화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.100, No.14, 5721-5728, 1996
Activation Free-Energy of the Nonadiabatic Processes of Electron-Transfer and the Reorganization Energy of the Inhomogeneous Nonlocal Medium
On the basis of the quantum-mechanical theory for the kinetics of the elementary act of an electrochemical reaction, expressions for the activation free energy of the nonadiabatic processes of electron transfer and for the reorganization energy of the inhomogeneous nonlocal medium are obtained. The physical meaning of the reorganization parameters entering the expression for the transition probability is established. The concept of the reorganization energy depending on the symmetry factor is introduced. A number of the forms of the free energy functional of the inhomogeneous medium with arbitrary inertial and inertialess polarizations are presented. The results are compared with others in the literature and are illustrated by the simple example of an electron transfer process in the inhomogeneous medium.