Journal of Physical Chemistry B, Vol.101, No.16, 3168-3173, 1997
Temperature-Dependence of the Transfer-Coefficient of Simple Electrochemical Redox Reactions Due to Slow Solvent Dynamics
It is shown that for simple electrochemical redox reactions in which both outer- and inner-sphere modes are reorganized, the transfer coefficient alpha may decrease with increasing temperature if the solvent dynamics along the outer-sphere coordinate is sufficiently slow. A similar trend is observed for the activation energy, The effect is due to a change in the most effective reaction path with temperature and is intimately related to the phenomenon of saddle-point avoidance. It is also shown that the effect enhances the potential dependence of the transfer coefficient.
Keywords:ELECTRON-TRANSFER REACTIONS;ACTIVATED RATE-PROCESSES;SADDLE-POINT AVOIDANCE;KRAMERS;BARRIER;PARAMETERS;INTERFACE;STATES