A reference-free stockholder partitioning method based on the force on electrons
© 2017 Wiley Periodicals, Inc.
| Publié dans: | Journal of computational chemistry. - 1984. - 39(2018), 17 vom: 30. Juni, Seite 1044-1050 |
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| Auteur principal: | |
| Autres auteurs: | , , , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2018
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| Accès à la collection: | Journal of computational chemistry |
| Sujets: | Journal Article atoms in molecules conceptual density functional theory ehrenfest force hirshfeld partitioning linear response function softness kernel stockholder population analysis |
| Résumé: | © 2017 Wiley Periodicals, Inc. We argue that when one divides a molecular property into atom-in-a-molecule contributions, one should perform the division based on the property density of the quantity being partitioned. This is opposition to the normal approach, where the electron density is given a privileged role in defining the properties of atoms-in-a-molecule. Because partitioning each molecular property based on its own property density is inconvenient, we design a reference-free approach that does not (directly) refer atomic property densities. Specifically, we propose a stockholder partitioning method based on relative influence of a molecule's atomic nuclei on the electrons at a given point in space. The resulting method does not depend on an "arbitrary" choice of reference atoms and it has some favorable properties, including the fact that all of the electron density at an atomic nucleus is assigned to that nucleus and the fact all the atoms in a molecule decay at a uniform asymptotic rate. Unfortunately, the resulting model is not easily applied to spatially degenerate ground states. Furthermore, the practical realizations of this strategy that we tried here gave disappointing numerical results. © 2017 Wiley Periodicals, Inc |
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| Description: | Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.25114 |