The cc-pV5Z-F12 basis set: reaching the basis set limit in explicitly correlated calculations

TL;DR

The paper introduces the cc-pV5Z-F12 basis set, which enables highly accurate explicitly correlated calculations approaching the basis set limit without extrapolation, significantly improving thermochemical and noncovalent interaction computations.

Contribution

A new extended basis set, cc-pV5Z-F12, is developed and benchmarked, achieving near basis set limit accuracy in explicitly correlated calculations.

Findings

cc-pV5Z-F12 yields CCSD component accuracy comparable to high-level extrapolations.

SCF components reach the basis set limit with this basis set.

Basis set superposition error is negligible for most noncovalent interaction calculations.

Abstract

We have developed and benchmarked a new extended basis set for explicitly correlated calculations, namely cc-pV5Z-F12. It is offered in two variants, cc-pV5Z-F12 and cc- pV5Z-F12(rev2), the latter of which has additional basis functions on hydrogen not present in the cc-pVnZ-F12 (n=D,T,Q) sequence.A large uncontracted 'reference' basis set is used for benchmarking. cc-pVnZ-F12 (n=D, T, Q, 5) is shown to be a convergent hierarchy. Especially the cc- pV5Z-F12(rev2) basis set can yield the valence CCSD component of total atomization energies (TAEs), without any extrapolation, to an accuracy normally associated with aug-cc-pV{5,6}Z extrapolations. SCF components are functionally at the basis set limit, while the MP2 limit can be approached to as little as 0.01 kcal/mol without extrapolation. The determination of (T) appears to be the most difficult of the three components and cannot presently be accomplished without extrapolation or scaling. (T) extrapolation from cc-pV{T,Q}Z-F12 basis sets, combined with CCSD-F12b/cc-pV5Z-F12 calculations appears to be an accurate combination for explicitly correlated thermochemistry. For accurate work on noncovalent interactions, basis set superposition error with the cc-pV5Z-F12 basis set is shown to be so small that counterpoise corrections can be neglected for all but the most exacting purposes.