Schemes for calculating the Faradaic current in the electron transfer reaction: Treatment outside quadratic relationships for the activation barrier

Simple schemes are proposed for calculating relations of the free energy fo r electron transfer reactions in the bulk solution and on the electrode. Fo r electrochemical reactions, these relations represent corrected Tafel depe ndences. The derived relations make it possible to take into account variat ion in vibrational frequencies, anharmonicity of vibrations, and quantum ef fects for local vibrational degrees of freedom using standard computer prog rams.