Does basis set superposition error significantly affect post-CCSD(T) corrections?
Abstract
We have investigated the title question for both a subset of the W4-11 total atomization energies benchmark, and for the A24x8 noncovalent interactions benchmark. Overall, counterpoise corrections to post-CCSD(T) contributions are about two orders of magnitude less important than those to the CCSD(T) interaction energy. Counterpoise corrections for connected quadruple substitutions (Q) are negligible, and or especially so. In contrast, for atomization energies, the counterpoise correction can reach about 0.05 \kcalmol~for small basis sets like cc-pVDZ, thought it rapidly tapers off with cc-pVTZ and especially aug-cc-pVTZ basis sets. It is reduced to insignificance by the extrapolation of applied in both W4 and HEAT thermochemistry protocols. In noncovalent dimers, the differential BSSE on post-CCSD(T) correlation contributions is negligible even in basis sets as small as the unpolarized split-valence cc-pVDZ(no d).
Cite
@article{arxiv.2408.10034,
title = {Does basis set superposition error significantly affect post-CCSD(T) corrections?},
author = {Vladimir Fishman and Emmanouil Semidalas and Margarita Shepelenko and Jan M. L. Martin},
journal= {arXiv preprint arXiv:2408.10034},
year = {2025}
}
Comments
Final published article under CC:BY license (Hans Lischka festschrift)