Coupled-cluster method for multideterminantal reference states

Abstract

A general coupled-cluster method valid for arbitrary multideterminantal reference states is formulated. The resulting cluster expansion for the wave function is a generalization of that introduced by Silverstone and Sinanoǧlu and applied by Sinanoǧlu and collaborators. The connected nature of the cluster operators and the effective interaction is proven in the case when the reference space is complete, i.e., is invariant under unitary transformations of partly occupied orbitals. For incomplete reference spaces the disconnected terms appearing in the effective interaction are properly generated by the coupled-cluster theory. Approximate schemes for solving coupled-cluster equations are proposed and their relation with perturbation theory is briefly discussed.