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Title: Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model

Abstract

We present a general perturbative method for correcting a singles and doubles coupled-cluster energy. The coupled-cluster wave function is used to define a similarity-transformed Hamiltonian, which is partitioned into a zeroth-order part that the reference problem solves exactly plus a first-order perturbation. Standard perturbation theory through second-order provides the leading correction. Applied to the valence optimized doubles (VOD) approximation to the full-valence complete active space self-consistent field method, the second-order correction, which we call (2), captures dynamical correlation effects through external single, double, and semi-internal triple and quadruple substitutions. A factorization approximation reduces the cost of the quadruple substitutions to only sixth order in the size of the molecule. A series of numerical tests are presented showing that VOD(2) is stable and well-behaved provided that the VOD reference is also stable. The second-order correction is also general to standard unwindowed coupled-cluster energies such as the coupled-cluster singles and doubles (CCSD) method itself, and the equations presented here fully define the corresponding CCSD(2) energy. (c) 2000 American Institute of Physics.

Authors:
 [1];  [1];  [1];  [2]
  1. Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720-1460 (United States)
  2. Department of Chemistry, University of Southern California, Los Angeles, California 90089 (United States)
Publication Date:
OSTI Identifier:
20217443
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 113; Journal Issue: 9; Other Information: PBD: 1 Sep 2000
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; VALENCE; ELECTRONIC STRUCTURE; PERTURBATION THEORY; SELF-CONSISTENT FIELD; MOLECULES; THEORETICAL DATA

Citation Formats

Gwaltney, Steven R., Sherrill, C. David, Head-Gordon, Martin, and Krylov, Anna I. Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model. United States: N. p., 2000. Web. doi:10.1063/1.1286597.
Gwaltney, Steven R., Sherrill, C. David, Head-Gordon, Martin, & Krylov, Anna I. Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model. United States. doi:10.1063/1.1286597.
Gwaltney, Steven R., Sherrill, C. David, Head-Gordon, Martin, and Krylov, Anna I. Fri . "Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model". United States. doi:10.1063/1.1286597.
@article{osti_20217443,
title = {Second-order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model},
author = {Gwaltney, Steven R. and Sherrill, C. David and Head-Gordon, Martin and Krylov, Anna I.},
abstractNote = {We present a general perturbative method for correcting a singles and doubles coupled-cluster energy. The coupled-cluster wave function is used to define a similarity-transformed Hamiltonian, which is partitioned into a zeroth-order part that the reference problem solves exactly plus a first-order perturbation. Standard perturbation theory through second-order provides the leading correction. Applied to the valence optimized doubles (VOD) approximation to the full-valence complete active space self-consistent field method, the second-order correction, which we call (2), captures dynamical correlation effects through external single, double, and semi-internal triple and quadruple substitutions. A factorization approximation reduces the cost of the quadruple substitutions to only sixth order in the size of the molecule. A series of numerical tests are presented showing that VOD(2) is stable and well-behaved provided that the VOD reference is also stable. The second-order correction is also general to standard unwindowed coupled-cluster energies such as the coupled-cluster singles and doubles (CCSD) method itself, and the equations presented here fully define the corresponding CCSD(2) energy. (c) 2000 American Institute of Physics.},
doi = {10.1063/1.1286597},
journal = {Journal of Chemical Physics},
number = 9,
volume = 113,
place = {United States},
year = {Fri Sep 01 00:00:00 EDT 2000},
month = {Fri Sep 01 00:00:00 EDT 2000}
}