English

Density-corrected DFT explained: Questions and answers

Chemical Physics 2021-10-18 v1

Abstract

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 re-analysis using DC-DFT shows that DC(HF)-DFT substantially improves DFT results precisely when SC densities are flawed.

Keywords

Cite

@article{arxiv.2110.07849,
  title  = {Density-corrected DFT explained: Questions and answers},
  author = {Suhwan Song and Stefan Vuckovic and Eunji Sim and Kieron Burke},
  journal= {arXiv preprint arXiv:2110.07849},
  year   = {2021}
}
R2 v1 2026-06-24T06:54:34.289Z