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Title: Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory

Abstract

Long considered a failure, second-order symmetry-adapted perturbation theory (SAPT) based on Kohn–Sham orbitals, or SAPT0(KS), can be resurrected for semiquantitative purposes using long-range corrected density functionals whose asymptotic behavior is adjusted separately for each monomer. As in other contexts, correct asymptotic behavior can be enforced via “optimal tuning” based on the ionization energy theorem of density functional theory, but the tuning procedure is tedious, expensive for large systems, and comes with a troubling dependence on system size. Here, we show that essentially identical results are obtained using a fast, convenient, and automated tuning procedure based on the size of the exchange hole. In conjunction with “extended” (X)SAPT methods that improve the description of dispersion, this procedure achieves benchmark-quality interaction energies, along with the usual SAPT energy decomposition, without the hassle of system-specific tuning.

Authors:
ORCiD logo [1]; ORCiD logo [1]
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  1. The Ohio State Univ., Columbus, OH (United States)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1833484
Alternate Identifier(s):
OSTI ID: 1808213
Grant/Contract Number:  
SC0008550
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 155; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; Ions and properties; HOMO and LUMO; Correlation-consistent basis sets; Dispersion; Amino acid; Chemical bonding; Perturbation theory; Nanoribbons; Density functional theory; Coupled-cluster methods

Citation Formats

Gray, Montgomery, and Herbert, John M. Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory. United States: N. p., 2021. Web. doi:10.1063/5.0059364.
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Gray, Montgomery, & Herbert, John M. Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory. United States. https://doi.org/10.1063/5.0059364
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Gray, Montgomery, and Herbert, John M. Thu . "Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory". United States. https://doi.org/10.1063/5.0059364. https://www.osti.gov/servlets/purl/1833484.
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@article{osti_1833484,
title = {Simplified tuning of long-range corrected density functionals for use in symmetry-adapted perturbation theory},
author = {Gray, Montgomery and Herbert, John M.},
abstractNote = {Long considered a failure, second-order symmetry-adapted perturbation theory (SAPT) based on Kohn–Sham orbitals, or SAPT0(KS), can be resurrected for semiquantitative purposes using long-range corrected density functionals whose asymptotic behavior is adjusted separately for each monomer. As in other contexts, correct asymptotic behavior can be enforced via “optimal tuning” based on the ionization energy theorem of density functional theory, but the tuning procedure is tedious, expensive for large systems, and comes with a troubling dependence on system size. Here, we show that essentially identical results are obtained using a fast, convenient, and automated tuning procedure based on the size of the exchange hole. In conjunction with “extended” (X)SAPT methods that improve the description of dispersion, this procedure achieves benchmark-quality interaction energies, along with the usual SAPT energy decomposition, without the hassle of system-specific tuning.},
doi = {10.1063/5.0059364},
journal = {Journal of Chemical Physics},
number = 3,
volume = 155,
place = {United States},
year = {Thu Jul 15 00:00:00 EDT 2021},
month = {Thu Jul 15 00:00:00 EDT 2021}
}
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