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Title: Analytic gradients for the single-reference driven similarity renormalization group second-order perturbation theory

Abstract

Herein we derive and implement analytic energy gradients for the single-reference driven similarity renormalization group second-order perturbation theory (DSRG-PT2). The resulting equations possess an asymptotic scaling that is identical to that of the second-order Møller–Plesset perturbation theory (MP2), indicating that the exponential regularizer in the DSRG equations does not introduce formal difficulties in the gradient theory. We apply the DSRG-PT2 method to optimizing the geometries of 15 small molecules. The equilibrium bond lengths computed with DSRG-PT2 are found similar to those of MP2, yielding a mean absolute error of 0.0033 Å and a standard deviation of 0.0045 Å when compared with coupled cluster with singles, doubles, and perturbative triples.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Emory Univ., Atlanta, GA (United States)
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1612370
Alternate Identifier(s):
OSTI ID: 1545915
Grant/Contract Number:  
SC0016004
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics; Potential energy surfaces; Renormalization and regularization; Electronic structure methods; Perturbation theory; Gradient method

Citation Formats

Wang, Shuhe, Li, Chenyang, and Evangelista, Francesco A. Analytic gradients for the single-reference driven similarity renormalization group second-order perturbation theory. United States: N. p., 2019. Web. doi:10.1063/1.5100175.
Wang, Shuhe, Li, Chenyang, & Evangelista, Francesco A. Analytic gradients for the single-reference driven similarity renormalization group second-order perturbation theory. United States. https://doi.org/10.1063/1.5100175
Wang, Shuhe, Li, Chenyang, and Evangelista, Francesco A. 2019. "Analytic gradients for the single-reference driven similarity renormalization group second-order perturbation theory". United States. https://doi.org/10.1063/1.5100175. https://www.osti.gov/servlets/purl/1612370.
@article{osti_1612370,
title = {Analytic gradients for the single-reference driven similarity renormalization group second-order perturbation theory},
author = {Wang, Shuhe and Li, Chenyang and Evangelista, Francesco A.},
abstractNote = {Herein we derive and implement analytic energy gradients for the single-reference driven similarity renormalization group second-order perturbation theory (DSRG-PT2). The resulting equations possess an asymptotic scaling that is identical to that of the second-order Møller–Plesset perturbation theory (MP2), indicating that the exponential regularizer in the DSRG equations does not introduce formal difficulties in the gradient theory. We apply the DSRG-PT2 method to optimizing the geometries of 15 small molecules. The equilibrium bond lengths computed with DSRG-PT2 are found similar to those of MP2, yielding a mean absolute error of 0.0033 Å and a standard deviation of 0.0045 Å when compared with coupled cluster with singles, doubles, and perturbative triples.},
doi = {10.1063/1.5100175},
url = {https://www.osti.gov/biblio/1612370}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
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Figures / Tables:

TABLE I TABLE I: Definition of the molecular spin orbital spaces used in this work.

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