Relatively Selective Production of the Simplest Criegee Intermediate in a CH4/O2 Electric Discharge: Kinetic Analysis of a Plausible Mechanism. Nguyen, T., L., McCarthy, M., C., & Stanton, J., F. The journal of physical chemistry. A, 11, 2014.
Relatively Selective Production of the Simplest Criegee Intermediate in a CH4/O2 Electric Discharge: Kinetic Analysis of a Plausible Mechanism. [pdf]Paper  Relatively Selective Production of the Simplest Criegee Intermediate in a CH4/O2 Electric Discharge: Kinetic Analysis of a Plausible Mechanism. [link]Website  abstract   bibtex   
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.

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