Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

Michał Hapka; Łukasz Rajchel; Marcin Modrzejewski; Grzegorz Chałasiński; Małgorzata M Szczęśniak

doi:10.1063/1.4896608

Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory

J Chem Phys. 2014 Oct 7;141(13):134120. doi: 10.1063/1.4896608.

Authors

Michał Hapka¹, Łukasz Rajchel², Marcin Modrzejewski¹, Grzegorz Chałasiński¹, Małgorzata M Szczęśniak³

Affiliations

¹ Faculty of Chemistry, University of Warsaw, 02-093 Warsaw, Pasteura 1, Poland.
² Faculty of Chemistry, University of Duisburg-Essen, Universitätsstraße 5, 45117 Essen, Germany.
³ Department of Chemistry, Oakland University, Rochester, Michigan 48309-4477, USA.

PMID: 25296797
DOI: 10.1063/1.4896608

Abstract

The aim of this study is to present a performance test of optimally tuned long-range corrected (LRC) functionals applied to the symmetry-adapted perturbation theory (SAPT). In the present variant, the second-order energy components are evaluated at the coupled level of theory. We demonstrate that the generalized Kohn-Sham (GKS) description of monomers with optimally tuned LRC functionals may be essential for the quality of SAPT interaction energy components. This is connected to the minimization of a many-electron self-interaction error and exemplified by two model systems: polyacetylenes of increasing length and stretching of He 3 (+). Next we provide a comparison of SAPT approaches based on Kohn-Sham and GKS description of the monomers. We show that LRC leads to results better or comparable with the hitherto prevailing asymptotically corrected functionals. Finally, we discuss the advantages and possible limitations of SAPT based on LRC functionals.