Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments
Name
Zhu18JCTC.pdf
Size
26.86 MB
Format
Adobe PDF
Checksum (MD5)
2ebc70f4ce81bd2dd5fcb7383d007415
Author(s)
de Silva, Piotr
Zhu, Tianyu
Van Voorhis, Troy
Date Issued
December 2017
Journal
Journal of Chemical Theory and Computation
Publisher
Journal of Chemical Theory and Computation
Citation
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.
Version
Author's final manuscript
Abstract
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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
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.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/acs.jctc.7b00931
