Santra Golokesh, Cho Minsik, Martin Jan M L
Department of Organic Chemistry, Weizmann Institute of Science, 7610001 Reḥovot, Israel.
Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
J Phys Chem A. 2021 Jun 3;125(21):4614-4627. doi: 10.1021/acs.jpca.1c01294. Epub 2021 May 19.
We have explored the use of range separation as a possible avenue for further improvement on our revDSD minimally empirical double hybrid functionals. Such ωDSD functionals encompass the XYG3 type of double hybrid (, DSD) as a special case for ω → 0. As in our previous studies, the large and chemically diverse GMTKN55 benchmark suite was used for evaluation. Especially when using the D4 rather than D3BJ dispersion model, DSD has a slight performance advantage in WTMAD2. As in previous studies, PBEP86 is the winning combination for the semilocal parts. DSD-PBEP86-D4 marginally outperforms the previous "best in class" ωB97M(2) Berkeley double hybrid but without range separation and using fewer than half the number of empirical parameters. Range separation turns out to offer only marginal further improvements on GMTKN55 itself. While ωB97M(2) still yields better performance for small-molecule thermochemistry, this is compensated in WTMAD2 by the superior performance of the new functionals for conformer equilibria. Results for two external test sets with pronounced static correlation effects may indicate that range-separated double hybrids are more resilient to such effects.
我们探索了使用范围分离作为进一步改进我们的revDSD最小经验双杂化泛函的可能途径。这种ωDSD泛函将XYG3类型的双杂化（即DSD）作为ω→0时的特殊情况包含在内。与我们之前的研究一样，使用了庞大且化学多样性丰富的GMTKN55基准套件进行评估。特别是在使用D4而非D3BJ色散模型时，DSD在WTMAD2中具有轻微的性能优势。与之前的研究一样，PBEP86是半局域部分的最佳组合。DSD-PBEP86-D4略微优于之前“同类最佳”的ωB97M(2)伯克利双杂化，但没有范围分离且使用的经验参数数量不到其一半。结果表明，范围分离对GMTKN55本身仅提供了边际上的进一步改进。虽然ωB97M(2)在小分子热化学方面仍具有更好的性能，但在WTMAD2中，新泛函在构象异构体平衡方面的卓越性能对此进行了弥补。具有明显静态相关效应的两个外部测试集的结果可能表明，范围分离的双杂化对这种效应更具弹性。
