Electrochemical electron transfer: Accounting for electron–hole excitations in the metal electrode
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Abstract
The transfer of an electron from a metal electrode to an ion in a polar liquid is probably the most important process in electrochemistry. As the electrons in the metal have a continuum of allowed energy levels, this transfer may be accompanied by the creation/annihilation of electron–hole excitations in the metal. Calculation of the rate of electron transfer, with these excitations and the solvent accounted for properly is a difficult problem to treat using the usual approaches of molecular reaction dynamics, as one now has a continuum of potential energy surfaces, on which the dynamics has to be considered. We suggest an approach in which the electron–hole excitations are treated as bosons. Using this, we have derived an expression for the rate, which accounts both for solvent dynamics and electron–hole excitations. Our analysis amounts to a solution of the problem of calculating the electronic transmission coefficient κ, for a continuum of crossing diabatic surfaces. Calculations of the rate using our ...