A statistical thermodynamics view of electron density polarisation: application to chemical selectivity

文献情報

出版日 2020-09-21

DOI 10.1039/D0CP03228J

インパクトファクター 3.676

著者

Frédéric Guégan, Vincent Tognetti, Jorge I. Martínez-Araya, Henry Chermette, Lynda Merzoud, Alejandro Toro-Labbé, Christophe Morell

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要旨

A fundamental link between conceptual density functional theory and statistical thermodynamics is herein drawn, showing that intermolecular electrostatic interactions can be understood in terms of effective work and heat exchange. From a more detailed analysis of the heat exchange in a perturbation theory framework, an associated entropy can be subsequently derived, which appears to be a suitable descriptor for the local polarisability of the electron density. A general rule of thumb is evidenced: the more the perturbation can be spread, both through space and among the excited states, the larger the heat exchange and entropy.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

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