Phys Chem Chem Phys. 2017 May 10;19(18):11588-11602. doi: 10.1039/c7cp00224f.

Going beyond the three-state ensemble model: the electronic chemical potential and Fukui function for the general case.

Physical chemistry chemical physics : PCCP

Marco Franco-Pérez, Farnaz Heidar-Zadeh, Paul W Ayers, José L Gázquez, Alberto Vela

PMID: 28429010 DOI: 10.1039/c7cp00224f

Abstract

Making use of the grand canonical ensemble the derivation of the analytical equations for the chemical potential and the Fukui function in the general case of any number of ground and excited states is presented. The expressions thus obtained allow one to establish that the ensemble of three consecutive ground states that has been usually used to analyze the effects of temperature in these quantities provides a satisfactory description for them at temperatures of chemical interest. Nevertheless, some situations must be considered cautiously, as for example, when the N + k and N + k + 1 (N is the electron number) ground states are (nearly) quasidegenerate or when the first excited state of both the anion and the cation (with respect to the reference state) is very low in energy. Results for the copper atom (with the ground state of Cu

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• Journal Article