An overview of self-consistent field calculations within finite basis sets

TL;DR

This paper provides a comprehensive, uniform derivation of self-consistent field equations in finite basis sets, covering various theories and discussing solution methods, invariance, and extensions to advanced functionals.

Contribution

It offers a unified derivation of SCF equations for multiple theories and discusses solution strategies, invariance, and extensions to advanced density functionals.

Findings

Derivation of SCF equations in non-orthogonal basis sets.

Discussion of invariance and localized orbitals.

Analysis of solution methods including diagonalization and direct minimization.

Abstract

A uniform derivation is presented of the self-consistent field equations in a finite basis set. Both restricted and unrestricted Hartree-Fock (HF) theory as well as various density functional (DF) approximations are considered. The unitary invariance of the HF and DF models is discussed, paving the way for the use of localized molecular orbitals. The self-consistent field equations are derived in a non-orthogonal basis set, and their solution is discussed in the presence of linear dependencies in the basis set. It is argued why iterative diagonalization of the Kohn-Sham-Fock matrix leads to the minimization of the total energy. Alternative methods for the solution of the self-consistent field equations via direct minimization as well as stability analysis are also briefly discussed. Explicit expressions are given for the contributions to the Kohn-Sham-Fock matrix up to meta-GGA functionals. Range-separated hybrids and non-local correlation functionals are also briefly discussed.