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Issue 41, 2020
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A statistical thermodynamics view of electron density polarisation: application to chemical selectivity

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Abstract

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.

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

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Article information


Submitted
16 Jun 2020
Accepted
16 Sep 2020
First published
21 Sep 2020

This article is Open Access

Phys. Chem. Chem. Phys., 2020,22, 23553-23562
Article type
Paper

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

F. Guégan, V. Tognetti, J. I. Martínez-Araya, H. Chermette, L. Merzoud, A. Toro-Labbé and C. Morell, Phys. Chem. Chem. Phys., 2020, 22, 23553
DOI: 10.1039/D0CP03228J

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