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

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{sub 3}{sup +}. 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.

Authors:
;  [1];  [2];  [1];  [3]
  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 (United States)
Publication Date:
OSTI Identifier:
22436546
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 13; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPARATIVE EVALUATIONS; ELECTRONS; HYBRIDIZATION; INTERACTIONS; MINIMIZATION; MONOMERS; PERTURBATION THEORY; POLYACETYLENES

Citation Formats

Hapka, Michał, Modrzejewski, Marcin, Rajchel, Łukasz, Interdisciplinary Centre for Mathematical and Computational Modelling, University of Warsaw, 00-838 Warsaw, Prosta 69, Chałasiński, Grzegorz, Department of Chemistry, Oakland University, Rochester, Michigan 48309-4477, and Szczęśniak, Małgorzata M. Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory. United States: N. p., 2014. Web. doi:10.1063/1.4896608.
Hapka, Michał, Modrzejewski, Marcin, Rajchel, Łukasz, Interdisciplinary Centre for Mathematical and Computational Modelling, University of Warsaw, 00-838 Warsaw, Prosta 69, Chałasiński, Grzegorz, Department of Chemistry, Oakland University, Rochester, Michigan 48309-4477, & Szczęśniak, Małgorzata M. Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory. United States. https://doi.org/10.1063/1.4896608
Hapka, Michał, Modrzejewski, Marcin, Rajchel, Łukasz, Interdisciplinary Centre for Mathematical and Computational Modelling, University of Warsaw, 00-838 Warsaw, Prosta 69, Chałasiński, Grzegorz, Department of Chemistry, Oakland University, Rochester, Michigan 48309-4477, and Szczęśniak, Małgorzata M. 2014. "Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory". United States. https://doi.org/10.1063/1.4896608.
@article{osti_22436546,
title = {Tuned range-separated hybrid functionals in the symmetry-adapted perturbation theory},
author = {Hapka, Michał and Modrzejewski, Marcin and Rajchel, Łukasz and Interdisciplinary Centre for Mathematical and Computational Modelling, University of Warsaw, 00-838 Warsaw, Prosta 69 and Chałasiński, Grzegorz and Department of Chemistry, Oakland University, Rochester, Michigan 48309-4477 and Szczęśniak, Małgorzata M.},
abstractNote = {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{sub 3}{sup +}. 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.},
doi = {10.1063/1.4896608},
url = {https://www.osti.gov/biblio/22436546}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 141,
place = {United States},
year = {Tue Oct 07 00:00:00 EDT 2014},
month = {Tue Oct 07 00:00:00 EDT 2014}
}