The exchange-correlation potential in ab initio density functional theory

Rodney J. Bartlett, Ireneusz Grabowski, So Hirata, Stanislav Ivanov

Research output: Contribution to journalArticle

Abstract

From coupled-cluster theory and many-body perturbation theory we derive the local exchange-correlation potential of density functional theory in an orbital dependent form. We show the relationship between the coupled-cluster approach and density functional theory, and connections and comparisons with our previous second-order correlation potential [OEP-MBPT(2) (OEP - optimized effective potential)] [I. Grabowski, S. Hirata, S. Ivanov, and R. J. Bartlett, J. Chem. Phys. 116, 4415 (2002)]. Starting from a general theoretical framework based on the density condition in Kohn-Sham theory, we define a rigorous exchange-correlation functional, potential and orbitals. Specifying initially to second-order terms, we show that our ab initio correlation potential provides the correct shape compared to those from reference quantum Monte Carlo calculations, and we demonstrate the superiority of using Fock matrix elements or more general infinite-order semicanonical transformations. This enables us to introduce a method that is guaranteed to converge to the right answer in the correlation and basis set limit, just as does ab initio wave function theory. We also demonstrate that the energies obtained from this generalized second-order method [OEP-MBPT(2)-f] and [OEP-MBPT(2)-sc] are often of coupled-cluster accuracy and substantially better than ordinary Hartree-Fock based second-order MBPT=MP2.

Original languageEnglish (US)
Article number034104
JournalJournal of Chemical Physics
Volume122
Issue number3
DOIs
StatePublished - Aug 8 2005
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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