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

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

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

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.

Original languageEnglish
Pages (from-to)23553-23562
Number of pages10
JournalPhysical chemistry chemical physics : PCCP
Volume22
Issue number41
DOIs
Publication statusPublished - 28 Oct 2020

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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