Does Basis Set Superposition Error Significantly Affect Post-CCSD(T) Corrections?

Vladimir Fishman, Emmanouil Semidalas, Margarita Shepelenko, Jan M.L. Martin

Research output: Contribution to journalArticlepeer-review

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 languageEnglish
Article numbere70006
JournalJournal of Computational Chemistry
Volume46
Issue number1
Early online date24 Dec 2024
DOIs
StatePublished - 5 Jan 2025

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Computational Mathematics

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