title: Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe(.).
abstract: The kinetics of the reaction CH3OCH3 + Fe(+) has been studied between 250 and 600 K in the buffer gas He at pressures between 0.4 and 1.6 Torr. Total rate constants and branching ratios for the formation of Fe(+)O(CH3)2 adducts and of Fe(+)OCH2 + CH4 products were determined. Quantum-chemical calculations provided the parameters required for an analysis in terms of statistical unimolecular rate theory. The analysis employed a recently developed simplified representation of the rates of complex-forming bimolecular reactions, separating association and chemical activation contributions. Satisfactory agreement between experimental results and kinetic modeling was obtained that allows for an extrapolation of the data over wide ranges of conditions. Possible reaction pathways with or without spin-inversion are discussed in relation to the kinetic modeling results.
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117-57776, United States.
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, United States.
authors.forename: Ryan S
authors.initials: RS
authors.lastname: Johnson
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117-57776, United States.
authors.forename: Oscar
authors.initials: O
authors.lastname: Martinez
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117-57776, United States.
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, United States.
authors.forename: Hua
authors.initials: H
authors.lastname: Guo
authors.affiliation: Max-Planck-Institut für Biophysikalische Chemie , Am Fassberg 11, D-37077 Göttingen, Germany.|Institut für Physikalische Chemie, Universität Göttingen , Tammannstrasse 6, D-37077 Göttingen, Germany.
authors.forename: Jürgen
authors.initials: J
authors.lastname: Troe
authors.affiliation: Air Force Research Laboratory, Space Vehicles Directorate, Kirtland Air Force Base, New Mexico 87117-57776, United States.
authors.forename: Albert
authors.initials: A
authors.lastname: Viggiano