Towards the Hartree-Fock and coupled-cluster singles and doubles basis set limit: A study of various models that employ single excitations into a complementary auxiliary basis set

Andreas Koehn*, David P. Tew

*Corresponding author for this work

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

27 Citations (Scopus)

Abstract

In explicitly correlated coupled-cluster singles and doubles [CCSD(F12)] calculations, the basis set incompleteness error in the double excitations is reduced to such an extent that the error in the Hartree-Fock energy and the error in the single excitations become important. Using arguments from perturbation theory to systematically truncate the coupled-cluster singles and CCSD(F12) Lagrangians, a series of coupled-cluster models are proposed and studied that reduce these basis set incompleteness errors through additional single excitations into a complementary auxiliary basis. Convergence with model and size of complementary basis is rapid and there appears to be no need to go beyond second-order models. Our iterative second-order approach is a slight improvement over the existing noniterative approach, but its main advantage is that it is suitable for response theory.

Original languageEnglish
Article number024101
Number of pages10
JournalJournal of Chemical Physics
Volume132
Issue number2
DOIs
Publication statusPublished - 14 Jan 2010

Keywords

  • coupled cluster calculations
  • excited states
  • HF calculations
  • perturbation theory
  • CORRELATED PERTURBATION-THEORY
  • MOLLER-PLESSET CALCULATIONS
  • ELECTRONIC-STRUCTURE THEORY
  • ZETA BASIS-SETS
  • DUAL BASIS-SETS
  • NUMERICAL QUADRATURES
  • CORRELATION ENERGIES
  • CORRELATION CUSP
  • WAVE-FUNCTIONS
  • ERRORS

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