Analysis of Different Sets of Spin-Adapted Substitution Operators in Open-Shell Coupled Cluster Theory

TL;DR

This paper investigates various sets of spin-adapted substitution operators in open-shell coupled cluster theory, analyzing their impact on wave function quality and correlation energy recovery, highlighting the importance of spin completeness.

Contribution

It introduces and compares different spin-adapted operator sets, demonstrating their effects on coupled cluster calculations and emphasizing the significance of spin completeness.

Findings

Fewer spectators generally improve accuracy.

Correlation energy differences up to 0.32%.

Spin-incomplete operators cause significant errors.

Abstract

In spin-adapted open-shell coupled cluster (CC) theory, the choice of spin-free spatial substitution operators is generally not unique. Due to an increasing linear dependence of the cluster operator (with increasing substitution level), the options to span identical linear spaces increase rapidly. In this work several sets of non-orthogonal as well as orthogonal spin-adapted substitution operators are generated and used in consecutive Configuration Interaction (CI) and CC calculations. All (full) operator sets were generated to span the same linear space. The results are analyzed in terms of the produced wave function quality and the amount of recovered correlation energy w.r.t. full CI. In particular, the influence of different amounts of spectators, the influence of orthogonality as well as the effect of spin incompleteness was investigated. It was found that CC calculations involving fewer spectators lead to more accurate results in general. Here correlation energy differences of up to 0.32\% for minimal to maximal spectating sets were obtained. As expected, all conducted calculations led to identical results for non-orthogonal and orthogonal operator sets. Spin completeness on the other hand was found to be of great importance. Spin-incomplete Cluster operators led to significant errors in both the correlation energies and the FCI overlap.