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The Dynamics of the Reaction of FeO + and H 2 : A Model for Inorganic Oxidation
Author(s) -
Essafi Stéphanie,
Tew David P.,
Harvey Jeremy N.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201702009
Subject(s) - chemistry , reactivity (psychology) , density functional theory , hydrogen atom abstraction , excited state , potential energy surface , potential energy , hydrogen atom , hydrogen , reaction dynamics , spin states , reaction mechanism , computational chemistry , chemical physics , spin (aerodynamics) , activation energy , atomic physics , catalysis , molecule , thermodynamics , physics , inorganic chemistry , group (periodic table) , medicine , biochemistry , alternative medicine , organic chemistry , pathology
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 H 2 O. A change in spin state is inefficient in the product region so that excited‐state 4 Fe + 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.