Perspective: Treating electron over-delocalization with the DFT+U method
Many people in the materials science and solid-state community are familiar with the acronym “DFT+U.” For those less familiar, this technique uses ideas from model Hamiltonians that permit the description of both metals and insulators to address problems of electron over-delocalization in practical...
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| Format: | Article |
| Language: | en_US |
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American Institute of Physics (AIP)
2016
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| Online Access: | http://hdl.handle.net/1721.1/101201 https://orcid.org/0000-0001-9342-0191 |
| _version_ | 1811093739815305216 |
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| author | Kulik, Heather J. |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Kulik, Heather J. |
| author_sort | Kulik, Heather J. |
| collection | MIT |
| description | Many people in the materials science and solid-state community are familiar with the acronym “DFT+U.” For those less familiar, this technique uses ideas from model Hamiltonians that permit the description of both metals and insulators to address problems of electron over-delocalization in practical implementations of density functional theory (DFT). Exchange-correlation functionals in DFT are often described as belonging to a hierarchical “Jacob’s ladder” of increasing accuracy in moving from local to non-local descriptions of exchange and correlation. DFT+U is not on this “ladder” but rather acts as an “elevator” because it systematically tunes relative energetics, typically on a localized subshell (e.g., d or f electrons), regardless of the underlying functional employed. However, this tuning is based on a metric of the local electron density of the subshells being addressed, thus necessitating physical or chemical or intuition about the system of interest. I will provide a brief overview of the history of how DFT+U came to be starting from the origin of the Hubbard and Anderson model Hamiltonians. This history lesson is necessary because it permits us to make the connections between the “Hubbard U” and fundamental outstanding challenges in electronic structure theory, and it helps to explain why this method is so widely applied to transition-metal oxides and organometallic complexes alike. |
| first_indexed | 2024-09-23T15:49:53Z |
| format | Article |
| id | mit-1721.1/101201 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T15:49:53Z |
| publishDate | 2016 |
| publisher | American Institute of Physics (AIP) |
| record_format | dspace |
| spelling | mit-1721.1/1012012022-09-29T16:27:12Z Perspective: Treating electron over-delocalization with the DFT+U method Kulik, Heather J. Massachusetts Institute of Technology. Department of Chemical Engineering Kulik, Heather J. Many people in the materials science and solid-state community are familiar with the acronym “DFT+U.” For those less familiar, this technique uses ideas from model Hamiltonians that permit the description of both metals and insulators to address problems of electron over-delocalization in practical implementations of density functional theory (DFT). Exchange-correlation functionals in DFT are often described as belonging to a hierarchical “Jacob’s ladder” of increasing accuracy in moving from local to non-local descriptions of exchange and correlation. DFT+U is not on this “ladder” but rather acts as an “elevator” because it systematically tunes relative energetics, typically on a localized subshell (e.g., d or f electrons), regardless of the underlying functional employed. However, this tuning is based on a metric of the local electron density of the subshells being addressed, thus necessitating physical or chemical or intuition about the system of interest. I will provide a brief overview of the history of how DFT+U came to be starting from the origin of the Hubbard and Anderson model Hamiltonians. This history lesson is necessary because it permits us to make the connections between the “Hubbard U” and fundamental outstanding challenges in electronic structure theory, and it helps to explain why this method is so widely applied to transition-metal oxides and organometallic complexes alike. Burroughs Wellcome Fund (Career Award at the Scientific Interface) Massachusetts Institute of Technology. Research Support Corporation National Science Foundation (U.S.) (ECCS-1449291) MIT Energy Initiative Massachusetts Institute of Technology. Department of Chemical Engineering (Startup Funds) 2016-02-17T18:09:38Z 2016-02-17T18:09:38Z 2015-06 2015-03 Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 http://hdl.handle.net/1721.1/101201 Kulik, Heather J. “Perspective: Treating Electron over-Delocalization with the DFT+U Method.” J. Chem. Phys. 142, no. 24 (June 28, 2015): 240901. © 2015 AIP Publishing LLC https://orcid.org/0000-0001-9342-0191 en_US http://dx.doi.org/10.1063/1.4922693 The Journal of Chemical Physics 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 Institute of Physics (AIP) MIT web domain |
| spellingShingle | Kulik, Heather J. Perspective: Treating electron over-delocalization with the DFT+U method |
| title | Perspective: Treating electron over-delocalization with the DFT+U method |
| title_full | Perspective: Treating electron over-delocalization with the DFT+U method |
| title_fullStr | Perspective: Treating electron over-delocalization with the DFT+U method |
| title_full_unstemmed | Perspective: Treating electron over-delocalization with the DFT+U method |
| title_short | Perspective: Treating electron over-delocalization with the DFT+U method |
| title_sort | perspective treating electron over delocalization with the dft u method |
| url | http://hdl.handle.net/1721.1/101201 https://orcid.org/0000-0001-9342-0191 |
| work_keys_str_mv | AT kulikheatherj perspectivetreatingelectronoverdelocalizationwiththedftumethod |