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Quantum-Chemical Description of Charge Transfer Processes at the Metal/Solution Interface: Yesterday, Today, and Tomorrow

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Abstract

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.

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  1. Kazan State Technological University, ul. Karla Marksa 68, Kazan, 420015, Tatarstan, Russia

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Nazmutdinov, R.R. Quantum-Chemical Description of Charge Transfer Processes at the Metal/Solution Interface: Yesterday, Today, and Tomorrow. Russian Journal of Electrochemistry 38, 111–122 (2002). https://doi.org/10.1023/A:1016853329468

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