Formation enthalpies by mixing GGA and GGA + U calculations
Standard approximations to the density functional theory exchange-correlation functional have been extraordinary successful, but calculating formation enthalpies of reactions involving compounds with both localized and delocalized electronic states remains challenging. In this work we examine the sh...
| Main Authors: | , , , , , , |
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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/1721.1/67053 |
| _version_ | 1826214616736202752 |
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| author | Jain, Anubhav Hautier, Geoffroy Ong, Shyue Ping Moore, Charles Jacob Fischer, Christopher C. Persson, Kristin A. Ceder, Gerbrand |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Jain, Anubhav Hautier, Geoffroy Ong, Shyue Ping Moore, Charles Jacob Fischer, Christopher C. Persson, Kristin A. Ceder, Gerbrand |
| author_sort | Jain, Anubhav |
| collection | MIT |
| description | Standard approximations to the density functional theory exchange-correlation functional have been extraordinary successful, but calculating formation enthalpies of reactions involving compounds with both localized and delocalized electronic states remains challenging. In this work we examine the shortcomings of the generalized gradient approximation (GGA) and GGA+U in accurately characterizing such difficult reactions. We then outline a methodology that mixes GGA and GGA+U total energies (using known binary formation data for calibration) to more accurately predict formation enthalpies. We demonstrate that for a test set of 49 ternary oxides, our methodology can reduce the mean absolute relative error in calculated formation enthalpies from approximately 7.7–21% in GGA+U to under 2%. As another example we show that neither GGA nor GGA+U alone accurately reproduces the Fe-P-O phase diagram; however, our mixed methodology successfully predicts all known phases as stable by naturally stitching together GGA and GGA+U results. As a final example we demonstrate how our technique can be applied to the calculation of the Li-conversion voltage of LiFeF[subscript 3]. Our results indicate that mixing energies of several functionals represents one avenue to improve the accuracy of total energy computations without affecting the cost of calculation. |
| first_indexed | 2024-09-23T16:08:38Z |
| format | Article |
| id | mit-1721.1/67053 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:08:38Z |
| publishDate | 2011 |
| publisher | American Physical Society |
| record_format | dspace |
| spelling | mit-1721.1/670532022-09-29T18:30:12Z Formation enthalpies by mixing GGA and GGA + U calculations Jain, Anubhav Hautier, Geoffroy Ong, Shyue Ping Moore, Charles Jacob Fischer, Christopher C. Persson, Kristin A. Ceder, Gerbrand Massachusetts Institute of Technology. Department of Materials Science and Engineering Ceder, Gerbrand Jain, Anubhav Hautier, Geoffroy Ong, Shyue Ping Moore, Charles Jacob Fischer, Christopher C. Persson, Kristin A. Ceder, Gerbrand Standard approximations to the density functional theory exchange-correlation functional have been extraordinary successful, but calculating formation enthalpies of reactions involving compounds with both localized and delocalized electronic states remains challenging. In this work we examine the shortcomings of the generalized gradient approximation (GGA) and GGA+U in accurately characterizing such difficult reactions. We then outline a methodology that mixes GGA and GGA+U total energies (using known binary formation data for calibration) to more accurately predict formation enthalpies. We demonstrate that for a test set of 49 ternary oxides, our methodology can reduce the mean absolute relative error in calculated formation enthalpies from approximately 7.7–21% in GGA+U to under 2%. As another example we show that neither GGA nor GGA+U alone accurately reproduces the Fe-P-O phase diagram; however, our mixed methodology successfully predicts all known phases as stable by naturally stitching together GGA and GGA+U results. As a final example we demonstrate how our technique can be applied to the calculation of the Li-conversion voltage of LiFeF[subscript 3]. Our results indicate that mixing energies of several functionals represents one avenue to improve the accuracy of total energy computations without affecting the cost of calculation. United States. Dept. of Energy (Grant DE-FG02-96ER4557) United States. Dept. of Energy (Grant DE-FG02-97ER25308) 2011-11-17T18:58:22Z 2011-11-17T18:58:22Z 2011-07 2011-04 Article http://purl.org/eprint/type/JournalArticle 1098-0121 1550-235X http://hdl.handle.net/1721.1/67053 Jain, Anubhav et al. “Formation enthalpies by mixing GGA and GGA + U calculations.” Physical Review B 84 (2011): n. pag. Web. 17 Nov. 2011. © 2011 American Physical Society en_US http://dx.doi.org/10.1103/PhysRevB.84.045115 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 | Jain, Anubhav Hautier, Geoffroy Ong, Shyue Ping Moore, Charles Jacob Fischer, Christopher C. Persson, Kristin A. Ceder, Gerbrand Formation enthalpies by mixing GGA and GGA + U calculations |
| title | Formation enthalpies by mixing GGA and GGA + U calculations |
| title_full | Formation enthalpies by mixing GGA and GGA + U calculations |
| title_fullStr | Formation enthalpies by mixing GGA and GGA + U calculations |
| title_full_unstemmed | Formation enthalpies by mixing GGA and GGA + U calculations |
| title_short | Formation enthalpies by mixing GGA and GGA + U calculations |
| title_sort | formation enthalpies by mixing gga and gga u calculations |
| url | http://hdl.handle.net/1721.1/67053 |
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