Adiabatic electrochemical electron-transfer reactions involving frequency changes of inner-sphere modes

被引：21
|
作者：
Schmickler, W [1 ]
Koper, MTM
机构：
[1] Univ Ulm, Abt Elektrochem, D-89069 Ulm, Germany
[2] Eindhoven Univ Technol, Schuit Inst Catalysis, Inorgan Chem & Catalysis Lab, NL-5600 MB Eindhoven, Netherlands
来源：
ELECTROCHEMISTRY COMMUNICATIONS | 1999年 / 1卷 / 09期
关键词：
electron-transfer reactions; free energy surfaces; transfer coefficients; frequency changes;
D O I：
10.1016/S1388-2481(99)00087-9
中图分类号：
O646 [电化学、电解、磁化学];
学科分类号：
081704 ;
摘要：
A Hamiltonian model is formulated for electrochemical electron-transfer reactions involving frequency changes of the inner-sphere modes. The adiabatic free energy surface is calculated and it is shown that this nonlinear coupling leads to a transfer coefficient different from 1/2, and that the transfer coefficient can no longer be identified with the electron occupation probability in the transition state saddle point, as in the linear coupling case. (C) 1999 Elsevier Science S.A. All rights reserved.
引用
收藏
页码：402 / 405
页数：4
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