Quantum mechanical theory of electron transfer reactions at metal electrodes

The quantum theory of electron transfer reactions at metal electrodes was studied. The obtained potential dependence of the electron transfer rate in the weak coupling case resembles the Butler-Volmer equation of classical electrochemistry. The volcano-shaped dependence of the hydrogen exchange current on the adsorption energy of hydrogen on various metals was explained microscopically, based on this theory. The mechanism of hydrogen evolution was also explained microscopically based on this theory. The exchange current density for hydrogen evolution at Pt electrode calculated quantitatively agreed well with the experimental value.