School of Chemistry, The University of Melbourne, Parkville, Australia.
J Comput Chem. 2020 Nov 15;41(30):2562-2572. doi: 10.1002/jcc.26411. Epub 2020 Sep 1.
Previously, we introduced DFT-D3(BJ)ωB97X-V and ωB97M-V functionals and assessed them for the GMTKN55 database [Najibi and Goerigk, J Chem. Theory Comput. 2018, 14, 5725]. In this study, we present DFT-D4 damping parameters to build the DFT-D4 counterparts of these functionals and assess these in comparison. We extend our analysis beyond GMTKN55 and especially turn our attention to enzymatically catalyzed and metal-organic reactions. We find that B97M-D4 is now the second-best performing meta-generalized-gradient approximation functional for the GMTKN55 database and it can provide noticeably better organometallic reaction energies compared to B97M-D3(BJ). Moreover, the aforementioned DFT-D3(BJ)-based functionals have not been thoroughly assessed for geometries and herein we close this gap by analyzing geometries of noncovalently bound dimers and trimers, peptide conformers, water hexamers and transition-metal complexes. We find that several of the B97(M)-based methods-particularly the DFT-D4 versions-surpass the accuracy of previously studied methods for peptide conformer, water hexamer, and transition-metal complex geometries, making them safe-to-use, cost-efficient alternatives to the original methods. The DFT-D4 variants can be easily used with ORCA4.1 and above.
此前，我们介绍了 DFT-D3(BJ)ωB97X-V 和 ωB97M-V 函数，并对它们在 GMTKN55 数据库中的性能进行了评估[Najibi 和 Goerigk，J Chem. Theory Comput. 2018, 14, 5725]。在这项研究中，我们提出了 DFT-D4 阻尼参数，以构建这些函数的 DFT-D4 对应物，并对它们进行了比较评估。我们的分析不仅限于 GMTKN55 数据库，尤其关注了酶催化和金属有机反应。我们发现，B97M-D4 现在是 GMTKN55 数据库中性能第二好的泛函，与 B97M-D3(BJ)相比，它可以提供明显更好的金属有机反应能。此外，上述基于 DFT-D3(BJ)的泛函还没有对几何形状进行全面评估，在这里，我们通过分析非共价键结合的二聚体和三聚体、肽构象、水六聚体和过渡金属配合物的几何形状来弥补这一空白。我们发现，几种 B97(M)-基方法——特别是 DFT-D4 版本——在肽构象、水六聚体和过渡金属配合物的几何形状方面超过了之前研究方法的准确性，因此它们是原始方法的安全、经济有效的替代方法。DFT-D4 变体可以很容易地与 ORCA4.1 及以上版本一起使用。
