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 the excitation manifolds defining higher-than-two-body components of the cluster operator inspired by the 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.