Sorting Out the Effects of Electron-Transfer Distance,the Electrical Double Layer and the Inner Reorganization Energy in Heterogeneous Electron-Transfer Reactions of Organic Compounds

摘要

The most easily studied electron-transfer reactions of neutral organic compounds are those that occur at relatively mild potentials,i.e.,potentials that are not too close to the cathodic or andodic potential limit.Most such compounds feature delocalization of charge in the radical ions (lowering the outer reorganization energy) and quite minor changes in structure (lowering the inner reorganization energy).Consequently,the electron-transfer reactions are quite facile and it is experimentally difficult to obtain reliable values of the electron-transfer rate constants,k_s,which are large.