Direct Measurement of the Unimolecular Decay Rate of Criegee Intermediates to OH Products.*

Ozonolysis of alkenes is an important non-photolytic source of OH radicals in the troposphere. The production of OH radicals proceeds though formation and unimolecular decay of Criegee intermediates such as syn-CH3CHOO and (CH3)2COO. These alkyl-substituted Criegee intermediates can undergo a 1,4-H transfer reaction to form an energized vinyl hydroperoxide species, which breaks apart to OH and vinoxy products. Recently, this laboratory used IR excitation in the C-H stretch overtone region to initiate the unimolecular decay of syn-CH3CHOO and (CH3)2COO Criegee intermediates, leading to OH formation. Here, direct time-domain measurements are performed to observe the rate of appearance of OH products under collision-free conditions utilizing UV laser-induced fluorescence for detection. The experimental rates are in excellent agreement with statistical RRKM calculations using barrier heights predicted from high-level electronic structure calculations. Accurate determination of the rates and barrier heights for unimolecular decay of Criegee intermediates is essential for modeling the kinetics of alkene ozonolysis reactions, a significant OH radical source in atmospheric chemistry, as well as the steady-state concentration of Criegee intermediates in the atmosphere.