3.5.

Hyperfine structure of the H atom

So far we have considered orbiting electron as a magnetic dipole, spinning electron as a magnetic
dipole …

Spinning proton (nucleus) can also act as a magnetic dipole

𝑞𝑞
In general, 𝜇𝜇⃗∎ = 𝑔𝑔∎ 𝑠𝑠⃗∎
2𝑚𝑚∎

For an electron (which is a fundamental standard model particle) ; 𝑔𝑔𝑒𝑒 ≈ 2

𝑒𝑒
𝜇𝜇⃗𝑒𝑒 = − 𝑆𝑆⃗
𝑚𝑚𝑒𝑒 𝑒𝑒

However for a composite structure like a proton (with three quarks), 𝑔𝑔𝑝𝑝 is complicated to calculate
(𝑔𝑔𝑝𝑝 ≈ 5.59)

𝑔𝑔𝑝𝑝 𝑒𝑒
𝜇𝜇⃗𝑝𝑝 = 𝑆𝑆⃗
2𝑚𝑚𝑝𝑝 𝑝𝑝

Also a magnetic field due to a dipole

𝜇𝜇0 2𝜇𝜇0 3
�⃑ =
𝐵𝐵 [3(𝜇𝜇⃑ ∙ 𝑟𝑟̂ )𝑟𝑟̂ − 𝜇𝜇⃑ ] + 𝜇𝜇⃑𝛿𝛿 (𝑟𝑟⃑)
4𝜋𝜋𝑟𝑟 3 3

𝜇𝜇⃑ here is 𝜇𝜇⃑𝑝𝑝

Proton
→ magnetic dipole
→ magnetic dipole moment
→ magnetic field (near electron)

Interaction Hamiltonian of the electron dipole moment and above field

�⃗𝑝𝑝
𝐻𝐻 = −𝜇𝜇⃗e ⋅ 𝐵𝐵

Note: Fine structure spin-orbit Hamiltonian also had the dame equation. There in fine interaction, 𝐵𝐵�⃗𝑝𝑝
�⃗𝑝𝑝
was a field due to the proton orbital motion around the electron. But here in hyperfine interaction 𝐵𝐵
is a dipole field is due to the proton spin. Also here we consider a spin : spin interaction

[1] 𝜇𝜇0 2𝜇𝜇0

�⃗𝑝𝑝 = −𝜇𝜇⃗e ⋅
𝐻𝐻ℎ𝑓𝑓 = −𝜇𝜇⃗e ⋅ 𝐵𝐵 �3�𝜇𝜇⃗𝑝𝑝 ∙ 𝑟𝑟̂ �𝑟𝑟̂ − 𝜇𝜇⃗𝑝𝑝 � + 𝜇𝜇⃗ 𝛿𝛿 3 (𝑟𝑟⃑)
4𝜋𝜋𝑟𝑟 3 3 𝑝𝑝

𝑒𝑒 𝜇𝜇0 𝑔𝑔𝑝𝑝 𝑒𝑒 𝑔𝑔𝑝𝑝 𝑒𝑒 2𝜇𝜇0 𝑔𝑔𝑝𝑝 𝑒𝑒

= (−) − 𝑆𝑆⃗𝑒𝑒 ⋅ �3 � 𝑆𝑆⃗𝑝𝑝 ∙ 𝑟𝑟̂ � 𝑟𝑟̂ − 𝑆𝑆⃗𝑝𝑝 � + 𝑆𝑆⃗ 𝛿𝛿 3 (𝑟𝑟⃑)
𝑚𝑚𝑒𝑒 4𝜋𝜋𝑟𝑟 3 2𝑚𝑚𝑝𝑝 2𝑚𝑚𝑝𝑝 3 2𝑚𝑚𝑝𝑝 𝑝𝑝

𝜇𝜇0 𝑒𝑒 𝑔𝑔𝑝𝑝 𝑒𝑒 2𝜇𝜇0 𝑒𝑒 𝑔𝑔𝑝𝑝 𝑒𝑒

= 𝑆𝑆⃗𝑒𝑒 ⋅ �3� 𝑆𝑆⃗𝑝𝑝 ∙ 𝑟𝑟̂ �𝑟𝑟̂ − 𝑆𝑆⃗𝑝𝑝 � + 𝑆𝑆⃗ ⋅ 𝑆𝑆⃗ 𝛿𝛿 3 (𝑟𝑟⃑)
3
4𝜋𝜋𝑟𝑟 𝑚𝑚𝑒𝑒 2𝑚𝑚𝑝𝑝 3 𝑚𝑚𝑒𝑒 2𝑚𝑚𝑝𝑝 𝑝𝑝 𝑒𝑒

𝜇𝜇0 𝑔𝑔𝑝𝑝 𝑒𝑒 2 1 𝜇𝜇 𝑔𝑔 𝑒𝑒 2
[1]
𝐻𝐻ℎ𝑓𝑓 = �3� ⃗𝑝𝑝 ∙ 𝑟𝑟̂ �(𝑆𝑆⃗𝑒𝑒 ⋅ 𝑟𝑟̂ ) − 𝑆𝑆⃗𝑝𝑝 ⋅ 𝑆𝑆⃗𝑒𝑒 � + 0 𝑝𝑝 𝑆𝑆⃗𝑝𝑝 ⋅ 𝑆𝑆⃗𝑒𝑒 𝛿𝛿 3 (𝑟𝑟⃑)
𝑆𝑆
8𝜋𝜋𝑚𝑚𝑝𝑝 𝑚𝑚𝑒𝑒 𝑟𝑟 3 3𝑚𝑚𝑝𝑝 𝑚𝑚𝑒𝑒
The 1st order energy correction is the expectation of this correction term in perturb states.
[1]
𝐸𝐸𝑛𝑛 = �Ψ𝑛𝑛0 �𝐻𝐻 [1] �Ψ𝑛𝑛0 �

[1] 𝜇𝜇0 𝑔𝑔𝑝𝑝 𝑒𝑒 2 1 𝜇𝜇0 𝑔𝑔𝑝𝑝 𝑒𝑒 2

𝐸𝐸ℎ𝑓𝑓 = ⃗ ⃗ ⃗ ⃗
〈 �3� 𝑆𝑆𝑝𝑝 ∙ 𝑟𝑟̂ �(𝑆𝑆𝑒𝑒 ⋅ 𝑟𝑟̂ ) − 𝑆𝑆𝑝𝑝 ⋅ 𝑆𝑆𝑒𝑒 �〉 + 〈𝑆𝑆⃗ ⋅ 𝑆𝑆⃗ 〉|𝜓𝜓(0)|2
8𝜋𝜋𝑚𝑚𝑝𝑝 𝑚𝑚𝑒𝑒 𝑟𝑟 3 3𝑚𝑚𝑝𝑝 𝑚𝑚𝑒𝑒 𝑝𝑝 𝑒𝑒

Lest consider the ground state

When 𝑙𝑙 = 0 the wave function is spherically symmetric, so the 1st term vanishes
[Griffiths, Problem 6.27]
1
Ground state wavefunction 𝜓𝜓100 (𝑟𝑟, 0, 𝜙𝜙) = 𝑒𝑒 −𝑟𝑟/𝑎𝑎
√𝜋𝜋𝑎𝑎3

1
|𝜓𝜓100 (0)|2 =
𝜋𝜋𝑎𝑎3

𝜇𝜇0 𝑔𝑔𝑝𝑝 𝑒𝑒 2 1
′
𝐸𝐸ℎ𝑓𝑓,𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠 = 〈𝑆𝑆⃗ ⋅ 𝑆𝑆⃗ 〉
3𝑚𝑚𝑝𝑝 𝑚𝑚𝑒𝑒 𝜋𝜋𝑎𝑎3 𝑝𝑝 𝑒𝑒

𝜇𝜇0  𝑔𝑔𝑝𝑝 𝑒𝑒 2
′
𝐸𝐸ℎ𝑓𝑓,𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 = 〈𝑆𝑆⃗ ⋅ 𝑆𝑆⃗ 〉
𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
3𝜋𝜋𝑚𝑚𝑝𝑝 𝑚𝑚𝑒𝑒 𝑎𝑎3 𝑝𝑝 𝑒𝑒

4𝜋𝜋𝜖𝜖0 ℏ2 1 4𝜋𝜋ℏ2
Using 𝑎𝑎 = and 𝑐𝑐 2 = ; 𝑒𝑒 2 = substituting above
𝑚𝑚𝑒𝑒 𝑒𝑒 2 𝜖𝜖0 𝜇𝜇0 𝑚𝑚𝑒𝑒 𝜇𝜇0 𝑐𝑐 2 𝑎𝑎

𝟒𝟒𝒈𝒈𝒑𝒑 ℏ𝟐𝟐  
𝑬𝑬′𝒉𝒉𝒉𝒉,𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈𝒈 𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔𝒔 = �⃗𝒑𝒑 ⋅ 𝑺𝑺
〈𝑺𝑺 �⃗𝒆𝒆 〉
𝟑𝟑𝒎𝒎𝒑𝒑 𝒎𝒎𝟐𝟐𝒆𝒆 𝒄𝒄𝟐𝟐 𝒂𝒂𝟒𝟒

This is spin-spin coupling.

Just like in spin-orbit coupling, individual (spin) angular momenta are no longer conserved
‘good’ quantum states are eigenvectors of the total spin operator;

𝑆𝑆⃑ ≡ 𝑆𝑆⃑𝑒𝑒 + 𝑆𝑆⃑𝑝𝑝

𝑆𝑆⃑ = 𝑆𝑆⃑𝑒𝑒 + 𝑆𝑆⃑𝑝𝑝

𝑆𝑆⃑ ⋅ 𝑆𝑆⃑ = �𝑆𝑆⃑𝑒𝑒 + 𝑆𝑆⃑𝑝𝑝 � ⋅ �𝑆𝑆⃑𝑒𝑒 + 𝑆𝑆⃑𝑝𝑝 �
𝑆𝑆 2 = 𝑆𝑆𝑒𝑒2 + 𝑆𝑆𝑝𝑝2 + 2𝑆𝑆⃑𝑒𝑒 ⋅ 𝑆𝑆⃑𝑝𝑝
1
𝑆𝑆⃑𝑒𝑒 ⋅ 𝑆𝑆⃑𝑝𝑝 = �𝑆𝑆 2 − 𝑆𝑆𝑒𝑒2 − 𝑆𝑆𝑝𝑝2 �
2
1
𝑠𝑠𝑒𝑒 = 𝑠𝑠𝑝𝑝 = ±
2

we know; 𝑆𝑆∎2 = 𝑠𝑠∎ (𝑠𝑠∎ + 1)ℏ2

3
so 𝑆𝑆𝑒𝑒2 = 𝑆𝑆𝑝𝑝2 = ℏ2
4
Two possibilities

A. Triplet States

Spins parallel {↑, ↑}

Three possible states with same energy;

1
|𝑆𝑆, 𝑚𝑚𝑠𝑠 ⟩; |1,1⟩ = {↑, ↑} , |1, −1⟩ = {↓, ↓} , |1,0⟩ = {↑, ↓ +↓, ↑}
√2

1 1
Total spin; 𝑆𝑆⃑ = 𝑆𝑆⃑𝑒𝑒 + 𝑆𝑆⃑𝑝𝑝 = + = 1
2 2

𝑆𝑆 2 = 1 (1 + 1)ℏ2 = 2ℏ2
1 1 3 3 1
𝑆𝑆⃑𝑒𝑒 ⋅ 𝑆𝑆⃑𝑝𝑝 = �𝑆𝑆 2 − 𝑆𝑆𝑒𝑒2 − 𝑆𝑆𝑝𝑝2 � = �2ℏ2 − ℏ2 − ℏ2 � = ℏ2
2 2 4 4 4

𝟏𝟏
�⃗𝒑𝒑 ⋅ 𝑺𝑺
〈𝑺𝑺 �⃗𝒆𝒆 〉𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻𝑻 = + ℏ𝟐𝟐
𝟒𝟒

A. Singlet State

Spins anti-parallel {↑, ↓}

1
One possible state; |𝑆𝑆, 𝑚𝑚𝑠𝑠 ⟩; |0,0⟩ = {↑, ↓ −↓, ↑}
√2

1 1
Total spin; 𝑆𝑆⃑ = 𝑆𝑆⃑𝑒𝑒 + 𝑆𝑆⃑𝑝𝑝 = − = 0
2 2

𝑆𝑆 2 = 0 (0 + 1) = 0
1 1 3 3 3
𝑆𝑆⃑𝑒𝑒 ⋅ 𝑆𝑆⃑𝑝𝑝 = �𝑆𝑆 2 − 𝑆𝑆𝑒𝑒2 − 𝑆𝑆𝑝𝑝2 � = �0 − ℏ2 − ℏ2 � = ℏ2
2 2 4 4 4

𝟑𝟑
�⃗𝒑𝒑 ⋅ 𝑺𝑺
〈𝑺𝑺 �⃗𝒆𝒆 〉𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺𝑺 = − ℏ𝟐𝟐
𝟒𝟒

[𝟏𝟏] 𝟒𝟒𝒈𝒈𝒑𝒑 ℏ𝟒𝟒 +𝟏𝟏/𝟒𝟒, (triplet)

𝑬𝑬𝒉𝒉𝒉𝒉 = �
𝟑𝟑𝒎𝒎𝒑𝒑 𝒎𝒎𝟐𝟐𝒆𝒆 𝒄𝒄𝟐𝟐 𝒂𝒂𝟒𝟒 −𝟑𝟑/𝟒𝟒, (singlet)

Hyperfine spin-spin coupling breaks the spin degeneracy of the ground state (triplet lifts up, singlet
sinks in energy)

Triplet
Unperturbed

Δ𝐸𝐸

Singlet
The energy split

4𝑔𝑔𝑝𝑝 ℏ4 1 3
Δ𝐸𝐸 = 2 2 4
� − �− �� = 5.88 × 10−6 eV
3𝑚𝑚P 𝑚𝑚𝑒𝑒 𝑐𝑐 𝑎𝑎 4 4

Photon frequency of triplet → singlet transition;

Δ𝐸𝐸
𝑓𝑓 = = 1420 MHz.
ℎ
𝑐𝑐
𝜆𝜆 = = 21 cm (Microwaves)
𝑟𝑟

Signature of hydrogen: used to study interstellar hydrogen clouds