Revisiting electroaccepting and electrodonating powers: proposals for local electrophilicity and local nucleophilicity descriptors

Abstract : The electrophilicity index, mu(2)/2 eta, where mu is the chemical potential and eta is the hardness, has been defined by Parr, Von Szentpaly, and Liu (J. Am. Chem. Soc., 1999, 121, 1922) as the lowering in energy of an electronic system during a process in which the chemical potential of the system raises from mu to zero, accepting -mu/eta electrons. In this work, it is shown that the electrophilicity index is also a rational choice for measuring nucleophilicity. Indeed, within the grand canonical ensemble, when the chemical potential of a system increases from mu to zero, the system gives away mu/eta electrons. During the process, the variation of the grand potential is mu(2)/2 eta. Additionally, through the use of a second order Taylor series expansion of the density as a function of the number of electrons, at constant external potential, which depends on the Fukui function and the dual descriptor, the local electrophilicity is defined as the actual variation of the electron density when the system acquires -mu/eta electrons, while the local nucleophilicity is similarly defined for the case when the system loses mu/eta electrons.
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Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2014, 16 (48), pp.26832-26842. 〈10.1039/c4cp03167a〉
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Contributeur : Agnès Bussy <>
Soumis le : mardi 17 novembre 2015 - 18:56:18
Dernière modification le : lundi 8 octobre 2018 - 20:32:01

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Christophe Morell, Jose L Gazquez, Alberto Vela, Frédéric Guégan, Henry Chermette. Revisiting electroaccepting and electrodonating powers: proposals for local electrophilicity and local nucleophilicity descriptors. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2014, 16 (48), pp.26832-26842. 〈10.1039/c4cp03167a〉. 〈hal-01230136〉

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