A companion perturbation theory for state-specific multireference coupled cluster methods

Abstract

A partitioning scheme is applied to the state-specific Mukherjee multireference coupled cluster method to derive a companion perturbation theory (Mk-MRPT2). A production-level implementation of Mk-MRPT2 is reported. The effectiveness of the Mk-MRPT2 method is demonstrated by application to the classic F₂ dissociation problem and the lowest-lying electronic states of meta-benzyne, including computations with up to 766 atomic orbitals. We show that Mk-MRPT2 theory is particularly useful in multireference focal point extrapolations to determine ab initio limits.