Quantum chemical modelling of the heterogeneous electron transfer: from qualitative analysis to a polarization curve

State-of-the-art in the field of quantum chemical modelling of the heteroge neous electron transfer processes is reviewed. Novel approaches originating from interplay between quantum chemistry and modern theory of charge trans fer ale discussed and illustrated by recent results on the calculation of r elevant kinetic parameters for various electrochemical systems. Emphasis is made on the modelling of the inner-sphere reorganization and the works of approach, as well as on the consideration of reaction layer as an orientati onal ensemble of reagents. Recent approaches to the estimation of electroni c transmission coefficient are analyzed. A possibility to employ traditiona l phenomenological theory to the analysis of experimental data is re-examin ed in the framework of microscopic treatment. (C) 2000 Elsevier Science Ltd . All rights reserved.