Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments

Tianyu Zhu, Piotr de Silva, Troy Van Voorhis

Research output: Contribution to journalJournal articleResearchpeer-review

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, 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 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 which simultaneously maximize 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.
Original languageEnglish
JournalJournal of Chemical Theory and Computation
Number of pages37
ISSN1549-9618
DOIs
Publication statusAccepted/In press - 2017
Externally publishedYes

Cite this

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title = "Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments",
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, 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 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 which simultaneously maximize 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.",
author = "Tianyu Zhu and {de Silva}, Piotr and Voorhis, {Troy Van}",
year = "2017",
doi = "10.1021/acs.jctc.7b00931",
language = "English",
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Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments. / Zhu, Tianyu ; de Silva, Piotr; Voorhis, Troy Van.

In: Journal of Chemical Theory and Computation, 2017.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments

AU - Zhu, Tianyu

AU - de Silva, Piotr

AU - Voorhis, Troy Van

PY - 2017

Y1 - 2017

N2 - 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, 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 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 which simultaneously maximize 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.

AB - 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, 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 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 which simultaneously maximize 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.

U2 - 10.1021/acs.jctc.7b00931

DO - 10.1021/acs.jctc.7b00931

M3 - Journal article

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

ER -