Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 56, Issue 21, Pages 5790-5794Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201702009
Keywords
iron oxide cation; molecular dynamics; reaction mechanisms; rebound mechanism; surface hopping
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Funding
- EPSRC [EP/L005913/1]
- KU Leuven grant [GKF-C9549-C14/15/052]
- Royal Society
- Engineering and Physical Sciences Research Council [EP/L005913/1] Funding Source: researchfish
- EPSRC [EP/L005913/1] Funding Source: UKRI
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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 Fe-4(+) 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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