Browsing by Author "Chermette H."

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    A statistical thermodynamics view of electron density polarisation: Application to chemical selectivity
    (Royal Society of Chemistry, 2020-11) Guégan F.; Tognetti V.; Martínez-Araya J.I.; Chermette H.; Merzoud L.; Toro-Labbé A.; Morell C.
    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.