Density-Corrected DFT Explained: Questions and Answers

Suhwan Song, Stefan Vuckovic, Eunji Sim, Kieron Burke

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

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

Original languageEnglish
Pages (from-to)817-827
Number of pages11
JournalJournal of Chemical Theory and Computation
Volume18
Issue number2
DOIs
Publication statusPublished - 2022 Feb 8

Bibliographical note

Funding Information:
S.S. and E.S. are grateful for support from the National Research Foundation of Korea (NRF-2020R1A2C2007468 and NRF-2020R1A4A1017737). K.B. acknowledges funding from NSF (CHEM 1856165). S.V. acknowledges funding from the Marie Skłodowska-Curie Grant 101033630 (EU’s Horizon 2020 programme). We thanks G. Santra and J. M. L. Martin for helpful discussions and providing the data on which ref was based.

Publisher Copyright:
© 2022 American Chemical Society.

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Fingerprint

Dive into the research topics of 'Density-Corrected DFT Explained: Questions and Answers'. Together they form a unique fingerprint.

Cite this