Quantum-Chemical Description of Charge Transfer Processes at the Metal/Solution Interface: Yesterday, Today, and Tomorrow
Quantum-Chemical Description of Charge Transfer Processes at the Metal/Solution Interface: Yesterday, Today, and Tomorrow
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金属/溶液界面电荷转移过程的量子化学描述：昨天、今天和明天
DOI：
10.1023/a:1016853329468
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发表时间：
2002
影响因子：
1.2
通讯作者：
R. Nazmutdinov
中科院分区：
文献类型：
--
作者：
R. Nazmutdinov
量子化学方法，最近已被用于计算电子转移反应的弗兰克-康登势垒进行了分析。注意力集中在其描述超出线性响应近似的过程上，包括具有化学键裂解的氧化还原反应。考虑到溶剂化效应的各种方法进行了讨论。强调了电极的簇模型在描述反应物和产物与电极表面的特定相互作用中所起的作用。重新解释了金属水配合物最近配位球的动力学对电子转移速率的影响。被认为是电子穿透概率的计算的例子，并与此参数的反应物取向和电极电荷的依赖性相关的重要的定性效果进行了分析。评述了量子电化学在近期内面临的迫切问题。
Quantum-chemical approaches that have been used lately for computing Franck–Condon barriers for electron transfer reactions are analyzed. Attention is focused on the processes whose description goes beyond the linear response approximation, including redox reactions with the cleavage of chemical bonds. Various approaches that take into account the solvation effects are discussed. The role played by the cluster models of the electrode in the description of specific interaction of reactants and products with the electrode surface is emphasized. The influence the dynamics of the nearest coordination sphere of metal aquacomplexes has on the electron transfer rate are interpreted anew. Examples of calculation of the electron penetration probability are considered, and important qualitative effects associated with the dependence of this parameter on the reactant orientation and the electrode charge are analyzed. Urgent problems the quantum electrochemistry faces in the near future are reviewed.