A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to electron transf...A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to electron transfer system.The activation parameter and activation energy of the system are obtained via the activation model. The slopes of the potential energy surfaces (curves) of the reacting system at the separated reactants are calculated from the fitted potential energy curves. The coupling matrix element is determined by using the perturbation theory and numerical integral method. Theoretical rate constants are obtained for the system at both UHF/6- 311G and UMP2/6- 311G levels.The agreement of the theoretical results with experimetal values is excellent.This fact indicates the scheme proposed is feasible and accurate in studying the self- exchange eletron transfer reaction.展开更多
文摘A theoretical scheme is presented which is based on an activation model for calculating the rate of the electron- exchange reaction between transition metal complexes in aqueous solution and applies to electron transfer system.The activation parameter and activation energy of the system are obtained via the activation model. The slopes of the potential energy surfaces (curves) of the reacting system at the separated reactants are calculated from the fitted potential energy curves. The coupling matrix element is determined by using the perturbation theory and numerical integral method. Theoretical rate constants are obtained for the system at both UHF/6- 311G and UMP2/6- 311G levels.The agreement of the theoretical results with experimetal values is excellent.This fact indicates the scheme proposed is feasible and accurate in studying the self- exchange eletron transfer reaction.
