Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments,Journal of Chemical Theory and Computation

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Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2017-12-26 00:00:00 , DOI: 10.1021/acs.jctc.7b00931
Tianyu Zhu ₁ , Piotr de Silva ₁ , Troy Van Voorhis ₁

Affiliation

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.

中文翻译：

自吸引式Hartree分解：将电子密度划分为平滑的局部碎片

化学键在化学的描述和理解中起着核心作用。已经提出了许多方法来从量子化学计算中提取有关键的信息，其中大多数方法是利用分子轨道作为基本的描述子。在这里，我们提出一种称为自吸引哈特里（SAH）分解的方法，以直接从电子密度中解散电子对，这与分子轨道不同，是一种可以通过实验获得的明确定义的观测值。关键思想是将密度划分为一个单电子碎片的总和，这些碎片可以同时使自排斥最大化并保持规则的形状。这导致了一组相当不寻常的方程式，其中每个电子除了具有所有电子共有的外部电势之外，还具有自吸引的Hartree电势。产生的对称性破坏和局部化与化学直觉出乎意料地一致。由于片段密度的平滑特性，SAH分解还可以有效显示单个/多个键，孤对和不寻常的键。此外，我们证明了它可以用于鉴定分子复合物中的特定化学键，并提供简单而准确的氢键静电模型。

更新日期：2017-12-26

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