Abstract
We apply the concepts of quantum-statistical mechanics to the problem of pure charge transfer on electrodes. Using Zwanzig's projection-operator technique and making certain assumptions which are common in chemical kinetics we are able to generalize the linear response theory and derive a nonlinear response theory applicable to a certain class of phenomena. The application to charge transfer leads to a relation between current and overpotential, which differs qualitatively from the prediction of the absolute reaction-rate theory, the Butler-Volmer equation. Comparison with experiments seems to favour the present theory, but more precise measurements are needed before a decisive conclusion can be drawn.
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