Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds
We compare the accuracy of conventional semilocal density functional theory (DFT), the DFT+U method, and the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional for structural parameters, redox reaction energies, and formation energies of transition metal compounds. Conventional DFT functionals signif...
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| Format: | Article |
| Language: | en_US |
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American Physical Society
2011
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| Online Access: | http://hdl.handle.net/1721.1/60988 https://orcid.org/0000-0002-5571-0814 |
| _version_ | 1826200173261357056 |
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| author | Ceder, Gerbrand Ong, Shyue Ping Chan, Maria K. Armiento, Rickard R. Chevrier, Vincent L. |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Ceder, Gerbrand Ong, Shyue Ping Chan, Maria K. Armiento, Rickard R. Chevrier, Vincent L. |
| author_sort | Ceder, Gerbrand |
| collection | MIT |
| description | We compare the accuracy of conventional semilocal density functional theory (DFT), the DFT+U method, and the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional for structural parameters, redox reaction energies, and formation energies of transition metal compounds. Conventional DFT functionals significantly underestimate redox potentials for these compounds. Zhou et al. [Phys. Rev. B 70, 235121 (2004)] addressed this issue with DFT+U and a linear-response scheme for calculating U values. We show that the Li intercalation potentials of prominent Li-ion intercalation battery materials, such as the layered LixMO2 (M=Co and Ni), LixTiS2; olivine LixMPO4 (M=Mn, Fe, Co, and Ni); and spinel-like LixMn2O4, LixTi2O4, are also well reproduced by HSE06, due to the self-interaction error correction from the partial inclusion of Hartree-Fock exchange. For formation energies, HSE06 performs well for transition metal compounds, which typically are not well reproduced by conventional DFT functionals but does not significantly improve the results of nontransition metal oxides. Hence, we find that hybrid functionals provide a good alternative to DFT+U for transition metal applications when the large extra computational effort is compensated by the benefits of (i) avoiding species-specific adjustable parameters and (ii) a more universal treatment of the self-interaction error that is not exclusive to specific atomic orbital projections on selected ions. |
| first_indexed | 2024-09-23T11:32:17Z |
| format | Article |
| id | mit-1721.1/60988 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:32:17Z |
| publishDate | 2011 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | mit-1721.1/609882022-09-27T20:10:18Z Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds Ceder, Gerbrand Ong, Shyue Ping Chan, Maria K. Armiento, Rickard R. Chevrier, Vincent L. Massachusetts Institute of Technology. Department of Materials Science and Engineering Ceder, Gerbrand Ceder, Gerbrand Ong, Shyue Ping Chan, Maria K. Armiento, Rickard R. Chevrier, Vincent L. We compare the accuracy of conventional semilocal density functional theory (DFT), the DFT+U method, and the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional for structural parameters, redox reaction energies, and formation energies of transition metal compounds. Conventional DFT functionals significantly underestimate redox potentials for these compounds. Zhou et al. [Phys. Rev. B 70, 235121 (2004)] addressed this issue with DFT+U and a linear-response scheme for calculating U values. We show that the Li intercalation potentials of prominent Li-ion intercalation battery materials, such as the layered LixMO2 (M=Co and Ni), LixTiS2; olivine LixMPO4 (M=Mn, Fe, Co, and Ni); and spinel-like LixMn2O4, LixTi2O4, are also well reproduced by HSE06, due to the self-interaction error correction from the partial inclusion of Hartree-Fock exchange. For formation energies, HSE06 performs well for transition metal compounds, which typically are not well reproduced by conventional DFT functionals but does not significantly improve the results of nontransition metal oxides. Hence, we find that hybrid functionals provide a good alternative to DFT+U for transition metal applications when the large extra computational effort is compensated by the benefits of (i) avoiding species-specific adjustable parameters and (ii) a more universal treatment of the self-interaction error that is not exclusive to specific atomic orbital projections on selected ions. United States. Dept. of Energy (Contract No. DE-FG02-96ER45571) Massachusetts Institute of Technology. Center for Materials Science and Engineering (Grant No. DMR-819762) Teragrid (Firm) (Grant No. TG-DMR970008S) 2011-02-18T19:14:31Z 2011-02-18T19:14:31Z 2010-08 2010-07 Article http://purl.org/eprint/type/JournalArticle 1098-0121 1550-235X http://hdl.handle.net/1721.1/60988 Chevrier, V. L. et al. “Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds.” Physical Review B 82.7 (2010): 075122. © 2010 The American Physical Society. https://orcid.org/0000-0002-5571-0814 en_US http://dx.doi.org/10.1103/PhysRevB.82.075122 Physical Review B Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Physical Society APS |
| spellingShingle | Ceder, Gerbrand Ong, Shyue Ping Chan, Maria K. Armiento, Rickard R. Chevrier, Vincent L. Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| title | Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| title_full | Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| title_fullStr | Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| title_full_unstemmed | Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| title_short | Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| title_sort | hybrid density functional calculations of redox potentials and formation energies of transition metal compounds |
| url | http://hdl.handle.net/1721.1/60988 https://orcid.org/0000-0002-5571-0814 |
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