Asymmetric Marcus theory: Application to electrode kinetics
Asymmetric Marcus theory: Application to electrode kinetics
复制标题
DOI：
10.1016/j.jelechem.2011.12.011
复制
发表时间：
2012-02-15
影响因子：
4.5
通讯作者：
Compton, Richard G.
中科院分区：
文献类型：
--
作者：
Laborda, Eduardo;Henstridge, Martin C.;Compton, Richard G.
用简单的Marcus-Hush （MH）形式拟合不同溶液氧化还原对的伏安实验响应是不成功的。迄今为止，这些和其他实验偏差暂时归因于氧化态和还原态的力常数的差异。因此，我们报告了不对称形式马库斯理论在电极反应动力学伏安研究中的应用。由此产生的四参数模型解释了内壳力常数值的差异，并对电极上电子转移过程的变化提供了更深入的了解。考察了电化学速率常数随外加电位的变化，发现与简单MH模型的实验偏差一致。进一步报道了不对称模型在循环伏安法和方波伏安法中的应用。(C) 2011 Elsevier B.V.版权所有
The application of the simple Marcus-Hush (MH) formalism to fit the voltammetric experimental response of various solution-phase redox couples is unsuccessful. These and other experimental deviations have hitherto been tentatively attributed to differences of the force constants of the oxidized and reduced species. Accordingly, we report application of the asymmetric form of Marcus theory to the voltammetric study of the kinetics of electrode reactions. The resulting four-parameter model accounts for discrepancies in the values of the inner-shell force constants and offers deeper insight to the changes involved in electron transfer processes at electrodes.The variation of the electrochemical rate constant with the applied potential is examined, and seen to be in agreement with reported experimental deviations from the simple MH model. The application of the asymmetric model to cyclic and square wave voltammetries is further reported. (C) 2011 Elsevier B.V. All rights reserved.