TY - JOUR
T1 - Does Basis Set Superposition Error Significantly Affect Post-CCSD(T) Corrections?
AU - Fishman, Vladimir
AU - Semidalas, Emmanouil
AU - Shepelenko, Margarita
AU - Martin, Jan M.L.
N1 - Publisher Copyright: © 2024 The Author(s). Journal of Computational Chemistry published by Wiley Periodicals LLC.
PY - 2025/1/5
Y1 - 2025/1/5
N2 - 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).
AB - 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).
UR - http://www.scopus.com/inward/record.url?scp=85212842636&partnerID=8YFLogxK
U2 - https://doi.org/10.1002/jcc.70007
DO - https://doi.org/10.1002/jcc.70007
M3 - مقالة
SN - 0192-8651
VL - 46
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
IS - 1
M1 - e70006
ER -