Does basis set superposition error significantly affect post-CCSD(T) corrections?
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arXiv
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| Format: | Preprint |
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2024
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| _version_ | 1866917883780530176 |
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| author | Fishman, Vladimir Semidalas, Emmanouil Shepelenko, Margarita Martin, Jan M. L. |
| author_facet | Fishman, Vladimir Semidalas, Emmanouil Shepelenko, Margarita Martin, Jan M. L. |
| contents | 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 $(Q)_Λ- (Q)$ or $T_4 - (Q)$ especially so. In contrast, for atomization energies, the $T_3-(T)$ 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 $T_3-(T)$ 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). |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2408_10034 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Does basis set superposition error significantly affect post-CCSD(T) corrections? Fishman, Vladimir Semidalas, Emmanouil Shepelenko, Margarita Martin, Jan M. L. Chemical Physics 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 $(Q)_Λ- (Q)$ or $T_4 - (Q)$ especially so. In contrast, for atomization energies, the $T_3-(T)$ 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 $T_3-(T)$ 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). |
| title | Does basis set superposition error significantly affect post-CCSD(T) corrections? |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2408.10034 |