Converging high-level coupled-cluster energetics via adaptive selection of excitation manifolds driven by moment expansions.

Abstract

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of excitation manifolds defining higher--than--two-body components of the cluster operator inspired by CC(P;Q) moment expansions. The usefulness of the resulting methodology is illustrated by molecular examples where the goal is to recover the electronic energies obtained using the CC method with a full treatment of singly, doubly, and triply excited clusters (CCSDT) when the noniterative triples corrections to CCSD fail.