The Dynamics of the Reaction of FeO+ and H2: A Model for Inorganic Oxidation |
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Authors: | Dr Stéphanie Essafi Dr David P Tew Prof Jeremy N Harvey |
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Institution: | School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS UK |
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Abstract: | Extensive density functional theory (DFT) calculations using the B3LYP functional were used to explore the sextet and quartet energy potential energy surfaces (PESs) of the title reaction, and as a basis to fit global analytical reactive PESs. Surface-hopping dynamics on these PESs reproduce the experimentally observed reactivity and confirm that hydrogen activation rather than spin-state change is rate-limiting at low reaction energy, where the main products are Fe+ and H2O. A change in spin state is inefficient in the product region so that excited-state 4Fe+ is the dominant product. At higher energies, spin-allowed hydrogen atom abstraction to form FeOH+ predominates. At intermediate energy, a previously unexpected rebound mechanism contributes significantly to the reactivity. |
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Keywords: | Eisenoxid-Kation Moleküldynamik Reaktionsmechanismen Rebound-Mechanismus Oberflächen-Hopping |
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