ELECTRONIC STATE DENSITIES OF FERROCENE AND ANTHRACENE IN NONAQUEOUS SOLVENTS DETERMINED BY ELECTROCHEMICAL TUNNELING SPECTROSCOPY

One-electron oxidations of ferrocene and anthracene to the corresponding radical cations have been used as model systems for studying solvent effects in heterogeneous charge-transfer kinetics. The energy dependencies of the electronic state densities of the reactants in several nonaqueous solvents have been investigated. The energy dependence of the state density of anthracene has shown a gaussian-shaped distribution function, whereas that of ferrocene has shown nongaussian distribution characterized by two reorganization energies. In the latter case, the reorganization energy corresponding to the main peak of the distribution function has been found to be correlated with the donor numer of the solvents, indicating the presence of a new inner-shell reorganization based on the donor-acceptor interaction. The two types of reorganization processes have been attributed to the solvation sites peculiar to the shape of the ferrocene molecule. copyright. © 1990, The Electrochemical Society, Inc. All rights reserved.