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

Molecular Physics, in press (Nicholas C. Handy memorial issue). DOI preassigned

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Cited by in corpus (13)

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• The S66 noncovalent interactions benchmark reconsidered using explicitly correlated methods near the basis set limit
• Explicitly correlated double hybrid DFT: a comprehensive analysis of the basis set convergence on the GMTKN55 database
• Performance of Localized-Orbital Coupled Cluster Approaches for the Conformational Energies of Longer n-alkane Chains
• Reduced-scaling double hybrid DFT with rapid basis set convergence through localized pair natural orbital F12
• Basis set extrapolation from the vanishing counterpoise correction condition
• Automatic generation of complementary auxiliary basis sets (CABS) for explicitly correlated methods
• Can G4-like Composite Ab Initio Methods Accurately Predict Vibrational Harmonic Frequencies?
• MP2-F12 Basis Set Convergence for the S66 Noncovalent Interactions Benchmark: Transferability of the Complementary Auxiliary Basis Set (CABS)
• MP2-F12 basis set convergence near the complete basis set limit: are $h$ functions sufficient?
• Is explicitly correlated double hybrid DFT advantageous for vibrational frequencies?
• Slimmer Geminals For Accurate F12 Electronic Structure Models
• Basis set convergence and extrapolation of connected triple excitation contributions (T) in computational thermochemistry: the W4-17 benchmark with up to k functions