Second-order surface phase transitions in electrode kinetics

A theory, based on the Landau-Ginzburg formalism, shows that remarkable singularities in currents of electrode charge transfer reactions occur near the critical potentials where second-order surface phase transitions take place. This happens if the fluctuations of the order parameter, which describes the transition, are exponentially coupled to the reaction system via fluctuating tunneling or activation barriers. Coupling depending on the sign of the order parameter is considered; the corresponding singularities in Arrhenius and Tafel plots for electrode currents are predicted, and the perspectives for their experimental investigation are discussed.