Towards the development and applications of manifestly spin-free multi-reference coupled electron-pair approximation-like methods: a state specific approach

Abstract

As a practical tool of being applicable to bigger molecules, a full-blown state-specific multi-reference coupled cluster formalism developed by us (Mahapatra et al. in J Chem Phys 110:6171, 1999) would be rather demanding computationally, and it is worthwhile to look for physically motivated approximation schemes which capture a substantial portion of the correlation of the full-blown theory. In this spirit, we have recently proposed coupled electron-pair approximation (CEPA)-like various approximants to the parent spin-adapted state-specific multi-reference coupled cluster (SS-MRCC) theory which depend on the inclusion of EPV terms to various degree. Here, the space of excitations is confined to the first order interactive virtual space generated by the cluster operator, but the EPV terms are included exactly. We call them spin-free state specific multi-reference CERA (SS-MRCEPA) theories. They work within the complete active space (CAS) and have been found to be very effective in bypassing the intruders, similar in performance to that of the parent SS-MRCC theory. The spin-adaptation of the working equations of both the SS-MRCC and the CEPA-like approximants is a non-trivial exercise. In this paper, we delineate briefly the essentials of a spin-free formulation of the SS-MRCC and SS-MRCEPA theories. This allows us to include open-shell configuration state functions (CSF) in the CAS. We consider three variants of SS-MRCEPA method. Two are explicitly orbital invariant: (1) SS-MRCEPA(0), a purely lineralized version of the SS-MRCC theory, (2) SS-MRCEPA(I), which includes all the EPV terms explicitly and exactly in an orbital invariant manner and (3) the SS-MRCEPA(D), which emerges when we keep only the diagonal terms of a set of dressed operators in the working equations. Unlike the first two, the third version is not invariant under the orbital transformation within the set of doubly occupied core, valence and virtual orbitals. The SS-MRCEPA methods produce very encouraging results as was evidenced in the applications on the computation of potential energy surfaces for the ground states of LiH and HF molecules.