title: Reorganization energy and pre-exponential factor from temperature-dependent experiments in electron transfer reactions. A typical example: the reduction of tert-nitrobutane.
abstract: The electrochemical one-electron reduction of tert-nitrobutane in N,N'-dimethylformamide is a typical reaction, which has been shown to follow the quadratic model of outersphere electron transfer. The variation of the standard rate constant with temperature allows a separate determination of the reorganization energy and of the pre-exponential factor. The value found for the former is in agreement with independent estimates of the solvent and intramolecular reorganization energies. The value of the latter, significantly larger than the collision frequency, implies that the reaction starts to take place before close contact with the electrode surface.
authors.affiliation: Univ Paris Diderot, Sorbonne Paris Cité, Laboratoire d'Electrochimie Moléculaire, UMR 7591 CNRS, 15 rue Jean-Antoine de Baïf, F-75205 Paris Cedex 13, France.
authors.forename: Cyrille
authors.initials: C
authors.lastname: Costentin
authors.forename: Cyril
authors.initials: C
authors.lastname: Louault
authors.forename: Marc
authors.initials: M
authors.lastname: Robert
authors.forename: Vincent
authors.initials: V
authors.lastname: Rogé
authors.forename: Jean-Michel
authors.initials: JM
authors.lastname: Savéant