Seniority-based coupled cluster theory

Thomas M. Henderson, Ireneusz W. Bulik, Tamar Stein, Gustavo E. Scuseria

Research output: Contribution to journalArticlepeer-review

101 Scopus citations

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 (N3, 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.

Original languageAmerican English
Article number244104
JournalJournal of Chemical Physics
Volume141
Issue number24
DOIs
StatePublished - 28 Dec 2014
Externally publishedYes

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