Secondorder perturbation corrections to singles and doubles coupledcluster methods: General theory and application to the valence optimized doubles model
Abstract
We present a general perturbative method for correcting a singles and doubles coupledcluster energy. The coupledcluster wave function is used to define a similaritytransformed Hamiltonian, which is partitioned into a zerothorder part that the reference problem solves exactly plus a firstorder perturbation. Standard perturbation theory through secondorder provides the leading correction. Applied to the valence optimized doubles (VOD) approximation to the fullvalence complete active space selfconsistent field method, the secondorder correction, which we call (2), captures dynamical correlation effects through external single, double, and semiinternal 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 wellbehaved provided that the VOD reference is also stable. The secondorder correction is also general to standard unwindowed coupledcluster energies such as the coupledcluster 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:

 Department of Chemistry, University of California, and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 947201460 (United States)
 Department of Chemistry, University of Southern California, Los Angeles, California 90089 (United States)
 Publication Date:
 OSTI Identifier:
 20217443
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 113; Journal Issue: 9; Other Information: PBD: 1 Sep 2000; Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 74 ATOMIC AND MOLECULAR PHYSICS; VALENCE; ELECTRONIC STRUCTURE; PERTURBATION THEORY; SELFCONSISTENT FIELD; MOLECULES; THEORETICAL DATA
Citation Formats
Gwaltney, Steven R, Sherrill, C David, HeadGordon, Martin, and Krylov, Anna I. Secondorder perturbation corrections to singles and doubles coupledcluster 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, HeadGordon, Martin, & Krylov, Anna I. Secondorder perturbation corrections to singles and doubles coupledcluster methods: General theory and application to the valence optimized doubles model. United States. doi:10.1063/1.1286597.
Gwaltney, Steven R, Sherrill, C David, HeadGordon, Martin, and Krylov, Anna I. Fri .
"Secondorder perturbation corrections to singles and doubles coupledcluster methods: General theory and application to the valence optimized doubles model". United States. doi:10.1063/1.1286597.
@article{osti_20217443,
title = {Secondorder perturbation corrections to singles and doubles coupledcluster methods: General theory and application to the valence optimized doubles model},
author = {Gwaltney, Steven R and Sherrill, C David and HeadGordon, Martin and Krylov, Anna I},
abstractNote = {We present a general perturbative method for correcting a singles and doubles coupledcluster energy. The coupledcluster wave function is used to define a similaritytransformed Hamiltonian, which is partitioned into a zerothorder part that the reference problem solves exactly plus a firstorder perturbation. Standard perturbation theory through secondorder provides the leading correction. Applied to the valence optimized doubles (VOD) approximation to the fullvalence complete active space selfconsistent field method, the secondorder correction, which we call (2), captures dynamical correlation effects through external single, double, and semiinternal 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 wellbehaved provided that the VOD reference is also stable. The secondorder correction is also general to standard unwindowed coupledcluster energies such as the coupledcluster 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},
issn = {00219606},
number = 9,
volume = 113,
place = {United States},
year = {2000},
month = {9}
}