A statistical thermodynamics view of electron density polarisation: application to chemical selectivity. Issue 41 (19th October 2020)

• Record Type: Journal Article
• Authors: Guégan, Frédéric; Tognetti, Vincent; Martínez-Araya, Jorge I.; Chermette, Henry; Merzoud, Lynda; Toro-Labbé, Alejandro; Morell, Christophe
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 41(2020)
• Page Start: 23553
• Page End: 23562
• Publication Date: 2020-10-19
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp03228j
• Languages: English
• ISSNs: 1463-9076

Abstract

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. 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.