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

IF 3.4 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Journal of Computational Chemistry Pub Date : 2024-12-24 DOI:10.1002/jcc.70007

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

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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 $T_{4} - (Q)$ especially so. In contrast, for atomization energies, the $T_{3} - (T)$ 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 $T_{3} - (T)$ 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).

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基集叠加误差显著影响后CCSD(T)校正吗？

我们研究了W4‐11总原子化能基准的一个子集和A24x8非共价相互作用基准的标题问题。总的来说，对后CCSD(T)贡献的平衡修正比CCSD(T)相互作用能的平衡修正要小两个数量级。连接的四重替换(Q)的平衡修正是可以忽略不计的，或者特别如此。相比之下，对于像cc - pVDZ这样的小基组，平衡校正可以达到0.05 kcal/mol左右，但随着cc - pVTZ，特别是aug - cc - pVTZ基组的减小，平衡校正会迅速减小。通过在W4和HEAT热化学协议中应用的外推，它减少到无关紧要。在非共价二聚体中，即使在像未极化分裂价cc - pVDZ（no d）这样小的基集中，CCSD(T)相关贡献的微分BSSE也可以忽略不计。

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来源期刊

Journal of Computational Chemistry 化学-化学综合

CiteScore

6.60

自引率

3.30%

发文量

247

审稿时长

1.7 months

期刊介绍： This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.