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Theoretica chimica acta

, Volume 89, Issue 1, pp 13–31 | Cite as

Valence bond corrected single reference coupled cluster approach

I. General formalism
  • J. Paldus
  • J. Planelles
Article

Summary

An extension of the single reference coupled cluster method truncated to 1- and 2-body cluster components (CCSD) to quasidegenerate systems, where 3-and 4-body connected cluster components play an important role, is proposed. The basic idea is to extract the information concerning the 3- and 4-body clusters from some independent source, similarly as was implicitly done in the so-called ACPQ or ACC(S)D methods, and correct accordingly the absolute term in the CCSD equations. As a source of these approximate 3- and 4-body clusters, simple valence bond (VB) type wave functions are employed, since they are capable of describing electronic structure of various molecular systems for a wide range of nuclear conformations including their dissociation. The cluster analysis of these VB wave functions, that provides the desired information concerning the connected 3- and 4-body cluster components, is outlined and the explicit form of required correction terms to the CCSD equations is given.

Key words

Coupled cluster method CCSD Quasidegeneracy effects Valence bond (VB) wave functions VB corrected CCSD method 3- and 4-body connected cluster amplitudes 

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Copyright information

© Springer-Verlag 1994

Authors and Affiliations

  • J. Paldus
    • 1
    • 2
  • J. Planelles
    • 1
  1. 1.Department of Applied MathematicsUniversity of WaterlooWaterlooCanada
  2. 2.the Department of Chemistry and Guelph-Waterloo Center for Graduate Work in Chemistry, Waterloo CampusUniversity of WaterlooWaterlooCanada

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