Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules
Density functional theory (DFT) is the method of choice for predicting structures and reaction energies of molecular systems. However, it remains a daunting task to systematically improve the accuracy of an approximate density functional. The recently proposed many-pair expansion (MPE) [Phys. Rev. B...
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| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2021
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| Online Access: | https://hdl.handle.net/1721.1/129453 |
| _version_ | 1811088631108993024 |
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| author | Zhu, Tianyu de Silva, Piotr Van Voorhis, Troy |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Zhu, Tianyu de Silva, Piotr Van Voorhis, Troy |
| author_sort | Zhu, Tianyu |
| collection | MIT |
| description | Density functional theory (DFT) is the method of choice for predicting structures and reaction energies of molecular systems. However, it remains a daunting task to systematically improve the accuracy of an approximate density functional. The recently proposed many-pair expansion (MPE) [Phys. Rev. B 2016, 93, 201108] is a density functional hierarchy that systematically corrects any deficiencies of an approximate functional to converge to the exact energy, and was shown to give accurate results for lattice models. In this work, we extend MPE to molecular systems and implement it using Gaussian basis sets. The self-attractive Hartree (SAH) decomposition [J. Chem. Theory Comput. 2018, 14, 92-103] is employed to generate localized v-representable pair densities for performing MPE calculations. We demonstrate that MPE at the second order (MPE2) already predicts accurate molecular and reaction energies for a series of small molecules and hydrogen chains, with the EXX functional as its starting point. We also show that MPE correctly describes the symmetric bond breaking in hydrogen rings, indicating its ability to remove strong correlation errors. MPE thus provides a promising framework to systematically improve density functional calculations of molecules. |
| first_indexed | 2024-09-23T14:05:03Z |
| format | Article |
| id | mit-1721.1/129453 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T14:05:03Z |
| publishDate | 2021 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1294532022-09-28T18:17:40Z Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules Zhu, Tianyu de Silva, Piotr Van Voorhis, Troy Massachusetts Institute of Technology. Department of Chemistry Density functional theory (DFT) is the method of choice for predicting structures and reaction energies of molecular systems. However, it remains a daunting task to systematically improve the accuracy of an approximate density functional. The recently proposed many-pair expansion (MPE) [Phys. Rev. B 2016, 93, 201108] is a density functional hierarchy that systematically corrects any deficiencies of an approximate functional to converge to the exact energy, and was shown to give accurate results for lattice models. In this work, we extend MPE to molecular systems and implement it using Gaussian basis sets. The self-attractive Hartree (SAH) decomposition [J. Chem. Theory Comput. 2018, 14, 92-103] is employed to generate localized v-representable pair densities for performing MPE calculations. We demonstrate that MPE at the second order (MPE2) already predicts accurate molecular and reaction energies for a series of small molecules and hydrogen chains, with the EXX functional as its starting point. We also show that MPE correctly describes the symmetric bond breaking in hydrogen rings, indicating its ability to remove strong correlation errors. MPE thus provides a promising framework to systematically improve density functional calculations of molecules. NSF (Grant CHE-1464804) 2021-01-19T20:59:17Z 2021-01-19T20:59:17Z 2019-02 2020-10-14T16:40:10Z Article http://purl.org/eprint/type/JournalArticle 1549-9626 1549-9618 https://hdl.handle.net/1721.1/129453 Zhu, Tianyu, Piotr de Silva, and Troy Van Voorhis. "Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules." Journal of Chemical Theory and Computation 15, 2 (February 2019): 1089-101 doi 10.1021/ACS.JCTC.8B01127 ©2019 Author(s) en 10.1021/ACS.JCTC.8B01127 Journal of Chemical Theory and Computation 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 Chemical Society (ACS) Prof. Van Voorhis via Ye Li |
| spellingShingle | Zhu, Tianyu de Silva, Piotr Van Voorhis, Troy Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules |
| title | Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules |
| title_full | Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules |
| title_fullStr | Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules |
| title_full_unstemmed | Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules |
| title_short | Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules |
| title_sort | implementation of the many pair expansion for systematically improving density functional calculations of molecules |
| url | https://hdl.handle.net/1721.1/129453 |
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