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

基组重叠误差是否会对 CCSD(T) 后的校正产生显著影响?

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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 (Q)Λ - (Q) or T4 - (Q) especially so. In contrast, for atomization energies, the T3 - (T) 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 T3 - (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).

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