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Title: Seniority-based coupled cluster theory

Abstract

Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling of such calculations remains combinatorial with system size. Pair coupled cluster doubles (pCCD) is very successful in reproducing DOCI energetically, but can do so with low polynomial scaling (N{sup 3}, disregarding the two-electron integral transformation from atomic to molecular orbitals). We show here several examples illustrating the success of pCCD in reproducing both the DOCI energy and wave function and show how this success frequently comes about. What DOCI and pCCD lack are an effective treatment of dynamic correlations, which we here add by including higher-seniority cluster amplitudes which are excluded from pCCD. This frozen pair coupled cluster approach is comparable in cost to traditional closed-shell coupled cluster methods with results that are competitive for weakly correlated systems and often superior for the description of strongly correlated systems.

Authors:
;  [1]; ;  [1]
  1. Department of Chemistry, Rice University, Houston, Texas 77005-1892 (United States)
Publication Date:
OSTI Identifier:
22415403
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 24; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; AMPLITUDES; COMPARATIVE EVALUATIONS; CONFIGURATION INTERACTION; CORRELATIONS; COUPLING; ELECTRONS; HILBERT SPACE; INTEGRAL TRANSFORMATIONS; POLYNOMIALS

Citation Formats

Henderson, Thomas M., Scuseria, Gustavo E., Department of Physics and Astronomy, Rice University, Houston, Texas 77005-1892, Bulik, Ireneusz W., and Stein, Tamar. Seniority-based coupled cluster theory. United States: N. p., 2014. Web. doi:10.1063/1.4904384.
Henderson, Thomas M., Scuseria, Gustavo E., Department of Physics and Astronomy, Rice University, Houston, Texas 77005-1892, Bulik, Ireneusz W., & Stein, Tamar. Seniority-based coupled cluster theory. United States. doi:10.1063/1.4904384.
Henderson, Thomas M., Scuseria, Gustavo E., Department of Physics and Astronomy, Rice University, Houston, Texas 77005-1892, Bulik, Ireneusz W., and Stein, Tamar. Sun . "Seniority-based coupled cluster theory". United States. doi:10.1063/1.4904384.
@article{osti_22415403,
title = {Seniority-based coupled cluster theory},
author = {Henderson, Thomas M. and Scuseria, Gustavo E. and Department of Physics and Astronomy, Rice University, Houston, Texas 77005-1892 and Bulik, Ireneusz W. and Stein, Tamar},
abstractNote = {Doubly occupied configuration interaction (DOCI) with optimized orbitals often accurately describes strong correlations while working in a Hilbert space much smaller than that needed for full configuration interaction. However, the scaling of such calculations remains combinatorial with system size. Pair coupled cluster doubles (pCCD) is very successful in reproducing DOCI energetically, but can do so with low polynomial scaling (N{sup 3}, disregarding the two-electron integral transformation from atomic to molecular orbitals). We show here several examples illustrating the success of pCCD in reproducing both the DOCI energy and wave function and show how this success frequently comes about. What DOCI and pCCD lack are an effective treatment of dynamic correlations, which we here add by including higher-seniority cluster amplitudes which are excluded from pCCD. This frozen pair coupled cluster approach is comparable in cost to traditional closed-shell coupled cluster methods with results that are competitive for weakly correlated systems and often superior for the description of strongly correlated systems.},
doi = {10.1063/1.4904384},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 24,
volume = 141,
place = {United States},
year = {2014},
month = {12}
}