Fast Hartree-Fock theory using local density fitting approximations

R Polly, HJ Werner*, FR Manby, PJ Knowles

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

240 Citations (Scopus)

Abstract

Density fitting approximations are applied to generate the Fock matrix in Hartree-Fock calculations. By localizing the orbitals in each iteration and performing separate fits for each orbital the O(N-4) scaling of the computational effort for the exchange can be reduced to O(N). We also use the Poisson method to replace almost all Coulomb integrals with simple overlaps, an efficient alternative to diagonalization, and dual basis sets such that the Hartree-Fock calculation is performed in a smaller basis than the subsequent treatment of electron correlation. The accuracy and efficiency of the method is demonstrated in calculations with almost 4000 basis functions. The errors introduced by the local approximations on HF and MP2 energies are small compared to those that arise from the density fitting, and the fitting errors themselves (typically 1-10 microhartree per atom) are very small compared, for example, to the effect of basis set variations.

Translated title of the contributionFast Hartree-Fock theory using local density fitting approximations
Original languageEnglish
Pages (from-to)2311-2321
Number of pages11
JournalMolecular Physics
Volume102
Issue number21-22
DOIs
Publication statusPublished - 10 Nov 2004
EventEuropean Network THEONET II Meeting - Bologna, Italy
Duration: 1 Nov 2003 → …

Bibliographical note

Publisher: Taylor & Francis
Other: On-line ISSN 1362-3028

Keywords

  • AUXILIARY BASIS-SETS
  • COUPLED-CLUSTER THEORY
  • PLESSET PERTURBATION-THEORY
  • EFFICIENCY
  • LINEAR-COMBINATION
  • ABINITIO
  • INTEGRALS

Fingerprint Dive into the research topics of 'Fast Hartree-Fock theory using local density fitting approximations'. Together they form a unique fingerprint.

Cite this