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基组叠加误差是否会显著影响后CCSD(T)校正?

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

作者信息

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

机构信息

Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, Rehovot, Israel.

出版信息

J Comput Chem. 2025 Jan 5;46(1):e70006. doi: 10.1002/jcc.70007.

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 or especially so. In contrast, for atomization energies, the 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 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).

摘要

我们针对W4 - 11全原子化能基准的一个子集以及A24x8非共价相互作用基准,对上述标题问题进行了研究。总体而言,后CCSD(T)贡献的平衡校正比CCSD(T)相互作用能的平衡校正重要性低约两个数量级。连接四重取代(Q)的平衡校正可忽略不计,或者说尤其如此。相比之下,对于原子化能,像cc - pVDZ这样的小基组,平衡校正可达约0.05 kcal/mol,但随着cc - pVTZ尤其是aug - cc - pVTZ基组的使用,它会迅速减小。在W4和HEAT热化学协议中应用的外推法会使其变得微不足道。在非共价二聚体中,即使在像非极化分裂价cc - pVDZ(no d)这样小的基组中,后CCSD(T)相关贡献上的微分基组叠加误差(BSSE)也可忽略不计。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e056/11668233/8d58dbf81639/JCC-46-0-g001.jpg

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