Fitting the Coulomb potential variationally in linear-combination-of-atomic-orbitals density-functional calculations

J. W. Mintmire and B. I. Dunlap
Phys. Rev. A 25, 88 – Published 1 January 1982
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Abstract

A previously developed method for self-consistent-field density-functional calculations involving a variational fit to the charge density is generalized to the case in which the total (electronic plus nuclear) Coulomb potential is fit. Previously the total energy E(ρ,ρ̃) was viewed as a functional of the exact ρ and fitted ρ̃ charge density. The energy expression was modified to be correct when ρ̃=ρ while at the same time allowing ρ̃ to be obtained variationally through E(ρ,ρ̃)ρ̃=0. Herein an expression for E(ρ,Ṽ), where Ṽ is the fit to the Coulomb potential, is derived with similar properties. In particular, Ṽ can be determined variationally through E(ρ,Ṽ)Ṽ=0. In various linear-combination-of-atomic-orbitals calculations on atomic neon, the superiority of variational over conventional least-squares-fitting methods is demonstrated.

  • Received 18 May 1981

DOI:https://doi.org/10.1103/PhysRevA.25.88

©1982 American Physical Society

Authors & Affiliations

J. W. Mintmire*

  • Quantum Theory Project, Williamson Hall, University of Florida, Gainesville, Florida 32611

B. I. Dunlap

  • Naval Research Laboratory, Code 6170, Washington, D.C. 20375

  • *Present address: Naval Research Laboratory, Code 6170, Washington, D.C. 20375.

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Vol. 25, Iss. 1 — January 1982

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