title: Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH(+) + H2/D2 → H2O(+)/HDO(+) + H/D reactions.
abstract: We have measured the temperature-dependent kinetics for the reactions of OH(+) with H2 and D2 using a selected ion flow tube apparatus. Reaction occurs via atom abstraction to result in H2O(+)/HDO(+) + H/D. Room temperature rate coefficients are in agreement with prior measurements and resulting temperature dependences are T(0.11) for the hydrogen and T(0.25) for the deuterated reactions. This work is prompted in part by recent theoretical work that mapped a full-dimensional global potential energy surface of H3O(+) for the OH(+) + H2 → H + H2O(+) reaction [A. Li and H. Guo, J. Phys. Chem. A 118, 11168 (2014)], and reported results of quasi-classical trajectory calculations, which are extended to a wider temperature range and initial rotational state specification here. Our experimental results are in excellent agreement with these calculations which accurately predict the isotope effect in addition to an enhancement of the reaction rate constant due to the molecular rotation of OH(+). The title reaction is of high importance to astrophysical models, and the temperature dependence of the rate coefficients determined here should now allow for better understanding of this reaction at temperatures more relevant to the interstellar medium.
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776, USA.
authors.forename: Oscar
authors.initials: O
authors.lastname: Martinez
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776, USA.
authors.forename: Shaun G
authors.initials: SG
authors.lastname: Ard
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
authors.forename: Anyang
authors.initials: A
authors.lastname: Li
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776, USA.
authors.forename: Nicholas S
authors.initials: NS
authors.lastname: Shuman
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
authors.forename: Hua
authors.initials: H
authors.lastname: Guo
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776, USA.
authors.forename: Albert A
authors.initials: AA
authors.lastname: Viggiano