˆ ~ˆ
~ A 2 ˆ2 2
AI · S = F̂ − I − Ŝ (6.39)
2
ˆ ˆ
The basis states |F, mF i are eigenstates of A~I · S~ :
ˆ~ ~ˆ A~2
AI · S |F, mF i = [F(F + 1) − I(I + 1) − S (S + 1)] |F, mF i (6.40)
2
A~2 A~2
" #
3 3
⇒F=1: 2− − = (3-fold degenerate) (6.41)
2 4 4 4
A~ 2 "
3 3
#
3A~2
F=0: 0− − =− (nondegenerate) (6.42)
2 4 4 4
The four-fold degeneracy of the 1s level is partially removed by Ŵh f .
The hyperfine structure of the 1s level
The n = 2 level
