Assessment of the accuracy of coupled cluster perturbation theory for open-shell systems. II. Quadruples expansions

TL;DR

This study evaluates the accuracy of various perturbative coupled cluster models for open-shell systems, highlighting the superior balanced performance of the CCSDT(Q-n) series in recovering energies and atomization data.

Contribution

It introduces and compares higher-order CCSDT(Q-n) models for open-shell systems, demonstrating their improved accuracy and reference-independence over existing models.

Findings

CCSDT(Q-n) models are reference-independent for open-shell systems.

CCSDT(Q-3) offers a cost-effective alternative with high accuracy.

Balanced treatment of closed- and open-shell species is crucial for reliable predictions.

Abstract

We extend our assessment of the potential of perturbative coupled cluster (CC) expansions for a test set of open-shell atoms and organic radicals to the description of quadruple excitations. Namely, the second- through sixth-order models of the recently proposed CCSDT(Q-n) quadruples series [J. Chem. Phys. 140, 064108 (2014)] are compared to the prominent CCSDT(Q) and lambda-CCSDT(Q) models. From a comparison of the models in terms of their recovery of total CC singles, doubles, triples, and quadruples (CCSDTQ) energies, we find that the performance of the CCSDT(Q-n) models is independent of the reference used (unrestricted or restricted (open-shell) Hartree-Fock), in contrast to the CCSDT(Q) and lambda-CCSDT(Q) models, for which the accuracy is strongly dependent on the spin of the molecular ground state. By further comparing the ability of the models to recover relative CCSDTQ atomization energies, the discrepancy between them is found to be even more pronounced, stressing how a balanced description of both closed- and open-shell species - as found in the CCSDT(Q-n) models - is indeed of paramount importance if any perturbative CC model is to be of chemical relevance for high-accuracy applications. In particular, the third-order CCSDT(Q-3) model is found to offer an encouraging alternative to the existing choices of quadruples models used in modern computational thermochemistry, since the model is still only of moderate cost, albeit markedly more costly than, e.g., the CCSDT(Q) and lambda-CCSDT(Q) models.