The orbital-specific virtual local triples correction: OSV-L(T)

Martin Schuetz*, Jun Yang, Garnet Kin-Lic Chan, Frederick R. Manby, Hans-Joachim Werner

*Corresponding author for this work

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

64 Citations (Scopus)

Abstract

A local method based on orbital specific virtuals (OSVs) for calculating the perturbative triples correction in local coupled cluster calculations is presented. In contrast to the previous approach based on projected atomic orbitals (PAOs), described by Schutz [J. Chem. Phys. 113, 9986 (2000)], the new scheme works without any ad hoc truncations of the virtual space to domains. A single threshold defines the pair and triple specific virtual spaces completely and automatically. It is demonstrated that the computational cost of the method scales linearly with molecular size. Employing the recommended threshold a similar fraction of the correlation energy is recovered as with the original PAO method at a somewhat lower cost. A benchmark for 52 reactions demonstrates that for reaction energies the intrinsic accuracy of the coupled cluster with singles and doubles excitations and a perturbative treatment of triples excitations method can be reached by OSV-local coupled cluster theory with singles and doubles and perturbative triples, provided a MP2 correction is applied that accounts for basis set incompleteness errors as well as for remaining domain errors. As an application example the interaction energies of the guanine-cytosine dimers in the Watson-Crick and stacked arrangements are investigated at the level of local coupled cluster theory with singles and doubles and perturbative triples. Based on these calculations we propose new complete-basis-set-limit estimates for these interaction energies at this level of theory. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4789415]

Original languageEnglish
Article number054109
Number of pages10
JournalJournal of Chemical Physics
Volume138
Issue number5
DOIs
Publication statusPublished - 7 Feb 2013

Keywords

  • BASIS-SETS
  • CORRECTION T
  • CHOLESKY DECOMPOSITIONS
  • CONFIGURATION-INTERACTION
  • CORRELATION ENERGIES
  • COUPLED-CLUSTER THEORY
  • PLESSET PERTURBATION-THEORY
  • DNA-BASE PAIRS
  • PNO-CI
  • ELECTRON CORRELATION METHODS

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