title: Vibrational spectroscopy of intermediates in methane-to-methanol conversion by FeO(+).
abstract: Gas phase FeO(+) can convert methane to methanol under thermal conditions. Two key intermediates of this reaction are the [HO-Fe-CH(3)](+) insertion intermediate and Fe(+)(CH(3)OH) exit channel complex. These intermediates are selectively formed by reaction of laser-ablated Fe(+) with organic precursors under specific source conditions and are cooled in a supersonic expansion. Vibrational spectra of the sextet and quartet states of the intermediates in the O-H and C-H stretching regions are measured by infrared multiple photon dissociation of Fe(+)(CH(3)OH) and [HO-Fe-CH(3)](+) and by monitoring argon atom loss following irradiation of Fe(+)(CH(3)OH)(Ar) and [HO-Fe-CH(3)](+)(Ar)(n) (n = 1, 2). Analysis of the experimental results is aided by comparison with hybrid density functional theory computed frequencies. Also, an improved potential energy surface for the FeO(+) + CH(4) reaction is developed based on CCSD(T) and CBS-QB3 calculations for the reactants, intermediates, transition states, and products.
authors.affiliation: Department of Chemistry, University of Massachusetts Amherst, Amherst, Massachusetts 01003, USA.
authors.forename: Gokhan
authors.initials: G
authors.lastname: Altinay
authors.forename: Murat
authors.initials: M
authors.lastname: Citir
authors.forename: Ricardo B
authors.initials: RB
authors.lastname: Metz