On the theory of electron transfer reactions at semiconductor/liquid interfaces. II. A free electron model

Electron transfer reactions at semiconductor/liquid interfaces are studied using the Fermi Golden rule and a free electron model for the semiconductor and the redox molecule. Bardeen's method is adapted to calculate the coupl ing matrix element between the molecular and semiconductor electronic state s where the effective electron mass in the semiconductor need not equal the actual electron mass. The calculated maximum electron transfer rate consta nts are compared with the experimental results as well as with the theoreti cal results obtained in Part I using tight-binding calculations. The result s, which are analytic for an s-electron in the redox agent and reduced to a quadrature for p(z)- and d(z)(2)-electrons, add to the insight of the earl ier calculations. (C) 2000 American Institute of Physics. [S0021-9606(00)70 739-2].