ASYMMETRY OF INNER-SPHERE REORGANIZATION ENERGY FOR HETEROGENEOUS ELECTRON-TRANSFER

The approach to the calculation of the activation energy of electroche mical charge transfer is considered for systems characterized by asymm etry of inner-sphere reorganization (i.e. by the difference in inner-s phere reorganization energies for direct and reverse reactions). Model calculations are carried out and the region of parameters is evaluate d for which the effect is pronounced. A quantum-chemical analysis of i nner-sphere reorganization is presented for four cobalt and chromium c helate aminocarboxylate complexes and the corresponding contribution t o activation energy is discussed in connection with the difference in rate constants. (C) 1998 Elsevier Science S.A. All rights reserved.