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Title: Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction

Abstract

In this study we introduce two size consistent forms of the non-orthogonal configuration interaction with second-order Møller-Plesset perturbation theory method, NOCI-MP2. We show that the original NOCI-MP2 formulation [S. R. Yost, T. Kowalczyk, and T. VanVoorh, J. Chem. Phys. 193, 174104 (2013)], which is a perturb-then-diagonalize multi-reference method, is not size consistent. We also show that this causes significant errors in large systems like the linear acenes. By contrast, the size consistent versions of the method give satisfactory results for singlet and triplet excited states when compared to other multi-reference methods that include dynamic correlation. For NOCI-MP2 however, the number of required determinants to yield similar levels of accuracy is significantly smaller. These results show the promise of the NOCI-MP2 method, though work still needs to be done in creating a more consistent black-box approach to computing the determinants that comprise the many-electron NOCI basis.

Authors:
ORCiD logo [1];  [1]
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  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), 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:
1477253
Alternate Identifier(s):
OSTI ID: 1279020
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 5; Related Information: © 2016 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; Acenes; Multi-reference Perturbation Theory; Non-Orthogonal Configuration Interaction

Citation Formats

Yost, Shane R., and Head-Gordon, Martin. Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction. United States: N. p., 2016. Web. doi:10.1063/1.4959794.
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Yost, Shane R., & Head-Gordon, Martin. Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction. United States. https://doi.org/10.1063/1.4959794
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Yost, Shane R., and Head-Gordon, Martin. Mon . "Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction". United States. https://doi.org/10.1063/1.4959794. https://www.osti.gov/servlets/purl/1477253.
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@article{osti_1477253,
title = {Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction},
author = {Yost, Shane R. and Head-Gordon, Martin},
abstractNote = {In this study we introduce two size consistent forms of the non-orthogonal configuration interaction with second-order Møller-Plesset perturbation theory method, NOCI-MP2. We show that the original NOCI-MP2 formulation [S. R. Yost, T. Kowalczyk, and T. VanVoorh, J. Chem. Phys. 193, 174104 (2013)], which is a perturb-then-diagonalize multi-reference method, is not size consistent. We also show that this causes significant errors in large systems like the linear acenes. By contrast, the size consistent versions of the method give satisfactory results for singlet and triplet excited states when compared to other multi-reference methods that include dynamic correlation. For NOCI-MP2 however, the number of required determinants to yield similar levels of accuracy is significantly smaller. These results show the promise of the NOCI-MP2 method, though work still needs to be done in creating a more consistent black-box approach to computing the determinants that comprise the many-electron NOCI basis.},
doi = {10.1063/1.4959794},
journal = {Journal of Chemical Physics},
number = 5,
volume = 145,
place = {United States},
year = {Mon Aug 01 00:00:00 EDT 2016},
month = {Mon Aug 01 00:00:00 EDT 2016}
}
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