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March13 Lecture

The document discusses the Condon-Slater rules and the Self-Consistent Field (SCF) method for the Helium atom, detailing the iterative process to achieve convergence in finding the best N-electron determinantal wavefunction. It highlights the Hartree-Fock SCF method, emphasizing the importance of orthonormal spinorbitals and the variational formulation to minimize energy. Additionally, it covers Koopmans' theorem for estimating ionization potential and electron affinity, along with the Fock operator and its role in the Hartree-Fock equations.

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Arnab Das
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15 views12 pages

March13 Lecture

The document discusses the Condon-Slater rules and the Self-Consistent Field (SCF) method for the Helium atom, detailing the iterative process to achieve convergence in finding the best N-electron determinantal wavefunction. It highlights the Hartree-Fock SCF method, emphasizing the importance of orthonormal spinorbitals and the variational formulation to minimize energy. Additionally, it covers Koopmans' theorem for estimating ionization potential and electron affinity, along with the Fock operator and its role in the Hartree-Fock equations.

Uploaded by

Arnab Das
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Condon-Slater Rules

Self-Consistent Field
For He atom
Hartree Product

Interaction energy of electron 1 with the charge density (field) of electron 2:

New Hamiltonian for electron 1


Self-Consistent Field
For He atom
Effective one-electron Hamiltonian

Iterative Solution
Self-Consistent Solution
Self-Consistent Field
For N-electron System

… … … repeat for each electron

… … … repeat for each electron


……

iterate the process till convergence (no change in spinorbitals)

Proposed by Hartree (Hartree’s SCF)


Hartree-Fock SCF SCF Scheme of Hartree, improved by Fock (and Slater)

Hartree SCF

Hartree-Fock SCF

❖ Find the best N-electron determinantal wavefunction (using variation


method) that gives the lowest energy (for a given nuclear configuration)
while making sure that the spinorbitals remain orthonormal.
Variational Formulation of HF-SCF
❖ Find the best N-electron determinantal wavefunction (using variation method) that gives the lowest
energy (for a given nuclear configuration) while making sure that the spinorbitals remain orthonormal.

N-electron determinantal wavefunction

Energy

Orthonormal spinorbitals

o Functional Variation
o Minimization with a constrain
HF-SCF Method
N-electron Hamiltonian N-electron deteminantal wavefunction

Deteminantal energy

(spinorbitals)

(spatial orbitals)
Molecular Hamiltonian vs HF-Hamiltonian
N-electron Hamiltonian
and its true solution

HF Solution

Comparison of Molecular Hamiltonian and HF Hamiltonian

Partial treatment of electron correlation


HF-Energy
HF wavefunction

HF Energy

Energy of spinorbital

Sum of HF orbital energy is NOT the HF energy


Ionization potential
HF wavefunction

Koopmans’ Theorem
• Ionization potential for removing
an electron from an orbital is the
negative of that orbital energy
Electron Affinity

Koopmans’ Theorem

Koopmans’ theorem, operating within ‘frozen orbital’ approximation,


provides a reasonable first approximation of IP, but EA estimations are
often poor.
Fock Operator

Fock Operator

Hartree-Fock Equations

Canonical HF Equation (with


transformed spinorbitals)

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