5 years ago

The Dynamics of the Reaction of FeO+ and H2: A Model for Inorganic Oxidation

The Dynamics of the Reaction of FeO+ and H2: A Model for Inorganic Oxidation
Stéphanie Essafi, Jeremy N. Harvey, David P. Tew
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. On the rebound: The reaction of the FeO+ cation with H2, a simple model for many oxidation processes, proceeds through a “rebound” as well as the known insertion–elimination mechanism. This was revealed by classical trajectory studies on the sextet and quartet potential energy surfaces of the title reaction.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702009

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