American Chemical Society
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Temperature-Dependent Approach to Electronic Charge Transfer

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journal contribution
posted on 2020-06-19, 06:34 authored by Marco Franco-Pérez, José L. Gázquez, Paul W. Ayers, Alberto Vela
A charge transfer model is developed within the framework of the grand canonical ensemble through the analysis of the behavior of the fractional charge as a function of the chemical potential of the bath when the temperature and the external chemical potential are kept fixed. Departing from the fact that, before the interaction between two species, each one has a zero fractional charge, one can identify two situations after the interaction occurs where the fractional charge of at least one of the species is different from zero, indicating that there has been charge transference. One of them corresponds to the case when one of the species is immersed in a bath conformed by the other one, while the other is related to the case in which both species are present in equal amounts (stoichiometric proportion). Correlations between the fractional charges and average energies, thus obtained with experimental equilibrium constants, kinetic rate constants, hydration constants, and bond enthalpies, indicate that, although at the experimental temperatures, they are very small quantities, they have chemically meaningful information. Additionally, in the stoichiometric case, one also finds a rather good correlation between the equalized chemical potential and the one obtained from experimental information for a test set of diatomic and triatomic molecules.