What Types of Chemical Problems Benefit from Density-Corrected DFT? A Probe Using an Extensive and Chemically Diverse Test Suite.

Abstract

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, and 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, HF-DFT is highly beneficial, particularly at low HF exchange percentages. This is especially true for noncovalent interactions where the electrostatic component is dominant, such as hydrogen and halogen bonds: for π-stacking, HF-DFT is detrimental. For subsets with significant nondynamical 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) as the use of HF orbitals greatly mitigates the error at 25% for barrier heights. 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 for 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 combinatorially optimized empirical range-separated hybrids ωB97X-V and ωB97M-V.