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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 paper 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:
;  [1];  [2]
  1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)
  2. (United States)
Publication Date:
OSTI Identifier:
22679018
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 145; Journal Issue: 5; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CONFIGURATION INTERACTION; DISTURBANCES; EXCITED STATES; EXPERIMENTAL DATA; PERTURBATION THEORY

Citation Formats

Yost, Shane R., Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. 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.
Yost, Shane R., Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu, & Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction. United States. doi:10.1063/1.4959794.
Yost, Shane R., Head-Gordon, Martin, E-mail: mhg@cchem.berkeley.edu, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Sun . "Size consistent formulations of the perturb-then-diagonalize Møller-Plesset perturbation theory correction to non-orthogonal configuration interaction". United States. doi:10.1063/1.4959794.
@article{osti_22679018,
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, E-mail: mhg@cchem.berkeley.edu and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720},
abstractNote = {In this paper 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 = {Sun Aug 07 00:00:00 EDT 2016},
month = {Sun Aug 07 00:00:00 EDT 2016}
}