Improving Aufbau Suppressed Coupled Cluster Through Perturbative Analysis

Abstract

Guided by perturbative analysis, we improve the accuracy of Aufbau suppressed coupled cluster theory in simple single excitations, multi-configurational single excitations, and charge transfer excitations while keeping the cost of its leading-order terms precisely in line with ground state coupled cluster. Combining these accuracy improvements with a more efficient implementation based on spin-adaptation, we observe high accuracy in a large test set of single excitations, and, in particular, a mean unsigned error for charge transfer states that outperforms equation-of-motion coupled cluster theory by 0.25 eV. We discuss how these results are achieved via a systematic identification of which amplitudes to prioritize for single- and multi-configurational excited states, and how this prioritization differs in important ways from the ground state theory. In particular, our data show that a partial linearization of the theory increases accuracy by mitigating unwanted side effects of Aufbau suppression.