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VII. Time‐Independent Perturbation Theory

Spin‐Orbital Coupling

Proton s • Magnetic dipole moment:

point of view 𝑒
Gyromagnetic ratio 𝜇 𝑖𝐴 𝜋𝑟
𝑇
Dirac equation
2𝜋
𝐿 𝐼𝜔 𝑚𝑟
𝑒 𝑇
𝑣
𝑒 𝑒 . . 𝑒
𝑒 𝝁 𝐒 ⟹𝜇 𝐿 𝝁 𝐒 if 𝐋 𝐒
𝑚 2𝑚 𝑚

Electron′s 1 𝑒 • “Effective” magnetic field:

point of view 𝐁 𝐋
4𝜋𝜖 𝑚𝑐 𝑟 𝜇 𝑖
𝜇 𝑒
𝐵
2𝑟
2𝑟𝑇
2𝜋𝑟
𝑒 𝑣 𝐿 𝑟𝑝 𝑟𝑚
𝑇
𝑒 𝐼 𝜇 𝑒
⟹𝐁 𝐋
4𝜋 𝑚𝑟
1

VII. Time‐Independent Perturbation Theory

Spin‐Orbital Coupling
• Spin‐orbital coupling: 𝐻 𝝁·𝐁
Proton s
point of view 𝑒 1
Gyromagnetic ratio 𝐒·𝐋
8𝜋𝜖 𝑚 𝑐 𝑟
Dirac equation
• Degeneracy in 𝐻 : same 𝐸 for |𝑙𝑠𝑚 𝑚 ⟩
𝑒
𝑣
𝑒 ℏ 𝜕 𝜕 𝐿
𝑒 𝝁 𝐒 𝐻 𝑟 𝑉 𝑟
𝑚 2𝑚 𝑟 𝜕𝑟 𝜕𝑟 2𝑚𝑟
• Good states?
Electron′s 1 𝑒 𝐴 𝐿 ,𝑆 ,𝐽 ,𝐽 𝐴, 𝐻 𝐴, 𝐻 0
point of view 𝐁 𝐋
4𝜋𝜖 𝑚𝑐 𝑟
𝐉≡𝐋 𝐒, 𝐉𝟐 𝐋 𝐒 · 𝐋 𝐒 𝐋𝟐 𝐒𝟐 2𝐒 · 𝐋

𝐉𝟐 𝑛𝑙𝑠𝑗𝑚 𝑗 𝑗 1 ℏ 𝑛𝑙𝑠𝑗𝑚 , 𝐽 𝑛𝑙𝑠𝑗𝑚 𝑚 ℏ 𝑛𝑙𝑠𝑗𝑚

𝑒 𝑣
• Spin‐orbital coupling correction:
𝑒 𝐼
/
𝐸 𝑛𝑙𝑠𝑗𝑚 𝐻′ 𝑛𝑙𝑠𝑗𝑚 𝛼 𝐸 𝑙 0
/
2

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VII. Time‐Independent Perturbation Theory

Relativistic Correction and Spin‐Orbital Coupling

• Spin‐orbital coupling correction 𝑙 0 :

𝑗 𝑗 1 𝑙 𝑙 1 3/4
𝐸 𝛼 𝐸
𝑛 𝑙 𝑙 1/2 𝑙 1

• Relativistic energy correction:

4 3
𝐸 𝛼 𝐸
𝑛 𝑙 1/2 𝑛

• Fine structure for all 𝑙 :

1 1 3
𝐸 𝐸 𝐸 𝛼 𝐸
𝑛 𝑗 1/2 4𝑛
Fine Structure

VII. Time‐Independent Perturbation Theory

“Normal” Zeeman Effect

• Ignore spins (fine structure) and assume 𝐁 𝐵 𝐳
𝐁
𝑒 𝑒
𝐻 𝝁 ·𝐁 𝐋·𝐁 𝐵 𝐿
2𝑚 2𝑚
• Degeneracy in 𝐻 : same 𝐸 for |𝑙𝑚⟩
𝑒
𝑣 • Good states: A 𝐿 , 𝐴, 𝐻 𝐴, 𝐻 0
𝑒 𝑒
𝝁 𝐋 𝐿 |𝑛𝑙𝑚⟩ 𝑚ℏ|𝑛𝑙𝑚⟩
2𝑚
• Energy correction:
𝑒𝐵 𝑒
𝐸 𝑛𝑙𝑚 𝐻 𝑛𝑙𝑚 𝑛𝑙𝑚 𝐿 𝑛𝑙𝑚 𝐵 𝑚
2𝑚 2𝑚
𝐸
𝑚 1
𝐸 𝑚 0
𝑚 1
𝐵
4

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VII. Time‐Independent Perturbation Theory

“Anomalous” Zeeman Effect

• Total magnetic moment: 𝝁 𝝁 𝝁 𝐒 𝐋
𝑒 𝑒𝐵
⟹ 𝐻 𝝁·𝐁 𝐋 2𝐒 · 𝐁 𝐿 2𝑆
2𝑚 2𝑚
𝑝
• Fine structure: 𝐻 𝝁 ·𝐁
8𝑚 𝑐

• Weak‐field Zeeman Effect: 𝐵 ≪𝐵

𝑒 1 𝑝
𝐻 𝐻 𝐻 𝐻 𝐒·𝐋 , 𝑛𝑙𝑠𝑗𝑚
8𝜋𝜖 𝑚 𝑐 𝑟 8𝑚 𝑐

𝐻 𝑛𝑙𝑠𝑗𝑚 𝐸 𝑛𝑙𝑠𝑗𝑚 , 𝐸 𝐸 𝛼 𝐸 (degenerate in 𝑚 )

/

𝑒𝐵
𝐻 𝐻 𝐿 2𝑆 not diagonal in 𝑛𝑙𝑠𝑗𝑚
2𝑚
5

VII. Time‐Independent Perturbation Theory

“Anomalous” Zeeman Effect

𝑒𝐵
𝐻 𝐻 𝐿 2𝑆
2𝑚
• 2p state: 𝑛 2, 𝑙 1, 𝑠 ⟹ 𝑗 , 𝟑 𝟑
𝟐 𝟐
,
𝟑 𝟏
𝟐 𝟐
,
𝟑
𝟐
,
𝟏
𝟐
𝟑
𝟐
,
𝟑
𝟐
𝟏 𝟏
,
𝟐 𝟐
𝟏
𝟐
,
𝟏
𝟐
𝑗𝑚
𝑗 3/2 𝑗 3/2
𝟑 𝟑
0 0 1/2 0 0 0 ,
1 0 0 0 0 0 𝟐 𝟐
𝟑 𝟏
0 1/3 0 0 2/3 0 0 1/6 0 0 2/3 0 𝟐 𝟐
,
𝟑 𝟏
0 0 1/3 0 0 2/3 0 0 1/6 0 0 2/3 ,
𝐿 ⟶ 𝑆 ⟶ 𝟐 𝟐
0 0 0 1 0 0 0 0 0 1/2 0 0
𝟑
𝟐 𝟐
,
𝟑

0 2/3 0 0 2/3 0 0 2/3 0 0 1/6 0 𝟏 𝟏

,
𝟐 𝟐
0 0 2/3 0 0 2/3 0 0 2/3 0 0 1/6 𝟏 𝟏
,
𝟐 𝟐
𝑗 1/2 𝑗 1/2

* Use 𝑗𝑚 ∑ , 𝑙𝑠𝑚 𝑚 ⟩ 𝑙𝑠𝑚 𝑚 𝑗𝑚 (Clebsch−Gordan coefficients) to calculate the

matrix elements
2 0 ,
0 0
3 𝑒ℏ 0 2/3 0 0 ,
𝑗 ⟹ 𝐻 ⟶ 𝐵 Zeeman energy shift
2 2𝑚 0 0 2/3 0 ,
0 0 0 2 , 6

3
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VII. Time‐Independent Perturbation Theory

“Anomalous” Zeeman Effect

• Energy correction:
𝑒𝐵
𝐸 𝑛𝑙𝑠𝑗𝑚 𝐻 𝑛𝑙𝑠𝑗𝑚 𝑗𝑚 𝐿 𝑗𝑚 2 𝑗𝑚 𝑆 𝑗𝑚
2𝑚
𝑗𝑚 𝐀 · 𝐉 𝑗𝑚
• Wigner‐Eckhart theorem: 𝑗𝑚 𝐴 𝑗𝑚 𝑗𝑚 𝐽 𝑗𝑚 𝐀 𝐋, 𝐒
ℏ 𝑗 𝑗 1
𝐉 𝐋 𝐒 ⟹ 2𝐋 · 𝐉 𝐽 𝐿 𝑆
ℏ
⟹ 𝑗𝑚 𝐋 · 𝐉 𝑗𝑚 𝑗 𝑗 1 𝑙 𝑙 1 𝑠 𝑠 1

⟹ 𝑗𝑚 𝐿 𝑗𝑚 𝑗𝑚 𝐽 𝑗𝑚 𝑚ℏ

𝑒ℏ
⟹𝐸 𝑔 𝐵 𝑚
2𝑚
H atom: 𝑠 ,𝑗 𝑙
𝑔 1 1
7

VII. Time‐Independent Perturbation Theory

“Anomalous” Zeeman Effect

• Strong‐field Zeeman Effect: 𝐵 ≫𝐵
𝑒𝐵
𝐻 𝐻 𝐻 𝐻 𝐿 2𝑆
2𝑚
𝐻 |𝑛𝑙𝑠𝑚 𝑚 ⟩ 𝐸 |𝑛𝑙𝑠𝑚 𝑚 ⟩

𝐸 𝐸 𝑛𝑙𝑠𝑚 𝑚 𝐻 𝑛𝑙𝑠𝑚 𝑚
𝑒𝐵 𝑒ℏ
𝐸 𝑛𝑙𝑠𝑚 𝑚 𝐿 2𝑆 𝑛𝑙𝑠𝑚 𝑚 𝐸 𝐵 𝑚 2𝑚
2𝑚 2𝑚
degenerate in 𝑙 and 𝑠
𝑝 𝑒 1 𝑝
𝐻 𝐻 𝝁 ·𝐁 𝐒·𝐋
8𝑚 𝑐 8𝜋𝜖 𝑚 𝑐 𝑟 8𝑚 𝑐
• Energy correction (𝐻 is still diagonal in each 𝑙 subspace):
1 𝑚𝑚
𝐸 𝑛𝑙𝑠𝑚 𝑚 𝐻 𝑛𝑙𝑠𝑚 𝑚 𝛼 𝑚𝑐
2 𝑛 𝑙 𝑙 1/2 𝑙 1

1 3 𝑙 𝑙 1 𝑚𝑚
⟹ 𝐸 𝛼 𝐸
𝑛 4𝑛 𝑙 𝑙 1/2 𝑙 1 8

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VII. Time‐Independent Perturbation Theory

“Anomalous” Zeeman Effect

• Intermediate‐field Zeeman Effect: 𝐵 ~𝐵 𝑛𝑙𝑠𝑗𝑚 |𝑛𝑙𝑠𝑚 𝑚 ⟩

𝐻 𝐻 degenerate in |𝑙𝑠𝑚 𝑚 ⟩ or 𝑙𝑠𝑗𝑚

𝐻 𝐻 𝐻
• 2p state: 𝑛 2, 𝑙 1, 𝑠 ⟹ 𝑗 ,

𝑎 2𝑏 0 0 0 0 0 𝟑 𝟑
𝟐 𝟐
,
0 𝑎 0 0 0 𝟑 𝟏
,
𝟐 𝟐

0 0 𝑎 0 0 𝟑
,
𝟏

𝐻 ⟶ 0 0
𝟐 𝟐
0 𝑎 2𝑏 0 0 𝟑
𝟐 𝟐
,
𝟑

𝟏 𝟏
0 0 5𝑎 0 ,
0 𝟐 𝟐

0 0 5𝑎
𝟏
,
𝟏
0 0 𝟐 𝟐

ℏ
𝑎 𝛼 𝑚𝑐 𝑏 𝐵
9

VII. Time‐Independent Perturbation Theory

Spin‐Spin Coupling
𝑔 𝑒
• Dipole moment of proton: 𝝁 𝐒 , 𝑔 5.6
2𝑚
𝐻 𝝁 ·𝐁
𝐁 𝜇 𝑔 𝑒 3 𝐒 · 𝑟̂ 𝐒 · 𝑟̂ 𝐒 ·𝐒 𝐒 ·𝐒 𝛿 𝐫
𝝁 𝑒 𝑚 𝑚 8𝜋𝑟 3
𝑣
𝑒
𝑒 𝝁 𝐒 • Good states: 𝐒 𝐒 𝐒
𝑚
• Energy correction in the ground state 𝑛 1 :
𝜇 𝑔 𝑒
𝐸 𝐒 ·𝐒 hyperfine structure
3𝜋𝑚 𝑚 𝑎
1
𝐒 ·𝐒 𝑆 𝑆 𝑆
2

ℏ𝟐 ⁄4 , triplet state 𝑆 1
3ℏ𝟐 /4, singlet state 𝑆 0
λ 21 cm H atom 10