Valence bond corrected single reference coupled cluster approach

Abstract

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.