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Title: Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory

Abstract

Extended symmetry-adapted perturbation theory (XSAPT) uses a self-consistent charge embedding to capture many-body polarization, in conjunction with a pairwise-additive SAPT calculation of intermolecular interaction energies. The original implementation of XSAPT is based on charges that are fit to reproduce molecular electrostatic potentials, but this becomes a computational bottleneck in large systems. Charge embedding based on modified Hirshfeld atomic charges is reported here, which dramatically reduces the computational cost without compromising accuracy. Exemplary calculations are presented for supramolecular complexes such as C60@C60H28, a DNA intercalation complex, and a 323-atom model of a drug molecule bound to an enzyme active site. The proposed charge embedding should be useful in other fragment-based quantum chemistry methods as well.

Authors:
ORCiD logo [1]; 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, and Biosciences Division
OSTI Identifier:
1604455
Alternate Identifier(s):
OSTI ID: 1542692
Grant/Contract Number:  
SC0008850; SC0008550
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; 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

Citation Formats

Liu, Kuan-Yu, Carter-Fenk, Kevin, and Herbert, John M. Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory. United States: N. p., 2019. Web. doi:10.1063/1.5111869.
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Liu, Kuan-Yu, Carter-Fenk, Kevin, & Herbert, John M. Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory. United States. https://doi.org/10.1063/1.5111869
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Liu, Kuan-Yu, Carter-Fenk, Kevin, and Herbert, John M. Tue . "Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory". United States. https://doi.org/10.1063/1.5111869. https://www.osti.gov/servlets/purl/1604455.
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@article{osti_1604455,
title = {Self-consistent charge embedding at very low cost, with application to symmetry-adapted perturbation theory},
author = {Liu, Kuan-Yu and Carter-Fenk, Kevin and Herbert, John M.},
abstractNote = {Extended symmetry-adapted perturbation theory (XSAPT) uses a self-consistent charge embedding to capture many-body polarization, in conjunction with a pairwise-additive SAPT calculation of intermolecular interaction energies. The original implementation of XSAPT is based on charges that are fit to reproduce molecular electrostatic potentials, but this becomes a computational bottleneck in large systems. Charge embedding based on modified Hirshfeld atomic charges is reported here, which dramatically reduces the computational cost without compromising accuracy. Exemplary calculations are presented for supramolecular complexes such as C60@C60H28, a DNA intercalation complex, and a 323-atom model of a drug molecule bound to an enzyme active site. The proposed charge embedding should be useful in other fragment-based quantum chemistry methods as well.},
doi = {10.1063/1.5111869},
journal = {Journal of Chemical Physics},
number = 3,
volume = 151,
place = {United States},
year = {Tue Jul 16 00:00:00 EDT 2019},
month = {Tue Jul 16 00:00:00 EDT 2019}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5111869
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Citation Metrics:
Cited by: 18 works
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Figures / Tables:

FIG. 1 FIG. 1: Timing data for XSAPT(KS)+aiD/hp-TZVPP calculations on C60@C60H28 (4,592 basis functions), using either the original ChElPG implementation of XSAPT (left-hand bar in each pair, using data from Ref 21), or else the new CM5 implementation reported here (right-hand bars). Both calculations were parallelized across all 28 cores of amore » single compute node. The total calculation time is broken down into three color-coded steps: the XPol self-consistent field procedure (in red); pseudocanonicalization to transform the monomer MOs to a dimer basis (in blue); and finally the SAPT calculation (in green). Charge derivatives are required in all three steps and these timing data are separated out and depicted in purple. Orange bars represent the Gram-Schmidt orthogonalization contribution to the pseudocanonicalization step, where the multithreading has been improved in the present implementation as compared to the one reported in Ref. 21.« less
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    Works referencing / citing this record:

    Fantasy versus reality in fragment-based quantum chemistry
    journal, November 2019

    • Herbert, John M.
    • The Journal of Chemical Physics, Vol. 151, Issue 17
    • DOI: 10.1063/1.5126216

    Recent developments in symmetry‐adapted perturbation theory
    journal, November 2019

    • Patkowski, Konrad
    • WIREs Computational Molecular Science, Vol. 10, Issue 3
    • DOI: 10.1002/wcms.1452
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