Approximate treatment of higher excitations in coupled-cluster theory

M. Kállay, Jürgen Gauss

Research output: Contribution to journalArticle

220 Citations (Scopus)

Abstract

The possibilities for the approximate treatment of higher excitations in coupled-cluster (CC) theory are discussed. Potential routes for the generalization of corresponding approximations to lower-level CC methods are analyzed for higher excitations. A general string-based algorithm is presented for the evaluation of the special contractions appearing in the equations specific to those approximate CC models. It is demonstrated that several iterative and noniterative approximations to higher excitations can be efficiently implemented with the aid of our algorithm and that the coding effort is mostly reduced to the generation of the corresponding formulas. The performance of the proposed and implemented methods for total energies is assessed with special regard to quadruple and pentuple excitations. The applicability of our approach is illustrated by benchmark calculations for the butadiene molecule. Our results demonstrate that the proposed algorithm enables us to consider the effect of quadruple excitations for molecular systems consisting of up to 10-12 atoms.

Original languageEnglish
Article number214105
JournalThe Journal of Chemical Physics
Volume123
Issue number21
DOIs
Publication statusPublished - 2005

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excitation
Atoms
butadiene
Molecules
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contraction
coding
strings
routes
evaluation
atoms
molecules
energy
1,3-butadiene

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Approximate treatment of higher excitations in coupled-cluster theory. / Kállay, M.; Gauss, Jürgen.

In: The Journal of Chemical Physics, Vol. 123, No. 21, 214105, 2005.

Research output: Contribution to journalArticle

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