Toward a W4-F12 approach: Can explicitly correlated and orbital-based ab initio CCSD(T) limits be reconciled?

TL;DR

This paper compares orbital-based and explicitly correlated CCSD(T) methods for high-accuracy thermochemistry, demonstrating that basis set flexibility and counterpoise corrections are crucial for reconciling their limits and improving computational efficiency.

Contribution

It shows that using flexible basis sets like ACV{5,6}Z and CCSD-F12b basis sets can reconcile differences between orbital-based and explicitly correlated CCSD(T) limits, enhancing accuracy and efficiency.

Findings

CCSD-F12b basis sets are close to the basis set limit.

Additional radial flexibility reduces differences between methods.

W4-F12 slightly outperforms W4 in agreement with ATcT data.

Abstract

In the context of high-accuracy computational thermochemistry, the valence CCSD correlation component of molecular atomization energies present the most severe basis set convergence problem, followed by the (T) component. In the present paper, we make a detailed comparison, for an expanded version of the W4-11 thermochemistry benchmark, between on the one hand orbital-based CCSD/AV{5,6}Z+d and CCSD/ACV{5,6}Z extrapolation, and on the other hand CCSD-F12b calculations with cc-pVQZ-F12 and cc-pV5Z-F12 basis sets. This latter basis set, now available for H--He, B--Ne, and Al--Ar, is shown to be very close to the basis set limit. Apparent differences (which can reach 0.35 kcal/mol for systems like CCl4) between orbital-based and CCSD-F12b basis set limits disappear if basis sets with additional radial flexibility, such as ACV{5,6}Z, are used for the orbital calculation. Counterpoise calculations reveal that, while TAEs with V5Z-F12 basis sets are nearly free of BSSE, orbital calculations have significant BSSE even with AV(6+d)Z basis sets, leading to non-negligible differences between raw and counterpoise-corrected extrapolated limits. This latter problem is greatly reduced by switching to ACV{5,6}Z core-valence basis sets, or simply adding an additional zeta to just the valence orbitals. Previous reports that all-electron approaches like HEAT lead to different CCSD(T) limits than valence limit+CV correction approaches like FPD and W4 theory can be rationalized in terms of the greater radial flexibility of core-valence basis sets. W4-F12 is found to agree slightly better than W4 with ATcT (active thermochemical tables) data, at a substantial saving in CPU time and especially I/O overhead. A W4-F12 calculation on benzene is presented as a proof of concept.