Post-complete-basis-set extrapolation of conventional and explicitly correlated coupled-cluster energies: can the convergence to the CBS limit be diagnosed?

• Published in: Physical chemistry chemical physics : PCCP 2021-04, Vol.23 (14), p.8717-873
• Main Author: Varandas, A. J. C
• Format: Article
• Language: English
• Subjects: Convergence; Correlation; Deviation; Diagnostic systems; Extrapolation
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d1cp00538c

We assess benchmark correlation energies for 130 systems in test sets A24 and TS-106 both with the canonical CCSD(T) and explicitly correlated CCSD(T)-F12 methods. Aiming at enhanced accuracy, the calculated raw energies from both sets are CBS extrapolated to the complete basis set (CBS) limit and subsequently post-CBS extrapolated. Attention is focused at total energies, since their accuracy reflects on that of the interaction energies. Using up to triple- ζ basis sets for CBS and an additional quadruple- ζ for post-CBS, the mean and standard unsigned deviations with canonical CCSD(T) theory are 0.257 ± 0.25 kcal mol −1 , while the corresponding values for CCSD(T)-F12 in its F12a and F12b variants with specialized basis sets up to V Q Z-F12 are 0.170 ± 0.13 kcal mol −1 and 0.048 ± 0.04 kcal mol −1 . Although these show gains at post-CBS level that vary from 0.08 to 0.20 kcal mol −1 relative to their CCSD(T)/V X Z analogues, the convergence is somewhat less clear when extending the basis up to V5Z-F12, the highest-rung available: 0.220 ± 0.17 kcal mol −1 and 0.142 ± 0.08 kcal mol −1 , in the same order. An explanation for the up to one order of magnitude smaller deviations in energy differences is detailed. Based on energy differences involving basis set pairs employed for extrapolating to the CBS limit, a convergence diagnostic is also suggested. Arising from irregularities in the basis set that directly correlate with non-dynamical correlation, the new diagnostic may complement popular ones that feature other aspects of correlation. We assess benchmark correlation energies for 130 systems in test sets A24 and TS-106 both with the canonical CCSD(T) and explicitly correlated CCSD(T)-F12 methods.