Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments
Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method calle...
| Main Authors: | , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
Journal of Chemical Theory and Computation
2018
|
| Online Access: | http://hdl.handle.net/1721.1/119508 https://orcid.org/0000-0002-4985-7350 https://orcid.org/0000-0003-2061-3237 https://orcid.org/0000-0001-7111-0176 |
| _version_ | 1826199934243700736 |
|---|---|
| author | de Silva, Piotr Zhu, Tianyu Van Voorhis, Troy |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry de Silva, Piotr Zhu, Tianyu Van Voorhis, Troy |
| author_sort | de Silva, Piotr |
| collection | MIT |
| description | Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding. |
| first_indexed | 2024-09-23T11:28:25Z |
| format | Article |
| id | mit-1721.1/119508 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T11:28:25Z |
| publishDate | 2018 |
| publisher | Journal of Chemical Theory and Computation |
| record_format | dspace |
| spelling | mit-1721.1/1195082022-09-27T19:46:44Z Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments de Silva, Piotr Zhu, Tianyu Van Voorhis, Troy Massachusetts Institute of Technology. Department of Chemistry Voorhis, Troy Van de Silva, Piotr Zhu, Tianyu Van Voorhis, Troy Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding. National Science Foundation (U.S.) (Grant CHE-1464804) David & Lucile Packard Foundation 2018-12-11T20:17:04Z 2018-12-11T20:17:04Z 2017-12 2017-09 Article http://purl.org/eprint/type/JournalArticle 1549-9618 1549-9626 http://hdl.handle.net/1721.1/119508 Zhu, Tianyu, Piotr de Silva, and Troy Van Voorhis. “Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments.” Journal of Chemical Theory and Computation 14, no. 1 (December 26, 2017): 92–103. https://orcid.org/0000-0002-4985-7350 https://orcid.org/0000-0003-2061-3237 https://orcid.org/0000-0001-7111-0176 en_US http://dx.doi.org/10.1021/acs.jctc.7b00931 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 Journal of Chemical Theory and Computation Prof. Van Voorhis via Erja Kajosalo |
| spellingShingle | de Silva, Piotr Zhu, Tianyu Van Voorhis, Troy Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments |
| title | Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments |
| title_full | Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments |
| title_fullStr | Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments |
| title_full_unstemmed | Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments |
| title_short | Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments |
| title_sort | self attractive hartree decomposition partitioning electron density into smooth localized fragments |
| url | http://hdl.handle.net/1721.1/119508 https://orcid.org/0000-0002-4985-7350 https://orcid.org/0000-0003-2061-3237 https://orcid.org/0000-0001-7111-0176 |
| work_keys_str_mv | AT desilvapiotr selfattractivehartreedecompositionpartitioningelectrondensityintosmoothlocalizedfragments AT zhutianyu selfattractivehartreedecompositionpartitioningelectrondensityintosmoothlocalizedfragments AT vanvoorhistroy selfattractivehartreedecompositionpartitioningelectrondensityintosmoothlocalizedfragments |