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Title: Addressing first derivative discontinuities in orbital-optimized opposite-spin scaled second-order perturbation theory with regularization

Abstract

Orbital-optimized opposite-spin scaled second-order perturbation theory (O2) generates a single-reference wave function composed of approximate Brueckner orbitals with fourth-order computational scaling. While O2 provides significantly improved treatment of radicals by reducing spin contamination, it has been shown to suffer from first derivative discontinuities for bond stretching near the unrestriction point. That qualitative failure is resolved in this work by the implementation of regularized O2, which includes a regularization parameter in the denominator of its second-order term. The value of the regularization parameter is semi-empirically chosen to qualitatively describe bond stretching energetics of hydrogen, ethane and ethene, while also considering the effect of the regularization parameter on thermochemical errors for the well-known Gaussian-2 (G2) test set. The generality of the empirical scaling and semi-empirical regularization parameter is studied by application to the 3dMLBE20, DBH24, RSE43 and W4-11 test sets. We demonstrate that accuracy of O2 is roughly maintained and sometimes even improved by regularization, with root mean squares of regularised O2 between factors of 1.6 and 0.8 from corresponding root mean squares of O2.

Authors:
 [1];  [1];  [1]
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  1. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1479330
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Volume: 115; Journal Issue: 17-18; Journal ID: ISSN 0026-8976
Publisher:
Taylor & Francis
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; Perturbation theory; Brueckner orbitals; spin polarization; regularization

Citation Formats

Razban, Rostam M., Stück, David, and Head-Gordon, Martin. Addressing first derivative discontinuities in orbital-optimized opposite-spin scaled second-order perturbation theory with regularization. United States: N. p., 2017. Web. doi:10.1080/00268976.2017.1284355.
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Razban, Rostam M., Stück, David, & Head-Gordon, Martin. Addressing first derivative discontinuities in orbital-optimized opposite-spin scaled second-order perturbation theory with regularization. United States. https://doi.org/10.1080/00268976.2017.1284355
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Razban, Rostam M., Stück, David, and Head-Gordon, Martin. Sun . "Addressing first derivative discontinuities in orbital-optimized opposite-spin scaled second-order perturbation theory with regularization". United States. https://doi.org/10.1080/00268976.2017.1284355. https://www.osti.gov/servlets/purl/1479330.
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@article{osti_1479330,
title = {Addressing first derivative discontinuities in orbital-optimized opposite-spin scaled second-order perturbation theory with regularization},
author = {Razban, Rostam M. and Stück, David and Head-Gordon, Martin},
abstractNote = {Orbital-optimized opposite-spin scaled second-order perturbation theory (O2) generates a single-reference wave function composed of approximate Brueckner orbitals with fourth-order computational scaling. While O2 provides significantly improved treatment of radicals by reducing spin contamination, it has been shown to suffer from first derivative discontinuities for bond stretching near the unrestriction point. That qualitative failure is resolved in this work by the implementation of regularized O2, which includes a regularization parameter in the denominator of its second-order term. The value of the regularization parameter is semi-empirically chosen to qualitatively describe bond stretching energetics of hydrogen, ethane and ethene, while also considering the effect of the regularization parameter on thermochemical errors for the well-known Gaussian-2 (G2) test set. The generality of the empirical scaling and semi-empirical regularization parameter is studied by application to the 3dMLBE20, DBH24, RSE43 and W4-11 test sets. We demonstrate that accuracy of O2 is roughly maintained and sometimes even improved by regularization, with root mean squares of regularised O2 between factors of 1.6 and 0.8 from corresponding root mean squares of O2.},
doi = {10.1080/00268976.2017.1284355},
journal = {Molecular Physics},
number = 17-18,
volume = 115,
place = {United States},
year = {Sun Feb 26 00:00:00 EST 2017},
month = {Sun Feb 26 00:00:00 EST 2017}
}
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https://doi.org/10.1080/00268976.2017.1284355
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    Works referencing / citing this record:

    Distinguishing artificial and essential symmetry breaking in a single determinant: approach and application to the C 60 , C 36 , and C 20 fullerenes
    journal, January 2019

    • Lee, Joonho; Head-Gordon, Martin
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    • DOI: 10.1039/c8cp07613h
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