Leduc Théo, Aubert Emmanuel, Espinosa Enrique, Jelsch Christian, Iordache Cristian, Guillot Benoît
Université de Lorraine, CNRS, CRM2 , F-54000 Nancy , France.
J Phys Chem A. 2019 Aug 15;123(32):7156-7170. doi: 10.1021/acs.jpca.9b05051. Epub 2019 Aug 4.
Polarizability is a key molecular property involved in either macroscopic (i.e., dielectric constant) and microscopic properties (i.e., interaction energies). In rigid molecules, this property only depends on the ability of the electron density (ED) to acquire electrostatic moments in response to applied electric fields. Databases of transferable electron density fragments are a cheap and efficient way to access molecular EDs. This approach is rooted in the relative conservation of the atomic ED between different molecules, termed transferability principle. The present work discusses the application of this transferability principle to the polarizability, an electron density-derived property, partitioned in atomic contributions using the Quantum Theory of Atoms In Molecules topology. The energetic consequences of accounting for in situ deformation (polarization) of database multipolar atoms are investigated in detail by using a high-quality quantum chemical benchmark.
极化率是一个关键的分子性质，涉及宏观性质（即介电常数）和微观性质（即相互作用能）。在刚性分子中，该性质仅取决于电子密度（ED）响应外加电场而获得静电矩的能力。可转移电子密度片段数据库是获取分子ED的一种廉价且高效的方法。这种方法基于不同分子间原子ED的相对守恒，即所谓的可转移原理。本工作讨论了这种可转移原理在极化率方面的应用，极化率是一种源自电子密度的性质，利用分子中的原子量子理论拓扑将其划分为原子贡献。通过使用高质量的量子化学基准，详细研究了考虑数据库多极原子原位变形（极化）的能量后果。
