Adiabatic electron transfer: comparison of modified theory with experiment.

Abstract

The radical cations of properly designed bishydrazines allow comparison of observed and calculated electron transfer rate constants. These compounds have rate constants small enough to be measured by dynamic electron spin resonance spectroscopy and show charge transfer bands corresponding to vertical excitation from the energy well for the charge occurring upon one hydrazine unit to that for the electron-transferred species. Analysis of the data for all six compounds studied indicates that the shape of the adiabatic surface on which electron transfer occurs can be obtained from the charge transfer band accurately enough to successfully predict the electron transfer rate constant and that explicit tunneling corrections are not required for these compounds.