A model of the surface molecule for adiabatic electrochemical electron transfer including electron correlation effects: the exact solution

A theory of the adiabatic interfacial electron transfer reactions is presen ted based on the exactly solvable surface molecule limit of the Anderson-Ne wns model. Unlike the other papers on this subject, the electron correlatio n effects are taken into account from the very beginning and exactly. It is shown that the electron correlation effects play an important role in the region of parameters describing adiabatic electron transfer and lead not on ly to quantitative corrections to the results obtained earlier in the spinl ess model or in the Hartree-Fock approximation but also to new qualitative effects. The critical regions, which correspond to different types of elect ron transfer processes, are obtained within the space of parameters of the model and classified. The corresponding kinetic regime diagram is construct ed and presented. Examples of the adiabatic Gibbs energy surfaces for a num ber of characteristic, electrochemical electron transfer reactions are give n and discussed. (C) 2001 Elsevier Science B.V. All rights reserved.