Coupled Cluster Externally Corrected by Adaptive Configuration Interaction

TL;DR

The paper introduces ACI-CC, an externally corrected coupled cluster method using adaptive configuration interaction wave functions to incorporate higher-order effects without increasing computational cost.

Contribution

It presents a novel ACI-CC method that integrates adaptive configuration interaction with coupled cluster, improving accuracy for strongly correlated systems.

Findings

ACI-CC outperforms traditional CCSD in benchmark tests.

Inclusion of external corrections improves upon CCSD(T) results.

Method remains computationally efficient by freezing higher-order terms.

Abstract

An externally corrected coupled cluster (CC) method, where an adaptive configuration interaction (ACI) wave function provides the external cluster amplitudes, named ACI-CC, is presented. By exploiting the connection between configuration interaction and coupled cluster through cluster analysis, the higher-order T3 and T4 terms obtained from ACI are used to augment the T1 and T2 amplitude equations from traditional coupled cluster. These higher-order contributions are kept frozen during the coupled cluster iterations and do not contribute to an increased cost with respect to CCSD. We have benchmarked this method on three closed-shell systems: beryllium dimer, carbonyl oxide, and cyclobutadiene, with good results compared to other corrected coupled cluster methods. In all cases, the inclusion of these external corrections improved upon the "gold standard" CCSD(T) results, indicating that ACI-CCSD(T) can be used to assess strong correlation effects in a system and as an inexpensive starting point for more complex external corrections.