title: Relatively Selective Production of the Simplest Criegee Intermediate in a CH4/O2 Electric Discharge: Kinetic Analysis of a Plausible Mechanism.
abstract: High -accuracy coupled cluster methods in combination with microcanonical semiclassical transition state theory are used to investigate a plausible formation mechanism of the simplest Criegee intermediate in a CH4/O2 discharge experiment. Our results suggest that the Criegee intermediate is produced in a three-step process: (i) production of methyl radical by cleavage of a C-H bond of CH4; (ii) association of methyl radical with molecular oxygen to form a vibrationally excited methyl peroxy, which is in a rapid microequilibrium with the reactants; and finally, (iii) H-abstraction of CH3OO by O2, which results in the formation of cool CH2OO, which has insufficient internal energy to rearrange to dioxirane.
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Mail Stop A5300, Austin, Texas 78712-0165, United States.
authors.forename: Thanh Lam
authors.initials: TL
authors.lastname: Nguyen
authors.affiliation: ‡Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, Massachusetts 02138, United States.
authors.forename: Michael C
authors.initials: MC
authors.lastname: McCarthy
authors.affiliation: †Department of Chemistry, The University of Texas at Austin, Mail Stop A5300, Austin, Texas 78712-0165, United States.
authors.forename: John F
authors.initials: JF
authors.lastname: Stanton