Non-iterative coupled-cluster methods employing multi-reference perturbation theory wave functions

Abstract

A new class of non-iterative coupled-cluster (CC) methods, which improve the results of standard CC and equation-of-motion (EOM) CC calculations for ground and excited-state potential energy surfaces along bond breaking coordinates and for excited states dominated by two-electron transitions, is explored. The proposed approaches combine the method of moments of coupled-cluster equations (MMCC), in which the a posteriori corrections due to higher-order correlations are added to standard CC/EOMCC energies, with the multi-reference many-body perturbation theory (MRMBPT), which provides information about the most essential non-dynamic and dynamic correlation effects that are relevant to electronic quasi-degeneracies. The performance of the basic MRMBPT-corrected MMCC approximation, in which inexpensive non-iterative corrections due to triple excitations are added to ground- and excited-state energies obtained with the CC/EOMCC singles and doubles approach, is illustrated by the results of a few test calculations, including bond breaking in HF and H 2O, and excited states of CH +.