A method of incorporating quadruple correction in the scheme of multi-reference singly and doubly excited configuration interaction ? a CSF based coupled pair approximation

Abstract

We develop an approximate size consistent method within a framework of the multi-reference configuration interaction scheme. The Rayleigh-Schrodinger perturbation theory is employed with a specific selection of the unperturbed part of the electronic Hamiltonian. The second order energy is obtained by a set of equations similar to the quasidegenerate variational perturbation theory of Cave and Davidson. The approximate fourth order energy is obtained by solving a set of equations similar to the coupled electron pair approximation (CEPA). The method has been tested for two simple systems, BeH2 and N2, and the results are quite encouraging.