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Title: Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C

Abstract

With the aim of mitigating the basis set error in density functional theory (DFT) calculations employing local basis sets, we herein develop two empirical corrections for basis set superposition error (BSSE) in the def2-SVPD basis, a basis which - when stripped of BSSE - is capable of providing near-complete-basis DFT results for non-covalent interactions. Specifically, we adapt the existing pairwise geometrical counterpoise (gCP) approach to the def2-SVPD basis, and we develop a beyond-pairwise approach, DFT-C, which we parameterize across a small set of intermolecular interactions. Both gCP and DFT-C are evaluated against the traditional Boys-Bernardi counterpoise correction across a set of 3402 non-covalent binding energies and isomerization energies. We find that the DFT-C method represents a significant improvement over gCP, particularly for non-covalently-interacting molecular clusters. Furthermore, DFT-C is transferable among density functionals and can be combined with existing functionals - such as B97M-V - to recover large-basis results at a fraction of the cost.

Authors:
ORCiD logo [1];  [2];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1477257
Alternate Identifier(s):
OSTI ID: 1364451
Grant/Contract Number:  
AC02-05CH11231; FG02-12ER16362
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 23; Related Information: © 2017 Author(s).; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Witte, Jonathon, Neaton, Jeffrey B., and Head-Gordon, Martin. Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C. United States: N. p., 2017. Web. doi:10.1063/1.4986962.
Witte, Jonathon, Neaton, Jeffrey B., & Head-Gordon, Martin. Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C. United States. doi:10.1063/1.4986962.
Witte, Jonathon, Neaton, Jeffrey B., and Head-Gordon, Martin. Tue . "Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C". United States. doi:10.1063/1.4986962. https://www.osti.gov/servlets/purl/1477257.
@article{osti_1477257,
title = {Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C},
author = {Witte, Jonathon and Neaton, Jeffrey B. and Head-Gordon, Martin},
abstractNote = {With the aim of mitigating the basis set error in density functional theory (DFT) calculations employing local basis sets, we herein develop two empirical corrections for basis set superposition error (BSSE) in the def2-SVPD basis, a basis which - when stripped of BSSE - is capable of providing near-complete-basis DFT results for non-covalent interactions. Specifically, we adapt the existing pairwise geometrical counterpoise (gCP) approach to the def2-SVPD basis, and we develop a beyond-pairwise approach, DFT-C, which we parameterize across a small set of intermolecular interactions. Both gCP and DFT-C are evaluated against the traditional Boys-Bernardi counterpoise correction across a set of 3402 non-covalent binding energies and isomerization energies. We find that the DFT-C method represents a significant improvement over gCP, particularly for non-covalently-interacting molecular clusters. Furthermore, DFT-C is transferable among density functionals and can be combined with existing functionals - such as B97M-V - to recover large-basis results at a fraction of the cost.},
doi = {10.1063/1.4986962},
journal = {Journal of Chemical Physics},
number = 23,
volume = 146,
place = {United States},
year = {Tue Jun 20 00:00:00 EDT 2017},
month = {Tue Jun 20 00:00:00 EDT 2017}
}

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Works referenced in this record:

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