The use of calculated reorganization energies in experimental electrochemical kinetics

Abstract

Calculated reorganization energies in solution using the polarizable continuum model implemented in Gaussian 03 are compared to experimental values of the heterogeneous rate constants for the reduction of a wide variety of neutral molecules in dimethylformamide. The calculated reorganization energies are fully consistent with the experimental data; the computational procedure may in fact be quite useful for estimating the reorganization energies for outer-sphere electrochemical reactions. From the comparison between the calculated reorganization energy values and the experimental values for the heterogeneous rate constants, the adiabaticity of the redox couples' is discussed.