Matrix-covariant representation of high-order configuration interaction and coupled cluster theories

Abstract

We present the closed form of the reduced density matrices (RDMs) of arbitrary order for configuration interaction (CI) wave functions at any excitation level, up to the full CI. A special operator technique due to Bogoliubov is applied and extended. It focuses on constructions of matrix-covariant expressions independent of the basis set used. The corresponding variational CI equations are given in an explicit form containing the matrices related to conventional excitation operators. A subsequent transformation of the latter to an irreducible form makes it possible to generate the matrix-covariant representation for coupled cluster (CC) models. Here this transformation is performed for a simplified high-order CC scheme somewhat reminiscent of the quadratic CI model. A generalized spin-flip approximation closely related to high-order CI and CC models is presented, stressing on a possible inclusion of nondynamical and dynamical correlation effects for multiple bond breaking. A derivation of the full CI and simple CC models for systems involving effective three-electron interactions is also given, thereby demonstrating the capability of the proposed method to deal with complicated many-body problem. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008