Density Functional Analysis: The Theory of Density-Corrected DFT

Stefan Vuckovic; Suhwan Song; John Kozlowski; Eunji Sim; Kieron Burke

doi:10.1021/acs.jctc.9b00826

Density Functional Analysis: The Theory of Density-Corrected DFT

Stefan Vuckovic, Suhwan Song, John Kozlowski, Eunji Sim, Kieron Burke

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

47 Citations (Scopus)

Abstract

Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for the analysis of any functional minimization with an approximate functional. We generalize DC-DFT to allow the comparison of any two functionals, not just comparison with the exact functional. We introduce a linear interpolation between any two approximations and use the results to analyze global hybrid density functionals. We define the basins of density space in which this analysis should apply and give quantitative criteria for when DC-DFT should apply. We also discuss the effects of strong correlation on the density-driven error, utilizing the restricted HF Hubbard dimer as an example.

Original language	English
Pages (from-to)	6636-6646
Number of pages	11
Journal	Journal of Chemical Theory and Computation
Volume	15
Issue number	12
DOIs	https://doi.org/10.1021/acs.jctc.9b00826
Publication status	Published - 2019 Dec 10

Bibliographical note

Funding Information:
K.B. and J.K. acknowledge funding from the NSF (CHE 1856165). S.V. acknowledges funding from the Rubicon project (019.181EN.026) which is financed by The Netherlands Organisation for Scientific Research (NWO). S.S. and E.S. were supported by a grant from the Korean Research Foundation (2017R1A2B2003552).

Funding Information:
K.B. and J.K. acknowledge funding from the NSF (CHE 1856165). S.V. acknowledges funding from the Rubicon project (019.181EN.026), which is financed by The Netherlands Organisation for Scientific Research (NWO). S.S. and E.S. were supported by a grant from the Korean Research Foundation (2017R1A2B2003552).

Publisher Copyright:
Copyright © 2019 American Chemical Society.

All Science Journal Classification (ASJC) codes

Computer Science Applications
Physical and Theoretical Chemistry

Access to Document

10.1021/acs.jctc.9b00826

Cite this

@article{5b6d5136e79b4f9ab0ead844d3fca7c5,

title = "Density Functional Analysis: The Theory of Density-Corrected DFT",

abstract = "Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for the analysis of any functional minimization with an approximate functional. We generalize DC-DFT to allow the comparison of any two functionals, not just comparison with the exact functional. We introduce a linear interpolation between any two approximations and use the results to analyze global hybrid density functionals. We define the basins of density space in which this analysis should apply and give quantitative criteria for when DC-DFT should apply. We also discuss the effects of strong correlation on the density-driven error, utilizing the restricted HF Hubbard dimer as an example.",

author = "Stefan Vuckovic and Suhwan Song and John Kozlowski and Eunji Sim and Kieron Burke",

note = "Funding Information: K.B. and J.K. acknowledge funding from the NSF (CHE 1856165). S.V. acknowledges funding from the Rubicon project (019.181EN.026) which is financed by The Netherlands Organisation for Scientific Research (NWO). S.S. and E.S. were supported by a grant from the Korean Research Foundation (2017R1A2B2003552). Funding Information: K.B. and J.K. acknowledge funding from the NSF (CHE 1856165). S.V. acknowledges funding from the Rubicon project (019.181EN.026), which is financed by The Netherlands Organisation for Scientific Research (NWO). S.S. and E.S. were supported by a grant from the Korean Research Foundation (2017R1A2B2003552). Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = dec,

day = "10",

doi = "10.1021/acs.jctc.9b00826",

language = "English",

volume = "15",

pages = "6636--6646",

journal = "Journal of Chemical Theory and Computation",

issn = "1549-9618",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Density Functional Analysis

T2 - The Theory of Density-Corrected DFT

AU - Vuckovic, Stefan

AU - Song, Suhwan

AU - Kozlowski, John

AU - Sim, Eunji

AU - Burke, Kieron

N1 - Funding Information: K.B. and J.K. acknowledge funding from the NSF (CHE 1856165). S.V. acknowledges funding from the Rubicon project (019.181EN.026) which is financed by The Netherlands Organisation for Scientific Research (NWO). S.S. and E.S. were supported by a grant from the Korean Research Foundation (2017R1A2B2003552). Funding Information: K.B. and J.K. acknowledge funding from the NSF (CHE 1856165). S.V. acknowledges funding from the Rubicon project (019.181EN.026), which is financed by The Netherlands Organisation for Scientific Research (NWO). S.S. and E.S. were supported by a grant from the Korean Research Foundation (2017R1A2B2003552). Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/12/10

Y1 - 2019/12/10

N2 - Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for the analysis of any functional minimization with an approximate functional. We generalize DC-DFT to allow the comparison of any two functionals, not just comparison with the exact functional. We introduce a linear interpolation between any two approximations and use the results to analyze global hybrid density functionals. We define the basins of density space in which this analysis should apply and give quantitative criteria for when DC-DFT should apply. We also discuss the effects of strong correlation on the density-driven error, utilizing the restricted HF Hubbard dimer as an example.

AB - Density-corrected density functional theory (DC-DFT) is enjoying substantial success in improving semilocal DFT calculations in a wide variety of chemical problems. This paper provides the formal theoretical framework and assumptions for the analysis of any functional minimization with an approximate functional. We generalize DC-DFT to allow the comparison of any two functionals, not just comparison with the exact functional. We introduce a linear interpolation between any two approximations and use the results to analyze global hybrid density functionals. We define the basins of density space in which this analysis should apply and give quantitative criteria for when DC-DFT should apply. We also discuss the effects of strong correlation on the density-driven error, utilizing the restricted HF Hubbard dimer as an example.

UR - http://www.scopus.com/inward/record.url?scp=85075457872&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85075457872&partnerID=8YFLogxK

U2 - 10.1021/acs.jctc.9b00826

DO - 10.1021/acs.jctc.9b00826

M3 - Article

C2 - 31682433

AN - SCOPUS:85075457872

SN - 1549-9618

VL - 15

SP - 6636

EP - 6646

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

IS - 12

ER -

Density Functional Analysis: The Theory of Density-Corrected DFT

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this