Guégan F.Tognetti V.Martínez-Araya J.I.Chermette H.Merzoud L.Toro-Labbé A.Morell C.2021-10-262021-10-262020-11Physical Chemistry Chemical Physics, Volume 22, Issue 41, Pages 23553 - 235627 November 202014639076http://repositorio.unab.cl/xmlui/handle/ria/20650Indexación ScopusA 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.enChemical ReactivityElectronegativityParrArtículo10.1039/d0cp03228j