Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost
The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT...
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| Format: | Article |
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AIP Publishing
2019
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| Online Access: | http://hdl.handle.net/1721.1/120572 https://orcid.org/0000-0001-7825-4797 https://orcid.org/0000-0001-9342-0191 |
| _version_ | 1826192598781394944 |
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| author | Bajaj, Akash Janet, Jon Paul Kulik, Heather Janine |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Bajaj, Akash Janet, Jon Paul Kulik, Heather Janine |
| author_sort | Bajaj, Akash |
| collection | MIT |
| description | The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT) fails to recover the flat plane, exhibiting convex fractional charge errors (FCE) and concave fractional spin errors (FSE) that are related to delocalization and static correlation errors. We previously showed that DFT+U eliminates FCE but now demonstrate that, like other widely employed corrections (i.e., Hartree-Fock exchange), it worsens FSE. To find an alternative strategy, we examine the shape of semi-local DFT deviations from the exact flat plane and we find this shape to be remarkably consistent across ions and molecules. We introduce the judiciously modified DFT (jmDFT) approach, wherein corrections are constructed from few-parameter, low-order functional forms that fit the shape of semi-local DFT errors. We select one such physically intuitive form and incorporate it self-consistently to correct semi-local DFT. We demonstrate on model systems that jmDFT represents the first easy-to-implement, no-overhead approach to recovering the flat plane from semi-local DFT. |
| first_indexed | 2024-09-23T09:22:39Z |
| format | Article |
| id | mit-1721.1/120572 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T09:22:39Z |
| publishDate | 2019 |
| publisher | AIP Publishing |
| record_format | dspace |
| spelling | mit-1721.1/1205722022-09-26T11:21:30Z Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost Bajaj, Akash Janet, Jon Paul Kulik, Heather Janine Massachusetts Institute of Technology. Department of Chemical Engineering Massachusetts Institute of Technology. Department of Materials Science and Engineering Bajaj, Akash Janet, Jon Paul Kulik, Heather Janine The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT) fails to recover the flat plane, exhibiting convex fractional charge errors (FCE) and concave fractional spin errors (FSE) that are related to delocalization and static correlation errors. We previously showed that DFT+U eliminates FCE but now demonstrate that, like other widely employed corrections (i.e., Hartree-Fock exchange), it worsens FSE. To find an alternative strategy, we examine the shape of semi-local DFT deviations from the exact flat plane and we find this shape to be remarkably consistent across ions and molecules. We introduce the judiciously modified DFT (jmDFT) approach, wherein corrections are constructed from few-parameter, low-order functional forms that fit the shape of semi-local DFT errors. We select one such physically intuitive form and incorporate it self-consistently to correct semi-local DFT. We demonstrate on model systems that jmDFT represents the first easy-to-implement, no-overhead approach to recovering the flat plane from semi-local DFT. United States. Department of Energy (Grant DE-SC0018096) United States. Office of Naval Research (Grant N00014-17-1-2956) 2019-02-28T16:54:40Z 2019-02-28T16:54:40Z 2017-11 2017-10 2019-02-05T13:29:39Z Article http://purl.org/eprint/type/JournalArticle 0021-9606 1089-7690 http://hdl.handle.net/1721.1/120572 Bajaj, Akash et al. “Communication: Recovering the Flat-Plane Condition in Electronic Structure Theory at Semi-Local DFT Cost.” The Journal of Chemical Physics 147, 19 (November 2017): 191101 © 2017 Author(s) https://orcid.org/0000-0001-7825-4797 https://orcid.org/0000-0001-9342-0191 http://dx.doi.org/10.1063/1.5008981 Journal of Chemical Physics Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf AIP Publishing arXiv |
| spellingShingle | Bajaj, Akash Janet, Jon Paul Kulik, Heather Janine Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost |
| title | Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost |
| title_full | Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost |
| title_fullStr | Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost |
| title_full_unstemmed | Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost |
| title_short | Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost |
| title_sort | communication recovering the flat plane condition in electronic structure theory at semi local dft cost |
| url | http://hdl.handle.net/1721.1/120572 https://orcid.org/0000-0001-7825-4797 https://orcid.org/0000-0001-9342-0191 |
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