Infrared spectral identification of the Criegee intermediate (CH3)(2)COO

Abstract

Criegee intermediates are carbonyl oxides that play critical roles in the ozonolysis of alkenes in the atmosphere. So far, the infrared spectra of only the simplest Criegee intermediates CH2OO and CH3CHOO are reported. We report the transient infrared spectrum of the next member (CH3)(2)COO, produced from ultraviolet irradiation of a mixture of (CH3)(2)CI2 + O-2 in a flow reactor and detected with a step-scan Fourier-transform spectrometer. The four observed bands near 1424, 1368, 1040, and 887.4 cm(-1) provide definitive identification of (CH3)(2)COO. The observed vibrational wavenumbers and rotational contours agree with those predicted with quantum-chemical calculations; contributions of the hot bands from excited states of the low-lying torsional modes are significant. The rapid decay yields an estimate of the rate coefficient similar to 1.6 x 10(-10) cm(3) molecule(-1) s(-1) for the self-reaction of (CH3)(2)COO. The direct IR detection of (CH3)(2)COO should prove useful for field measurements and laboratory investigations of related Criegee mechanism. Published by AIP Publishing.