Abstract
Mechanism of electroreduction of copper(I) cyanide complexes from aqueous electrolytic solutions is studied within a quantum-chemical method of a density functional and a quantum-mechanical theory of charge transfer in polar environment. The electrochemically active form directly participating in an elementary electroreduction act is shown to be the [Cu(CN)2]– complex. Modeling calculations of the activation energy for an elementary charge transfer act reveal for the first time that the transfer of heavy particles along an adiabatic potential energy curve is a more probable mechanism of electroreduction of copper(I) cyanocomplexes than an outer-sphere electron transfer.
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Kuznetsov, A.M., Maslii, A.N. & Shapnik, M.S. Quantum-Chemical Study of Electroreduction Mechanism of Copper(I) Cyanide Complexes. Russian Journal of Electrochemistry 38, 123–131 (2002). https://doi.org/10.1023/A:1016860013538
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DOI: https://doi.org/10.1023/A:1016860013538