Density-Corrected DFT Explained: Questions and Answers

HF-DFT, the practice of evaluating approximate density functionals on Hartree-Fock densities, has long been used in testing density functional approximations. Density-corrected DFT (DC-DFT) is a general theoretical framework for identifying failures of density functional approximations by separating errors in a functional from errors in its self-consistent (SC) density. Most modern DFT calculations yield highly accurate densities, but important characteristic classes of calculation have large density-driven errors, including reaction barrier heights, electron affinities, radicals and anions in solution, dissociation of heterodimers, and even some torsional barriers. Here, the HF density (if not spin-contaminated) usually yields more accurate and consistent energies than those of the SC density. We use the term DC(HF)-DFT to indicate DC-DFT using HF densities only in such cases. A recent comprehensive study (J. Chem. Theory Comput. 2021, 17, 1368-1379) of HF-DFT led to many unfavorable conclusions. A reanalysis using DC-DFT shows that DC(HF)-DFT substantially improves DFT results precisely when SC densities are flawed.

Automated summary

HF-DFT is a common method for evaluating approximate density functionals, while DC-DFT is a theoretical framework for identifying failures of density functional approximations. Research on HF-DFT has found that in certain cases, using HF densities instead of self-consistent densities can provide more accurate and consistent energy results. A recent study reanalyzed HF-DFT and showed that DC(HF)-DFT substantially improves DFT results when SC densities are flawed.