Ilmu Komputasi

Material
Aproksimasi 3

Post Hartree-Fock
 Energi Korelasi Elektron
Aproksimasi Hartree-Fock (HF)

𝐸 𝐻𝐹 > 𝐸 𝐸𝑥𝑎𝑐𝑡

𝐸 𝐻𝐹

𝐸 𝐸 𝑒𝑥𝑎𝑐𝑡

+ Correlation Energy
 Post Hartree-Fock (HF)

• All-electron full potential • Local density approx. (LDA)

• Full-relativistic • All-electron muffin-tin • Gradient correction approx. (GGA)
• Scalar-relativistic • All-electron PAW • Beyond GGA
• Non-relativistic • Pseudopotential

• Gaussian (GTO)
• Slater (STO)
• Non-periodic • Numerical
• Periodic • Atomic orbital (LCAO)
• symmetry • Plane waves • Augmented plane waves
• Augmentation (APW)
• Fully numerical • Linearized augmented plane
• Non-spin polarized waves (LAPW)
• Spin polarized • Spherical waves (LMTO,
ASW)
 Post Hartree-Fock

I. Configurational Interaction (CI)

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𝑋 1(𝒓 𝟏 ) 𝑋 2(𝒓 𝟏 ) … 𝑋𝑁 ( 𝒓𝟏)
1 𝑋 1(𝒓 𝟐 ) 𝑋 2(𝒓 𝟐 ) … 𝑋𝑁 ( 𝒓𝟐)
𝜓 ( 𝒓 𝟏 , 𝒓 𝟐 , … , 𝒓 𝑵)=
√𝑁! ⋮ ⋮⋱ ⋮
𝑋 1( 𝒓 𝑵) 𝑋 2( 𝒓 𝑵) … 𝑋 𝑁 (𝒓 𝑵 )

𝑆𝐷
𝜓 ( 𝒓 𝟏 , 𝒓 𝟐 , … , 𝒓 𝑵 ) =𝜓
Post Hartree-Fock

I. Configurational Interaction (CI)

Virtual Occ. (V)

Single Occ. (S)

Double Occ. (D)

 Post Hartree-Fock

I. Configurational Interaction (CI)

Single
Excitation
 Post Hartree-Fock

I. Configurational Interaction (CI)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

𝑖
Keadaan Dasar Keadaan Eksitasi
(Ground State) (Excited State)
 Post Hartree-Fock

I. Configurational Interaction (CI)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

Hartree-Fock

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𝑋 1( 𝒓 𝟏) 𝑋 2( 𝒓 𝟏) … 𝑋 𝑁 (𝒓 𝟏 )
1 𝑋 1( 𝒓 𝟐) 𝑋 2( 𝒓 𝟐) … 𝑋 𝑁 (𝒓 𝟐 )
𝜓 0𝑆𝐷 =
√𝑁! ⋮ ⋮⋱ ⋮
𝑋 1 (𝒓 𝑵) 𝑋 2 (𝒓 𝑵) … 𝑋 𝑁 (𝒓 𝑵 )
 Post Hartree-Fock

I. Configurational Interaction (CI)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

Hartree-Fock

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𝑋∗
1 (𝒓 𝟏 ) 𝑋 2 (𝒓 𝟏 ) … 𝑋 𝑁 (𝒓 𝟏 )
𝜓 1𝑆𝐷 =
1 𝑋∗
1 (𝒓 𝟐 )
𝑋 2 (𝒓 𝟐 ) … 𝑋 𝑁 (𝒓 𝟐 )
√ 𝑁! ⋮ ⋮⋱ ⋮
∗
𝑋 (𝒓 𝑵 )
1 𝑋 2 (𝒓 𝑵 ) … 𝑋 𝑁 (𝒓 𝑵 )
 Post Hartree-Fock

I. Configurational Interaction (CI)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

Hartree-Fock

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∗ ∗
𝑋1 ( 𝒓 𝟏 ) 𝑋2 ( 𝒓𝟏) … 𝑋 𝑁 (𝒓 𝟏 )
𝜓 1𝑆𝐷 =
1 𝑋∗
1 (𝒓 𝟐 ) 𝑋∗
2 ( 𝒓𝟐) …
𝑋 𝑁 (𝒓 𝟐 )
√𝑁! ⋮ ⋮⋱ ⋮
∗ ∗
𝑋 (𝒓 𝑵 )
1 𝑋 (𝒓 𝑵 ) …
2 𝑋 𝑁 (𝒓 𝑵 )
 Post Hartree-Fock

I. Configurational Interaction (CI) Sangat Berat!

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

Hartree-Fock

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∗ ∗ ∗
𝑋1 ( 𝒓 𝟏 ) 𝑋2 ( 𝒓𝟏) … 𝑋 𝑁 (𝒓 𝟏 )
𝜓 1𝑆𝐷 =
1 𝑋∗
1 (𝒓 𝟐 ) 𝑋∗
2 ( 𝒓𝟐) … 𝑋 ∗𝑁 ( 𝒓 𝟐 )
√𝑁! ⋮ ⋮⋱ ⋮
∗ ∗ ∗
𝑋 (𝒓 𝑵 )
1 𝑋 (𝒓 𝑵 ) …
2 𝑋 𝑁 (𝒓 𝑵 )
 Post Hartree-Fock

II. Møller-Plesset (MP)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

𝑖 MP1=HF

→ Teori Gangguan Rayleigh-Schrödinger (RS)

^
𝐻 =^ ^
𝐻0 + 𝜆𝑉
 Post Hartree-Fock

II. Møller-Plesset (MP)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

𝑖 MP-N
MP1:

1 1
𝜓1 =∫ 𝜙𝑖 ∗ (𝒓𝟏) 𝜙 𝑗 ∗ (𝒓𝟐) 𝜙𝑖 (𝒓𝟏) 𝜙 𝑗 ( 𝒓𝟐) 𝑑𝑟𝑑𝑟 −∫ 𝜙𝑖 ∗ (𝒓𝟐) 𝜙 𝑗 ∗ (𝒓 𝟏) 𝜙𝑖 (𝒓𝟐) 𝜙 𝑗 ( 𝒓𝟏) 𝑑𝑟𝑑𝑟′
Occupied Occupied
𝑆𝐷 ′

|𝒓𝟏 −𝒓𝟐| |𝒓𝟏 −𝒓𝟐|

Occupied Occupied

𝜓 1 =( 𝐽 − 𝐾 ) =⟨ 𝑖𝑗|𝑖𝑗 ⟩
𝑆𝐷
Dirac Notation
 Post Hartree-Fock

II. Møller-Plesset (MP)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

𝑖 MP-N

MP1:
MP2:
MP3:
MP4:
 Post Hartree-Fock

II. Møller-Plesset (MP)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

𝑖 MP-N
MP2:

1 1
𝜓2 =⟨𝑖𝑗|𝑎𝑏⟩=∫ 𝜙𝑖 ∗ (𝒓𝟏) 𝜙 𝑗 ∗ (𝒓𝟐) 𝜙𝑎( 𝒓𝟏) 𝜙𝑏 (𝒓𝟐) 𝑑𝑟𝑑𝑟 −∫ 𝜙𝑖 ∗(𝒓 𝟐) 𝜙 𝑗 ∗( 𝒓𝟏) 𝜙𝑏 (𝒓 𝟐) 𝜙𝑎(𝒓 𝟏) 𝑑𝑟𝑑𝑟′
Occupied Virtual
𝑆𝐷 ′

|𝒓𝟏 −𝒓𝟐| |𝒓 𝟏−𝒓 𝟐|

Occupied Virtual
 Post Hartree-Fock

III. Multi-confugurational Self-consistent-field (MCSCF)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

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𝑖𝑗 𝑖𝑗 𝑎𝑏 𝑎𝑏
𝑋 1 ( 𝒓 𝟏 ) … 𝑋 𝑁 (𝒓 𝟏 ) 𝑋 1 (𝒓 𝟏 ) … 𝑋 𝑀 ( 𝒓 𝟏)
⋮ ⋮
𝑖𝑗 𝑎𝑏
𝑀𝐶𝑆𝐶𝐹 1 𝑋1 ( 𝒓 𝑁 ) 𝑋𝑀 ( 𝒓 𝑵)
𝜓 =
√𝑁+ 𝑀 ! 𝑖𝑗
𝑋 1 (𝒓 ′ 𝟏 )
𝑎𝑏
𝑋 𝑀 (𝒓 ′ 𝟏 )
⋮ ⋮.
𝑋 1 ( 𝒓 ′ 𝑴 ) … 𝑋 𝑁 (𝒓 𝑴 ) 𝑋 1 (𝒓 𝑴 ) … 𝑋 𝑀 ( 𝒓 ′ 𝟏 )
𝑖𝑗 𝑖𝑗 ′ 𝑎𝑏 ′ 𝑎𝑏
 Post Hartree-Fock

IV. Coupled Cluster (CC)

𝜓 =∑ 𝐶 𝑖 𝜓𝑖 =𝐶 0 𝜓0 +𝐶 1 𝜓 1 +𝐶 2 𝜓 2 +…+𝐶 𝑁 𝜓 𝑁
𝐶𝐼 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷 𝑆𝐷

Operator
Cluster
𝐶𝐶 𝑇
𝜓 = 𝑒 𝜓 𝐻𝐹 Deret Taylor
𝑇 1 2
𝑇 =𝑇 1 +𝑇 2+ …+𝑇 𝑁 𝑒 =1+𝑇 + 𝑇 +…
2!
Second Quantization
Creation/Annihilation
Exchange: Slater Determinant
Kasus Banyak Partikel
Thank You!