Abstract

An earlier major investigation of solvent effects upon the kinetics for the forward electron transfer by the porphyrin-amidoquinone molecule reported substantial changes in rate constants in going from aprotic dipolar to hydrogen bonding media. Such changes were interpreted previously in semiquantitative terms by using the Marcus theory for solvent reorganizational energy contributions to a Franck-Condon transition for the electron transfer. The original kinetics data have now been reexamined with respect to solvent type and an alternate solvation free energy model related to the Lay extension of the Marcus theory has been proposed.

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