Atom-Based Bootstrap Embedding For Molecules
Recent developments in quantum embedding have offered an attractive approach to describing electron correlation in molecules. However, previous methods such as density matrix embedding theory (DMET) require rigid partitioning of the system into fragments, which creates significant ambiguity for mole...
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| Format: | Article |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/128160 |
| _version_ | 1826211740825681920 |
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| author | Ye, Hongzhou Van Voorhis, Troy |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Ye, Hongzhou Van Voorhis, Troy |
| author_sort | Ye, Hongzhou |
| collection | MIT |
| description | Recent developments in quantum embedding have offered an attractive approach to describing electron correlation in molecules. However, previous methods such as density matrix embedding theory (DMET) require rigid partitioning of the system into fragments, which creates significant ambiguity for molecules. Bootstrap embedding (BE) is more flexible because it allows overlapping fragments, but when done on an orbital-by-orbital basis, BE introduces ambiguity in defining the connectivity of the orbitals. In this Letter, we present an atom-based fragment definition that significantly augments BE’s performance in molecules. The resulting method, which we term atom-based BE, is very effective at recovering valence electron correlation in moderate-sized bases and delivers near-chemical-accuracy results using extrapolation. We anticipate atom-based BE may lead to a low-scaling and highly accurate approach to electron correlation in large molecules. |
| first_indexed | 2024-09-23T15:10:42Z |
| format | Article |
| id | mit-1721.1/128160 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T15:10:42Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1281602022-09-29T13:12:37Z Atom-Based Bootstrap Embedding For Molecules Ye, Hongzhou Van Voorhis, Troy Massachusetts Institute of Technology. Department of Chemistry Recent developments in quantum embedding have offered an attractive approach to describing electron correlation in molecules. However, previous methods such as density matrix embedding theory (DMET) require rigid partitioning of the system into fragments, which creates significant ambiguity for molecules. Bootstrap embedding (BE) is more flexible because it allows overlapping fragments, but when done on an orbital-by-orbital basis, BE introduces ambiguity in defining the connectivity of the orbitals. In this Letter, we present an atom-based fragment definition that significantly augments BE’s performance in molecules. The resulting method, which we term atom-based BE, is very effective at recovering valence electron correlation in moderate-sized bases and delivers near-chemical-accuracy results using extrapolation. We anticipate atom-based BE may lead to a low-scaling and highly accurate approach to electron correlation in large molecules. NSF (Grant CHE-1464804) 2020-10-23T16:06:27Z 2020-10-23T16:06:27Z 2019-10 2019-08 Article http://purl.org/eprint/type/JournalArticle 1948-7185 https://hdl.handle.net/1721.1/128160 Ye, Hongzhou and Troy Van Voorhis. "Atom-Based Bootstrap Embedding For Molecules." Journal of Physical Chemistry Letters 10, 20 (October 2019): 6368–6374 © 2019 American Chemical Society https://pubs.acs.org/doi/10.1021/acs.jpclett.9b02479 Journal of Physical Chemistry Letters 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 |
| spellingShingle | Ye, Hongzhou Van Voorhis, Troy Atom-Based Bootstrap Embedding For Molecules |
| title | Atom-Based Bootstrap Embedding For Molecules |
| title_full | Atom-Based Bootstrap Embedding For Molecules |
| title_fullStr | Atom-Based Bootstrap Embedding For Molecules |
| title_full_unstemmed | Atom-Based Bootstrap Embedding For Molecules |
| title_short | Atom-Based Bootstrap Embedding For Molecules |
| title_sort | atom based bootstrap embedding for molecules |
| url | https://hdl.handle.net/1721.1/128160 |
| work_keys_str_mv | AT yehongzhou atombasedbootstrapembeddingformolecules AT vanvoorhistroy atombasedbootstrapembeddingformolecules |