Assessment of basis sets for F12 explicitly-correlated molecular electronic-structure methods

Florian A. Bischoff, Sandra Wolfsegger, David P. Tew, Wim Klopper*

*Corresponding author for this work

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

61 Citations (Scopus)

Abstract

One-electron basis sets for F12 explicitly-correlated molecular electronic-structure methods are assessed by analysing the accuracy of Hartree-Fock energies and valence-only second-order correlation energies of a test set of 106 small molecules containing the atoms H, C, N, O and F. For these molecules, near Hartree-Fock-limit energies and benchmark second-order correlation energies (accurate to within 99.95% of the basis-set limit) are provided. Absolute energies are analysed as well as the Hartree-Fock and second-order correlation contributions to the atomisation energies of the molecules. Standard basis sets such as the Karlsruhe def2-TZVPP and def2-QZVPP sets and the augmented correlation-consistent polarised valence X-tuple zeta (aug-cc-p VXZ, X = D, T, Q, 5) sets are compared with the specialised cc-pVXZ-F12 (X D, T, Q) sets that were recently optimised by Peterson and co-workers [J. Chem. Phys. 128, 084102 (2008)] for use in F12 theory. The results obtained from F12 explicitly-correlated molecular electronic-structure calculations are compared with those that are obtained by standard electronic-structure calculations followed by basis-set extrapolation based on the X (3) convergence behaviour of the aug-cc-pVXZ basis sets. The most important conclusions are that the cc-pVXZ-F12 sets are the preferred basis sets for F12 theory and that the X(-3) extrapolation from the aug-cc-pVQZ and aug-cc-pV5Z is slightly more accurate than F12 theory in the cc-pVTZ-F12 basis but less accurate than F12 theory in the cc-pVQZ-F12 basis.

Original languageEnglish
Pages (from-to)963-975
Number of pages13
JournalMolecular Physics
Volume107
Issue number8-12
DOIs
Publication statusPublished - 2009

Keywords

  • basis sets
  • explicitly-correlated wave functions
  • F12 methods
  • atomisation energies
  • 2ND-ORDER PERTURBATION-THEORY
  • COUPLED-CLUSTER METHODS
  • AUXILIARY BASIS-SETS
  • ZETA BASIS-SETS
  • GAUSSIAN-BASIS SETS
  • PI-PI INTERACTIONS
  • CORRELATION ENERGIES
  • WAVE-FUNCTIONS
  • WATER DIMER
  • ACCURACY

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