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VII. Time‐Independent Perturbation Theory

Relativistic Correction of Hydrogen Atom

ℏ 𝑒 1 𝑝
• Hydrogen atom: 𝐻 ∇ 𝐻 ≡𝐻 𝐻′
2𝑚 4𝜋𝜖 𝑟 8𝑚 𝑐

𝑝 𝑝
𝑇 𝑝 𝑐 𝑚 𝑐 𝑚𝑐
2𝑚 8𝑚 𝑐
• Degeneracy: Same 𝐸 for different 𝑙, 𝑚
• Good states? 𝐿 , 𝐻 𝐿 ,𝐻 𝐿 ,𝐻 𝐿 ,𝐻 0
⟹ |𝑛𝑙𝑚⟩
For the same 𝐸 , |𝑙𝑚⟩ has 𝑑𝑖𝑠𝑡𝑖𝑛𝑐𝑡 𝑙, 𝑚
• Relativistic energy correction:

1 𝑒 1 𝑒 1
𝐸 𝑛𝑙𝑚 𝐻′ 𝑛𝑙𝑚 𝐸 𝐸
2𝑚𝑐 2𝜋𝜖 𝑟 4𝜋𝜖 𝑟

4 3
𝛼 𝐸
𝑛 𝑙 1/2 𝑛
Fine structure constant, 𝛼 ~1/137 1

VII. Time‐Independent Perturbation Theory

Spin‐Orbital Coupling

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

Electron′s 1 𝑒 𝜇 𝑖
𝜇 𝑖𝑒
𝐁 𝐋
point of view 4𝜋𝜖 𝑚𝑐 𝑟 𝐵
2𝑟2𝑟𝑇
2𝜋𝑟
𝐿 𝑟𝑝 𝑟𝑚
𝑒 𝑣 𝑇
𝜇 𝑒
𝑒 𝐼 ⟹𝐁 𝐋
4𝜋 𝑚𝑟
2

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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 |𝑛𝑙𝑠𝑚 𝑚 ⟩
𝑒
𝑣 • Good states?
𝑒
𝑒 𝝁 𝐒
𝑚 ℏ 𝜕 𝜕 𝐿
𝐻 𝑟 𝑉 𝑟
2𝑚 𝑟 𝜕𝑟 𝜕𝑟 2𝑚𝑟
Electron′s 1 𝑒 𝐿 ,𝑆 ,𝐿 ,𝑆 ,𝐻 0 ⟹ 𝐻 : |𝑛𝑙𝑠𝑚 𝑚 ⟩
point of view 𝐁 𝐋
4𝜋𝜖 𝑚𝑐 𝑟
𝐉 𝐋 𝐒 ⟹ 𝐽 ,𝐽 ,𝐻 0 ⟹ 𝐻 : 𝑛𝑙𝑠𝑗𝑚
𝐿 ,𝑆 ,𝐽 ,𝐽 ,𝐒· 𝐋 0 ⟹ 𝐻 : 𝑛𝑙𝑠𝑗𝑚 𝑙𝑠𝑗𝑚 𝑑𝑖𝑠𝑡𝑖𝑛𝑐𝑡
𝑒 𝑣 for the same 𝐸
• Spin‐orbital coupling correction:
𝑒 𝐼
/
𝐸 𝑛𝑙𝑠𝑗𝑚 𝐻′ 𝑛𝑙𝑠𝑗𝑚 𝛼 𝐸 𝑙 0
/
3

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

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VII. Time‐Independent Perturbation Theory

“Normal” Zeeman Effect

• Ignore spins (fine structure, too) and assume 𝐁 𝐵 𝐳
𝐁
𝑒 𝑒
𝐻 𝝁 ·𝐁 𝐋·𝐁 𝐵 𝐿
2𝑚 2𝑚
• Degeneracy: |𝑙𝑚⟩ for the same 𝐸
𝑒
𝑣 • Good states: 𝐿 , 𝐻 𝐿 ,𝐻 0 ⟹ |𝑛𝑙𝑚⟩ 𝐿 diagonal
𝑒 𝑒
𝝁 𝐋 • Energy correction:
2𝑚
𝑒𝐵 𝑒
𝐸 𝑛𝑙𝑚 𝐻 𝑛𝑙𝑚 𝑛𝑙𝑚 𝐿 𝑛𝑙𝑚 𝐵 𝑚
2𝑚 2𝑚

𝐸
𝑚 1
𝐸 𝑚 0
𝑚 1
𝐵
5

VII. Time‐Independent Perturbation Theory

“Anomalous” Zeeman Effect

• Total magnetic moment: 𝝁 𝝁 𝝁 𝐒 𝐋

𝑒 𝑒𝐵
• Zeeman effect: 𝐻 𝝁·𝐁 𝐋 2𝐒 · 𝐁 𝐿 2𝑆
2𝑚 2𝑚

𝑝
• Fine structure: 𝐻 𝝁 ·𝐁
8𝑚 𝑐

Weak‐field Zeeman effect: 𝐁 ≪𝐁 𝐻 𝐻 𝐻 , 𝐻 𝐻

Strong‐field Zeeman effect: 𝐁 ≫𝐁 𝐻 𝐻 𝐻 , 𝐻 𝐻

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VII. Time‐Independent Perturbation Theory

Weak‐Field Zeeman Effect

• Unperturbed Hamiltonian 𝐻 : 𝐻 𝐻 𝐻 𝐒·𝐋

• Unperturbed states: 𝑛𝑙𝑠𝑗𝑚 , 𝐸 𝛼 𝐸

/

• Perturbed Hamiltonian 𝐻′ : 𝐻 𝐿 2𝑆 only diagonal in |𝑛𝑙𝑠𝑚 𝑚 ⟩

𝑗𝑚 𝑙𝑠𝑚 𝑚 ⟩ 𝑙𝑠𝑚 𝑚 𝑗𝑚 Clebsch Gordan coefficients

,

• 2p state: 𝑛 2, 𝑙 1, 𝑠 , 𝑗 ,

1 1 1 0 , 1 1 1 0

⟹ 𝐿 1 1 𝐿 1 1 1 0 𝐿 1 0 ℏ

VII. Time‐Independent Perturbation Theory

Weak‐Field Zeeman Effect

• Unperturbed Hamiltonian 𝐻 : 𝐻 𝐻 𝐻 𝐒·𝐋

• Unperturbed states: 𝑛𝑙𝑠𝑗𝑚 , 𝐸 𝛼 𝐸

/

• Perturbed Hamiltonian 𝐻′ : 𝐻 𝐿 2𝑆 only diagonal in |𝑛𝑙𝑠𝑚 𝑚 ⟩

𝑗 3/2
0 0 , 0 0
1 0 0 0 1/2 0 0 0
0 1/3 0 0 2/3 0 , 0 1/6 0 0 2/3 0
0 0 1/3 0 0 2/3 , 0 0 1/6 0 0 2/3
𝐿 ⟶ 𝑆 ⟶
0 0 0 1 0 0 , 0 0 0 1/2 0 0
0 2/3 0 0 2/3 0 , 0 2/3 0 0 1/6 0
0 0 2/3 0 0 2/3 , 0 0 2/3 0 0 1/6
𝑗 1/2

2 0 ,
0 0
3 𝑒ℏ 0 2/3 0 0 ,
𝑗 ⟹ 𝐻 ⟶ 𝐵
2 2𝑚 0 0 2/3 0 ,
0 0 0 2 ,
8

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VII. Time‐Independent Perturbation Theory

Weak‐Field Zeeman Effect

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 𝑠 𝑠 1 𝑙 𝑙 1

⟹ 𝑗𝑚 𝐿 𝑗𝑚 𝑗𝑚 𝐽 𝑗𝑚

• Energy correction:
𝐸 𝑛𝑙𝑠𝑗𝑚 𝐻 𝑛𝑙𝑠𝑗𝑚
ℏ
𝑗𝑚 𝐿 𝑗𝑚 2 𝑗𝑚 𝑆 𝑗𝑚 𝑔 𝐵 𝑚

𝑔 1 1 for H: 𝑠 ,𝑗 𝑙