Abstract
A generalized Anderson−Newns Hamiltonian is employed to model electrochemical electron transfer kinetics via a potential energy surface approach. Important novel features of this treatment are inclusion of the electrode induced broadening of the reactant level and the effect of solvent dynamics on the pre-exponential factor, which is determined by a numerical integration of the Kramers’ diffusion controlled barrier crossing rate expression. An interpolation scheme is provided to treat nonadiabatic, transition state theory adiabatic, and solvent dynamical effects in the weak coupling (nonadiabatic) and strong coupling (adiabatic) limits in a unified manner. The derived rate expressions are valid for arbitrary values of the electrode−reactant coupling term V, solvent polarization mode frequency ωr, and longitudinal solvent dielectric relaxation time τL. A comparison of the results obtained here with the earlier treatments of electron transfer reactions is presented, and the relevance of the present formalis...
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
