Journal of Chemical Physics, volume 127, issue 2, pages 24103

Why does the B3LYP hybrid functional fail for metals?

Paier Joachim ^{1, 2}

Marsman Martijn ^{1, 2}

Kresse Georg ^{1, 2}

Hide authors affiliations Show authors affiliations: 2 affiliations

Universität Wien Faculty of Physics, and , Sensengasse 8/12, A-1090 Wien, Austria |

Center for Computational Materials Science Faculty of Physics, and , Sensengasse 8/12, A-1090 Wien, Austria |

Publication type: Journal Article

Publication date: 2007-07-10

American Institute of Physics (AIP)

Journal: Journal of Chemical Physics

Quartile SCImago

Quartile WOS

Impact factor: 4.4

ISSN: 00219606, 10897690

DOI: 10.1063/1.2747249

Copy DOI

Physical and Theoretical Chemistry

General Physics and Astronomy

Abstract

The B3LYP hybrid functional has shown to successfully predict a wide range of molecular properties. For periodic systems, however, the failure to attain the exact homogeneous electron gas limit as well as the semiempirical construction turns out to be a major drawback of the functional. We rigorously assess the B3LYP functional for solids through calculations of lattice parameters, bulk moduli, and thermochemical properties (atomization energies and reaction energies). The theoretical lattice constants overestimate the experimental ones by approximately 1%, and hence behave similarly to the PBE gradient-corrected exchange-correlation functional. B3LYP atomization energies of solids are drastically worse than those of nonempirical hybrid Hartree-Fock/density functionals (HF/DFT) such as PBE0 and HSE03. These large errors can be traced back to the lack of a proper description of “free-electron-like” systems with a significant itinerant character (metals and small gap semiconductors). Similar calculations using the popular semiempirical B3PW91 hybrid functional, which fulfills the uniform electron gas limit, show a clear improvement over B3LYP regarding atomization energies. Finally, theoretical values for heats of formation for both the B3LYP as well as the B3PW91 functionals are presented. These document a most likely fortuitously good agreement with experiment for the B3LYP hybrid functional.

By date By citations

Citations by journals

	5 10 15 20 25 30 35 40
Journal of Chemical Physics	Journal of Chemical Physics, 36, 7.59% Journal of Chemical Physics 36 publications, 7.59%
Journal of Physical Chemistry C	Journal of Physical Chemistry C, 30, 6.33% Journal of Physical Chemistry C 30 publications, 6.33%
Physical Review B	Physical Review B, 29, 6.12% Physical Review B 29 publications, 6.12%
Physical Chemistry Chemical Physics	Physical Chemistry Chemical Physics, 27, 5.7% Physical Chemistry Chemical Physics 27 publications, 5.7%
Journal of Chemical Theory and Computation	Journal of Chemical Theory and Computation, 25, 5.27% Journal of Chemical Theory and Computation 25 publications, 5.27%
Journal of Physics Condensed Matter	Journal of Physics Condensed Matter, 16, 3.38% Journal of Physics Condensed Matter 16 publications, 3.38%
Journal of Physical Chemistry A	Journal of Physical Chemistry A, 15, 3.16% Journal of Physical Chemistry A 15 publications, 3.16%
International Journal of Quantum Chemistry	International Journal of Quantum Chemistry, 11, 2.32% International Journal of Quantum Chemistry 11 publications, 2.32%
Chemical Reviews	Chemical Reviews, 9, 1.9% Chemical Reviews 9 publications, 1.9%
Journal of Molecular Modeling	Journal of Molecular Modeling, 8, 1.69% Journal of Molecular Modeling 8 publications, 1.69%
Applied Surface Science	Applied Surface Science, 8, 1.69% Applied Surface Science 8 publications, 1.69%
Journal of the Electrochemical Society	Journal of the Electrochemical Society, 6, 1.27% Journal of the Electrochemical Society 6 publications, 1.27%
Theoretical Chemistry Accounts	Theoretical Chemistry Accounts, 6, 1.27% Theoretical Chemistry Accounts 6 publications, 1.27%
Computational and Theoretical Chemistry	Computational and Theoretical Chemistry, 6, 1.27% Computational and Theoretical Chemistry 6 publications, 1.27%
Journal of Computational Chemistry	Journal of Computational Chemistry, 6, 1.27% Journal of Computational Chemistry 6 publications, 1.27%
Journal of the American Chemical Society	Journal of the American Chemical Society, 6, 1.27% Journal of the American Chemical Society 6 publications, 1.27%
Chemistry of Materials	Chemistry of Materials, 5, 1.05% Chemistry of Materials 5 publications, 1.05%
Journal of Physical Chemistry Letters	Journal of Physical Chemistry Letters, 5, 1.05% Journal of Physical Chemistry Letters 5 publications, 1.05%
Physical Review Letters	Physical Review Letters, 5, 1.05% Physical Review Letters 5 publications, 1.05%
Physical Review Materials	Physical Review Materials, 5, 1.05% Physical Review Materials 5 publications, 1.05%
Journal of Molecular Structure	Journal of Molecular Structure, 5, 1.05% Journal of Molecular Structure 5 publications, 1.05%
New Journal of Physics	New Journal of Physics, 5, 1.05% New Journal of Physics 5 publications, 1.05%
Chemical Physics Letters	Chemical Physics Letters, 5, 1.05% Chemical Physics Letters 5 publications, 1.05%
RSC Advances	RSC Advances, 5, 1.05% RSC Advances 5 publications, 1.05%
Molecules	Molecules, 4, 0.84% Molecules 4 publications, 0.84%
Journal of Physical Chemistry B	Journal of Physical Chemistry B, 4, 0.84% Journal of Physical Chemistry B 4 publications, 0.84%
Applied Physics A: Materials Science and Processing	Applied Physics A: Materials Science and Processing, 3, 0.63% Applied Physics A: Materials Science and Processing 3 publications, 0.63%
Physica Status Solidi (B): Basic Research	Physica Status Solidi (B): Basic Research, 3, 0.63% Physica Status Solidi (B): Basic Research 3 publications, 0.63%
Organometallics	Organometallics, 3, 0.63% Organometallics 3 publications, 0.63%
	5 10 15 20 25 30 35 40

Citations by publishers

	20 40 60 80 100 120 140
American Chemical Society (ACS)	American Chemical Society (ACS), 121, 25.53% American Chemical Society (ACS) 121 publications, 25.53%
Elsevier	Elsevier, 61, 12.87% Elsevier 61 publications, 12.87%
Royal Society of Chemistry (RSC)	Royal Society of Chemistry (RSC), 47, 9.92% Royal Society of Chemistry (RSC) 47 publications, 9.92%
Springer Nature	Springer Nature, 46, 9.7% Springer Nature 46 publications, 9.7%
American Physical Society (APS)	American Physical Society (APS), 41, 8.65% American Physical Society (APS) 41 publications, 8.65%
American Institute of Physics (AIP)	American Institute of Physics (AIP), 40, 8.44% American Institute of Physics (AIP) 40 publications, 8.44%
Wiley	Wiley, 32, 6.75% Wiley 32 publications, 6.75%
IOP Publishing	IOP Publishing, 26, 5.49% IOP Publishing 26 publications, 5.49%
Multidisciplinary Digital Publishing Institute (MDPI)	Multidisciplinary Digital Publishing Institute (MDPI), 10, 2.11% Multidisciplinary Digital Publishing Institute (MDPI) 10 publications, 2.11%
The Electrochemical Society	The Electrochemical Society, 7, 1.48% The Electrochemical Society 7 publications, 1.48%
Taylor & Francis	Taylor & Francis, 7, 1.48% Taylor & Francis 7 publications, 1.48%
Science in China Press	Science in China Press, 2, 0.42% Science in China Press 2 publications, 0.42%
Annual Reviews	Annual Reviews, 2, 0.42% Annual Reviews 2 publications, 0.42%
Canadian Science Publishing	Canadian Science Publishing, 1, 0.21% Canadian Science Publishing 1 publication, 0.21%
Mineralogical Society of America	Mineralogical Society of America, 1, 0.21% Mineralogical Society of America 1 publication, 0.21%
The Royal Society	The Royal Society, 1, 0.21% The Royal Society 1 publication, 0.21%
Frontiers Media S.A.	Frontiers Media S.A., 1, 0.21% Frontiers Media S.A. 1 publication, 0.21%
Pleiades Publishing	Pleiades Publishing, 1, 0.21% Pleiades Publishing 1 publication, 0.21%
American Institute of Mathematical Sciences (AIMS)	American Institute of Mathematical Sciences (AIMS), 1, 0.21% American Institute of Mathematical Sciences (AIMS) 1 publication, 0.21%
Chinese Physical Society	Chinese Physical Society, 1, 0.21% Chinese Physical Society 1 publication, 0.21%
Hindawi Limited	Hindawi Limited, 1, 0.21% Hindawi Limited 1 publication, 0.21%
Optical Society of India	Optical Society of India, 1, 0.21% Optical Society of India 1 publication, 0.21%
	20 40 60 80 100 120 140

We do not take into account publications that without a DOI.
Statistics recalculated only for publications connected to researchers, organizations and labs registered on the platform.
Statistics recalculated weekly.

{"yearsCitations":{"type":"bar","data":{"show":true,"labels":[2007,2008,2009,2010,2011,2012,2013,2014,2015,2016,2017,2018,2019,2020,2021,2022,2023,2024],"ids":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"codes":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"imageUrls":["","","","","","","","","","","","","","","","","",""],"datasets":[{"label":"Citations number","data":[3,22,34,29,33,34,39,29,30,29,25,16,26,29,28,36,27,5],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":["0.63","4.64","7.17","6.12","6.96","7.17","8.23","6.12","6.33","6.12","5.27","3.38","5.49","6.12","5.91","7.59","5.7","1.05"],"barThickness":null}]},"options":{"indexAxis":"x","maintainAspectRatio":true,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"}},"x":{"ticks":{"stepSize":1,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"}}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Citations per year","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"journals":{"type":"bar","data":{"show":true,"labels":["Journal of Chemical Physics","Journal of Physical Chemistry C","Physical Review B","Physical Chemistry Chemical Physics","Journal of Chemical Theory and Computation","Journal of Physics Condensed Matter","Journal of Physical Chemistry A","International Journal of Quantum Chemistry","Chemical Reviews","Journal of Molecular Modeling","Applied Surface Science","Journal of the Electrochemical Society","Theoretical Chemistry Accounts","Computational and Theoretical Chemistry","Journal of Computational Chemistry","Journal of the American Chemical Society","Chemistry of Materials","Journal of Physical Chemistry Letters","Physical Review Letters","Physical Review Materials","Journal of Molecular Structure","New Journal of Physics","Chemical Physics Letters","RSC Advances","Molecules","Journal of Physical Chemistry B","Applied Physics A: Materials Science and Processing","Physica Status Solidi (B): Basic Research","Organometallics"],"ids":[544,8859,25280,1773,58,4579,15255,15897,13718,6610,12539,5297,19212,12461,423,4813,6428,21963,4343,7673,9347,431,5579,3100,1770,14990,14766,11584,1409],"codes":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"imageUrls":["\/storage\/images\/resized\/ARM4e6URKRsbRZvIF0vFis9DjxGloBjnBYJXbHmZ_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/nrK64iXHTzj43wMrfN1ZoUQ0vanswGzWPN45K3jA_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/LsKy6OnmmmRGcAU6CZgWQvNiP1polbaSLNrN7zqj_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/s6nfxitVCZUsdJiJZESaAXqdmMJxom8q4Ps6ayL2_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/nrK64iXHTzj43wMrfN1ZoUQ0vanswGzWPN45K3jA_medium.webp","\/storage\/images\/resized\/nrK64iXHTzj43wMrfN1ZoUQ0vanswGzWPN45K3jA_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/LsKy6OnmmmRGcAU6CZgWQvNiP1polbaSLNrN7zqj_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/MjH1ITP7lMYGxeqUZfkt2BnVLgjkk413jwBV97XX_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp"],"datasets":[{"label":"","data":[36,30,29,27,25,16,15,11,9,8,8,6,6,6,6,6,5,5,5,5,5,5,5,5,4,4,3,3,3],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":[7.59,6.33,6.12,5.7,5.27,3.38,3.16,2.32,1.9,1.69,1.69,1.27,1.27,1.27,1.27,1.27,1.05,1.05,1.05,1.05,1.05,1.05,1.05,1.05,0.84,0.84,0.63,0.63,0.63],"barThickness":13}]},"options":{"indexAxis":"y","maintainAspectRatio":false,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"}},"x":{"ticks":{"stepSize":null,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"}}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Journals","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}},"publishers":{"type":"bar","data":{"show":true,"labels":["American Chemical Society (ACS)","Elsevier","Royal Society of Chemistry (RSC)","Springer Nature","American Physical Society (APS)","American Institute of Physics (AIP)","Wiley","IOP Publishing","Multidisciplinary Digital Publishing Institute (MDPI)","The Electrochemical Society","Taylor & Francis","Science in China Press","Annual Reviews","Canadian Science Publishing","Mineralogical Society of America","The Royal Society","Frontiers Media S.A.","Pleiades Publishing","American Institute of Mathematical Sciences (AIMS)","Chinese Physical Society","Hindawi Limited","Optical Society of India"],"ids":[40,17,123,8,1539,250,11,2075,202,6916,18,6481,6941,6942,3076,259,208,101,411,3809,6921,5397],"codes":[0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0,0],"imageUrls":["\/storage\/images\/resized\/iLiQsFqFaSEx6chlGQ5fbAwF6VYU3WWa08hkss0g_medium.webp","\/storage\/images\/resized\/GDnYOu1UpMMfMMRV6Aqle4H0YLLsraeD9IP9qScG_medium.webp","\/storage\/images\/resized\/leiAYcRDGTSl5B1eCnwpSGqmDEUEfDPPoYisFGhT_medium.webp","\/storage\/images\/resized\/voXLqlsvTwv5p3iMQ8Dhs95nqB4AXOG7Taj7G4ra_medium.webp","\/storage\/images\/resized\/nrK64iXHTzj43wMrfN1ZoUQ0vanswGzWPN45K3jA_medium.webp","\/storage\/images\/resized\/ARM4e6URKRsbRZvIF0vFis9DjxGloBjnBYJXbHmZ_medium.webp","\/storage\/images\/resized\/bRyGpdm98BkAUYiK1YFNpl5Z7hPu6Gd87gbIeuG3_medium.webp","\/storage\/images\/resized\/LsKy6OnmmmRGcAU6CZgWQvNiP1polbaSLNrN7zqj_medium.webp","\/storage\/images\/resized\/MjH1ITP7lMYGxeqUZfkt2BnVLgjkk413jwBV97XX_medium.webp","\/storage\/images\/resized\/s6nfxitVCZUsdJiJZESaAXqdmMJxom8q4Ps6ayL2_medium.webp","\/storage\/images\/resized\/5YZtvLvkPZuc2JHOaZsjCvGSHFCuC3drUwN3YAc5_medium.webp","","\/storage\/images\/resized\/A7oGMwx1m3fFJlKJvQUVra8h0itmEa7JZW0q3Q0b_medium.webp","\/storage\/images\/resized\/qZfu8vVyaDIo81Au73p6SNE8AGGzf73yfiTC33bu_medium.webp","\/storage\/images\/resized\/kqh8gNMJsbhoJ45HnRhw63ESYFTLLbtJitEsevPA_medium.webp","\/storage\/images\/resized\/BHBStD1OkQqtKFRRjS5njgNe7bXCAEgaDQVK7GTA_medium.webp","\/storage\/images\/resized\/4QWA67eqfcfyOiA8Wk7YnqroHFqQbTsmDJUYTCTg_medium.webp","\/storage\/images\/resized\/oZgeErrVFhuDksyqFURLvYS1wtVSBWczh001igGo_medium.webp","\/storage\/images\/resized\/aNCVPuZHdlcDPPU6lLLRLMJmFvhYoNbgJ8kdsJQz_medium.webp","\/storage\/images\/resized\/uHl9M7oE4uFd6rEwxtu87cdHS4Etul2pdLbot8Qu_medium.webp","\/storage\/images\/resized\/hqfzhQAjTGlNSRs6yzFNITgjSMm9Jr2QuotJHIvE_medium.webp","\/storage\/images\/resized\/V0ahwkzp9hrsvrljh50lHUEHKtdNrQAw6nzOMOZp_medium.webp"],"datasets":[{"label":"","data":[121,61,47,46,41,40,32,26,10,7,7,2,2,1,1,1,1,1,1,1,1,1],"backgroundColor":["#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6","#3B82F6"],"percentage":[25.53,12.87,9.92,9.7,8.65,8.44,6.75,5.49,2.11,1.48,1.48,0.42,0.42,0.21,0.21,0.21,0.21,0.21,0.21,0.21,0.21,0.21],"barThickness":13}]},"options":{"indexAxis":"y","maintainAspectRatio":false,"scales":{"y":{"ticks":{"precision":0,"autoSkip":false,"font":{"family":"Montserrat"},"color":"#000000"}},"x":{"ticks":{"stepSize":null,"precision":0,"font":{"family":"Montserrat"},"color":"#000000"}}},"plugins":{"legend":{"position":"top","labels":{"font":{"family":"Montserrat"},"color":"#000000"}},"title":{"display":true,"text":"Publishers","font":{"size":24,"family":"Montserrat","weight":600},"color":"#000000"}}}}}

Publication PDF

Metrics

Cite this

GOST |

Cite this

GOST Copy

Paier J. et al. Why does the B3LYP hybrid functional fail for metals? // Journal of Chemical Physics. 2007. Vol. 127. No. 2. p. 24103.

GOST all authors (up to 50) Copy

Paier J., Marsman M., Kresse G. Why does the B3LYP hybrid functional fail for metals? // Journal of Chemical Physics. 2007. Vol. 127. No. 2. p. 24103.

RIS |

Cite this