论文标题
通过密度校正的DFT，哪些类型的化学问题受益？使用广泛且化学多样的测试套件的探测器
What types of chemical problems benefit from density-corrected DFT? A probe using an extensive and chemically diverse test suite
论文作者
论文摘要
For the large and chemically diverse GMTKN55 benchmark suite, we have studied the performance of density-corrected density functional theory (HF-DFT), compared to self-consistent DFT, for several pure and hybrid GGA and meta-GGA exchange-correlation (XC) functionals (PBE, BLYP, TPSS, SCAN) as a function of the percentage of HF exchange in the hybrid. D4经验分散校正均已添加。对于由动态相关性（尤其是非共价相互作用子集）主导的子集，HF-DFT非常有益，尤其是在HF交换率低的情况下。对于具有显着静态相关性的子集（即，在Hartree-fock决定因素不是良好的零级波函数）中，HF-DFT可能弊大于利。虽然这四个XC功能的自洽系列显示了Optiama在37.5％（即3/8）的接近或接近37.5％（即3/8），这与Grimme对PBE38功能的提议一致-HF-BNLYP-D4，HF-PBEN-D4，HF-PBEN-D4和HF-TPSSN-D4均展示了所有展示最小值25％（I.E.E.E.E.E.E.，1/4）。有趣的是，对于HF-SCANN-D4，最小值接近10％，但是GMTKN55的加权平均绝对误差（WTMAD2）仅低于HF-SCAN-D4的加权平均误差（WTMAD2）（即HF-SCAN-D4（即HF后HF步骤是纯Meta-GGA）。后者成为一个有吸引力的选择，仅比纯Hartree-fock稍高，并且没有分散校正中三个以外的可调节参数。此外，其WTMAD2仅被高度经验的M06-2X和组合优化的经验范围分离的混合动力车WB97X-V和WB97M-V所超越。
For the large and chemically diverse GMTKN55 benchmark suite, we have studied the performance of density-corrected density functional theory (HF-DFT), compared to self-consistent DFT, for several pure and hybrid GGA and meta-GGA exchange-correlation (XC) functionals (PBE, BLYP, TPSS, SCAN) as a function of the percentage of HF exchange in the hybrid. The D4 empirical dispersion correction has been added throughout. For subsets dominated by dynamical correlation -- particularly noncovalent interaction subsets -- HF-DFT is highly beneficial, particularly at low HF exchange percentages. For subsets with significant static correlation (i.e., where a Hartree-Fock determinant is not a good zero-order wavefunction), HF-DFT may do more harm than good. While the self-consistent series show optima at or near 37.5% (i.e., 3/8) for all four XC functionals -- consistent with Grimme's proposal of the PBE38 functional -- HF-BnLYP-D4, HF-PBEn-D4, and HF-TPSSn-D4 all exhibit minima nearer 25% (i.e., 1/4). Intriguingly, for HF-SCANn-D4, the minimum is near 10%, but the weighted mean absolute error (WTMAD2) for GMTKN55 is only barely lower than that of HF-SCAN-D4 (i.e., where the post-HF step is a pure meta-GGA). The latter becomes an attractive option, only slightly more costly than pure Hartree-Fock, and devoid of adjustable parameters other than the three in the dispersion correction. Moreover, its WTMAD2 is only surpassed by the highly empirical M06-2X and by the combinatorically optimized empirical range-separated hybrids wB97X-V and wB97M-V.
