Quantum Chemical Modeling of Electrochemical Consecutive Reduction of Fe(III) Aqua- and Aqua-Hydroxocomplexes
| Autor: | A. F. Dresvyannikov, R. R. Nazmutdinov, T. T. Zinkicheva, M. E. Kolpakov |
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| Rok vydání: | 2019 |
| Předmět: |
Materials science
Aqueous solution Activation energy Inner sphere electron transfer 010402 general chemistry 010403 inorganic & nuclear chemistry Electrochemistry 01 natural sciences Redox 0104 chemical sciences Marcus theory Inorganic Chemistry Electron transfer Reagent Materials Chemistry Physical chemistry Physical and Theoretical Chemistry |
| Zdroj: | Journal of Structural Chemistry. 60:1226-1233 |
| ISSN: | 1573-8779 0022-4766 |
| DOI: | 10.1134/s0022476619080031 |
| Popis: | Quantum chemical modeling of Fe(III), Fe(II), and Fe(I) aqua-, aqua-hydroxo-, and aquadihydroxocomplexes is presented. The mechanism of a consecutive transfer of two electrons is studied as these forms are electrochemically reduced from an aqueous solution. The reorganization energy of the solvent and the inner sphere of studied reagents is calculated, standard redox potentials are estimated. Based on Marcus theory, the activation energy of two steps of Fe(III) reduction is estimated and the second electron transfer is shown to be rate controlling, while the energy barrier is increased due to the products of Fe(III) hydrolysis. The model predictions are in qualitative agreement with previously reported experimental data. |
| Databáze: | OpenAIRE |
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