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VII. Time‐Independent Perturbation Theory

First‐Order Perturbation Theory

0, 0 𝑥 𝑎 0, 0 𝑥 𝑎
𝑉 𝑥 𝑉 𝑥
∞, otherwise ∞, otherwise

𝑉′ 𝑥

𝑎 𝑛𝜋 𝐸 𝐸 𝐸
𝜓 𝑥 sin 𝑥
2 𝑎
𝐸 𝜓 𝐻 𝜓
𝑛 𝜋 ℏ
𝐸 𝑎 𝑛𝜋
2𝑚𝑎 𝑉′ 𝑥 sin 𝑥 𝑑𝑥
2 𝑎
1

VII. Time‐Independent Perturbation Theory

Second‐Order Perturbation Theory

𝜆 :𝐻 𝜓 𝐻𝜓 𝐸 𝜓 𝐸 𝜓 𝐸 𝜓
∗
⟹ 𝜓 𝐻 𝜓 𝐻𝜓 𝐸 𝜓 𝐸 𝜓 𝐸 𝜓 𝑑𝑥

or 𝜓 𝐻 𝜓 𝜓 𝐻𝜓 𝐸 𝜓 𝜓 𝐸 𝜓 𝜓 𝐸 𝜓 𝜓 1
𝜑 𝑄𝜙 𝑄 𝜑 𝜙 for Hermitian operators 𝜓 ∑ 𝑐 𝜓 0

𝜓 𝐻 𝜓 𝜓 𝑥 ∗ 𝐻 𝜓 𝑥 𝑑𝑥 𝐻 𝜓 𝑥 ∗𝜓 𝑥 𝑑𝑥

∗
𝐸 𝜓 𝑥 𝜓 𝑥 𝑑𝑥 𝐸 𝜓 𝜓

𝜓 𝐻 𝜓 𝜓 𝐻 𝜓
⟹ 𝐸 𝜓 𝐻 𝜓 𝑐 𝜓 𝐻 𝜓
𝐸 𝐸
𝜓 𝐻 𝜓
⟹ 𝐸 if the unperturbed spectrum 𝐸 𝑖𝑠 𝑛𝑜𝑛𝑑𝑒𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑒
𝐸 𝐸
2

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VII. Time‐Independent Perturbation Theory

Degenerate Perturbation Theory

• Nondegenerate case: 𝐻 𝜓 𝐸 𝜓 , 𝐸 𝐸 if 𝑛 𝑚

𝜓 𝜓 𝜆𝜓 𝜆 𝜓 ⋯
𝜓 𝐻 𝜓
𝜓 𝑐 𝜓 𝜓
𝐸 𝐸

• Degenerate case: 𝐻 𝜓 𝐸 𝜓 , 𝐻 𝜓 𝐸 𝜓 two‐fold degeneracy, 𝐸 𝐸 𝐸

Look for the “good” states 𝜓 and 𝜓 such that 𝜓 𝐻 𝜓 0 diagonalization of 𝐻′ :

𝐴𝜓 𝜇𝜓 , 𝐴𝜓 𝜈𝜓 𝜇 𝜈

where 𝐴 is Hermitian and 𝐴, 𝐻 𝐴, 𝐻′ 0 works for higer-order degeneracy, too .

𝐏𝐫𝐨𝐨𝐟: 𝜓 𝐴, 𝐻′ 𝜓 𝜓 𝐴𝐻′𝜓 𝜓 𝐻′𝐴𝜓 𝐴𝜓 𝐻′𝜓 𝜓 𝐻′𝐴𝜓

𝜇 𝜓 𝐻′𝜓 𝜈 𝜓 𝐻′𝜓 𝜇 𝜈 𝜓 𝐻′𝜓 0

3

VII. Time‐Independent Perturbation Theory

Degenerate Perturbation Theory

𝑛 ,𝑛 0,0
𝑝 1
𝐻 𝑚𝜔 𝑥 𝑦 , 𝐸 𝑛 𝑛 1 ℏ𝜔
2𝑚 2

𝜓 𝑥, 𝑦 𝜓 𝑥 𝜓 𝑦 𝑦𝑒 ℏ
ℏ

𝑛 ,𝑛 1,0 𝜓 𝑥, 𝑦 𝜓 𝑥 𝜓 𝑦 𝑥𝑒 ℏ
ℏ

𝐻 𝜀 𝑚𝜔 𝑥𝑦

𝑄 𝑥, 𝑦 𝑄 𝑦, 𝑥 ⟹ 𝐴, 𝐻 𝐴, 𝐻′ 0
𝑛 ,𝑛 0,1
𝐴 𝜓 𝜓 𝜓 𝜓 𝜓 𝜓

Good states: 𝜓 𝜓 𝜓

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VII. Time‐Independent Perturbation Theory

Degenerate Perturbation Theory

𝜆: 𝐻 𝐸 𝜓 𝐻 𝐸 𝜓
𝛼𝜓 𝛽𝜓
𝜓 𝛼𝜓 𝛽𝜓

𝐻 𝐻 𝜆𝐻′ ⟹ 𝐻 𝜓 𝐻 𝛼𝜓 𝛽𝜓 𝐸 𝜓 𝐸 𝛼𝜓 𝛽𝜓

𝛼′𝜓 𝛽′𝜓
𝛼𝜓 𝐻 𝜓 𝛽𝜓 𝐻 𝜓 𝛼𝐸
⟹
𝛼𝜓 𝐻 𝜓 𝛽𝜓 𝐻 𝜓 𝛽𝐸

• N‐fold degeneracy: 𝑊 𝑊 𝛼 𝛼
⟹ 𝐸
𝑊 𝑊 𝛽 𝛽
𝑊 𝜓 𝐻 𝜓
1
𝑖, 𝑗 1,2, … , 𝑁 ⟹ 𝐸 𝑊 𝑊 𝑊 𝑊 4𝑊
2

VII. Time‐Independent Perturbation Theory

Fine Structure of H Atom

𝑛 3→2

Fine Structure

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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⟩

• 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 7

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
𝑒 𝑣
• Spin‐orbital coupling correction:
𝑒 𝐼
/
𝐸 𝑛𝑙𝑠𝑗𝑚 𝐻′ 𝑛𝑙𝑠𝑗𝑚 𝛼 𝐸
/
8

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VII. Time‐Independent Perturbation Theory

Relativistic Correction and Spin‐Orbital Coupling

• Spin‐orbital coupling correction:

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:

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