Density-Corrected DFT Explained: Questions and Answers

Suhwan Song, Stefan Vuckovic, Eunji Sim*, Kieron Burke

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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
Early online date28 Jan 2022
DOIs
Publication statusPublished - 8 Feb 2022

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.

Funding

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.

FundersFunder number
EU’s Horizon 2020 programme
National Research Foundation of KoreaNRF-2020R1A2C2007468, NRF-2020R1A4A1017737
Horizon 2020 Framework Programme101033630
National Science Foundation1856165
Marie Skłodowska-Curie101033630

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