Theoretische Organische Chemie, Organisch-Chemisches Institut der Universität Münster, Corrensstraβe 40, and NRW Graduate School of Chemistry, Wilhelm-Klemm-Straβe 10, D-48149 Münster, Germany.
J Chem Theory Comput. 2011 Feb 8;7(2):291-309. doi: 10.1021/ct100466k. Epub 2010 Dec 23.
We present an extended and improved version of our recently published database for general main group thermochemistry, kinetics, and noncovalent interactions [J. Chem. Theory Comput. 2010, 6, 107], which is dubbed GMTKN30. Furthermore, we suggest and investigate two new double-hybrid-meta-GGA density functionals called PTPSS-D3 and PWPB95-D3. PTPSS-D3 is based on reparameterized TPSS exchange and correlation contributions; PWPB95-D3 contains reparameterized PW exchange and B95 parts. Both functionals contain fixed amounts of 50% Fock-exchange. Furthermore, they include a spin-opposite scaled perturbative contribution and are combined with our latest atom-pairwise London-dispersion correction [J. Chem. Phys. 2010, 132, 154104]. When evaluated with the help of the Laplace transformation algorithm, both methods scale as N(4) with system size. The functionals are compared with the double hybrids B2PLYP-D3, B2GPPLYP-D3, DSD-BLYP-D3, and XYG3 for GMTKN30 with a quadruple-ζ basis set. PWPB95-D3 and DSD-BLYP-D3 are the best functionals in our study and turned out to be more robust than B2PLYP-D3 and XYG3. Furthermore, PWPB95-D3 is the least basis set dependent and the best functional at the triple-ζ level. For the example of transition metal carbonyls, it is shown that, mainly due to the lower amount of Fock-exchange, PWPB95-D3 and PTPSS-D3 are better applicable than the other double hybrids. Finally, we discuss in some detail the XYG3 functional [Proc. Nat. Acad. Sci. U.S.A. 2009, 106, 4963], which makes use of B3LYP orbitals and electron densities. We show that it is basically a highly nonlocal variant of B2PLYP and that its partially good performance is mainly due to a larger effective amount of perturbative correlation compared to other double hybrids. We finally recommend the PWPB95-D3 functional in general chemistry applications.
我们提出了最近发表的通用主族热化学、动力学和非共价相互作用数据库的扩展和改进版本[J. Chem. Theory Comput. 2010, 6, 107]，称为 GMTKN30。此外，我们建议并研究了两种新的双杂交-混合泛函，分别称为 PTPSS-D3 和 PWPB95-D3。PTPSS-D3 基于重新参数化的 TPSS 交换和相关贡献；PWPB95-D3 包含重新参数化的 PW 交换和 B95 部分。这两种泛函都包含固定的 50% Fock 交换量。此外，它们包含自旋相反的缩放微扰贡献，并与我们最新的原子对伦敦分散修正[J. Chem. Phys. 2010, 132, 154104]结合使用。当借助拉普拉斯变换算法进行评估时，这两种方法的系统大小都按 N(4) 缩放。使用四元基组，将这两种方法与双杂交 B2PLYP-D3、B2GPPLYP-D3、DSD-BLYP-D3 和 XYG3 进行了比较。在我们的研究中，PWPB95-D3 和 DSD-BLYP-D3 是最好的泛函，并且比 B2PLYP-D3 和 XYG3 更稳健。此外，PWPB95-D3 在三重 ζ 水平上是最不依赖基组的，也是最好的泛函。对于过渡金属羰基的例子，主要由于 Fock 交换量较低，表明 PWPB95-D3 和 PTPSS-D3 比其他双杂交更适用。最后，我们详细讨论了 XYG3 泛函[Proc. Nat. Acad. Sci. U.S.A. 2009, 106, 4963]，它利用了 B3LYP 轨道和电子密度。我们表明，它基本上是 B2PLYP 的高度非局域变体，其部分良好的性能主要是由于与其他双杂交相比，其微扰相关的有效量较大。最后，我们推荐在一般化学应用中使用 PWPB95-D3 泛函。
