dorsal/arxiv
View SchemaUsing molecular similarity to construct accurate semiempirical electron structure theories
| Authors | Benjamin G. Janesko, David Yaron |
|---|---|
| Categories | |
| ArXiv ID | physics/0311091 |
| URL | https://arxiv.org/abs/physics/0311091 |
| DOI | 10.1063/1.1785771 |
| Journal | Journal of Chemical Physics, 121 (12), 5635-5645 (2004) |
Abstract
Ab initio electronic structure methods give accurate results for small systems, but do not scale well to large systems. Chemical insight tells us that molecular functional groups will behave approximately the same way in all molecules, large or small. This molecular similarity is exploited in semiempirical methods, which couple simple electronic structure theories with parameters for the transferable characteristics of functional groups. We propse that high-level calculations on small molecules provide a rich source of parametrization data. In principle, we can select a functional group, generate a large amount of ab initio data on the group in various small-molecule environments, and "mine" this data to build a sophisticated model for the group's behavior in large molecules. This work details such a model for electron correlation: a semiempirical, subsystem-based correlation functional that predicts a subsystem's two-electron density as a functional of its one-electron density. This model is demonstrated on two small systems: chains of linear, minimal-basis (H-H)5, treated as a sum of four overlapping (H-H)2 subsystems; and the aldehyde group of a set of HOC-R molecules. The results provide an initial demonstration of the feasibility of this approach.
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"abstract": "Ab initio electronic structure methods give accurate results for small\nsystems, but do not scale well to large systems. Chemical insight tells us that\nmolecular functional groups will behave approximately the same way in all\nmolecules, large or small. This molecular similarity is exploited in\nsemiempirical methods, which couple simple electronic structure theories with\nparameters for the transferable characteristics of functional groups. We propse\nthat high-level calculations on small molecules provide a rich source of\nparametrization data. In principle, we can select a functional group, generate\na large amount of ab initio data on the group in various small-molecule\nenvironments, and \"mine\" this data to build a sophisticated model for the\ngroup\u0027s behavior in large molecules. This work details such a model for\nelectron correlation: a semiempirical, subsystem-based correlation functional\nthat predicts a subsystem\u0027s two-electron density as a functional of its\none-electron density. This model is demonstrated on two small systems: chains\nof linear, minimal-basis (H-H)5, treated as a sum of four overlapping (H-H)2\nsubsystems; and the aldehyde group of a set of HOC-R molecules. The results\nprovide an initial demonstration of the feasibility of this approach.",
"arxiv_id": "physics/0311091",
"authors": [
"Benjamin G. Janesko",
"David Yaron"
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1063/1.1785771",
"journal_ref": "Journal of Chemical Physics, 121 (12), 5635-5645 (2004)",
"title": "Using molecular similarity to construct accurate semiempirical electron structure theories",
"url": "https://arxiv.org/abs/physics/0311091"
},
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