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

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. © the Owner Societies.

item.page.dc.description

Indexación Scopus

Keywords

Chemical Reactivity, Electronegativity, Parr

Citation

Physical Chemistry Chemical Physics, Volume 22, Issue 41, Pages 23553 - 235627 November 2020

DOI

10.1039/d0cp03228j

URI

http://repositorio.unab.cl/xmlui/handle/ria/20650

Collections

FCE - Artículos de Revista

Full item page