Temperature dependence of the electronic factor in the nonadiabatic electron transfer at metal and semiconductor electrodes

The temperature dependence of the electronic contribution to the nonadiabat ic electron transfer rate constant (k(ET)) at metal electrodes is discussed . It is found in these calculations that this contribution is proportional to the absolute temperature T. A simple interpretation is given. We also co nsider the nonadiabatic rate constant for electron transfer at a semiconduc tor electrode. Under conditions for the maximum rate constant, the electron ic contribution is also estimated to be proportional to T, but for differen t reasons than in the case of metals (Boltzmann statistics and transfer at the conduction band edge for the semiconductor versus Fermi-Dirac statistic s and transfer at the Fermi level, which is far from the band edge, of the metal). (C) 2001 Elsevier Science B.V. All rights reserved.