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 (Formula presented.) or (Formula presented.) especially so. In contrast, for atomization energies, the (Formula presented.) counterpoise correction can reach about 0.05 kcal/mol 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 (Formula presented.) 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).
| Original language | English |
|---|---|
| Article number | e70006 |
| Number of pages | 8 |
| Journal | Journal of Computational Chemistry |
| Volume | 46 |
| Issue number | 1 |
| Early online date | 24 Dec 2024 |
| DOIs | |
| State | Published - 5 Jan 2025 |
All Science Journal Classification (ASJC) codes
- General Chemistry
- Computational Mathematics
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