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Ozonolysis of alkenes in the troposphere proceeds through a Criegee intermediate, or carbonyl oxide, which has only recently been detected in the gas phase. The present study focuses on the production of an alkyl-substituted Criegee intermediate, CHCHOO, in a pulsed supersonic expansion, and then utilizes VUV photoionization at 118 nm and UV-induced depletion of the m/z = 60 signal to probe the A A transition. The UV-induced depletion approaches 100% near the peak of the profile at 320 nm, indicating rapid dynamics in the state, and corresponds to a peak absorption cross section of ∼5 × 10 cm molecule. The electronic spectrum for CHCHOO is similar to that reported recently for CHOO, but shifted 15 nm to shorter wavelength, which will result in a longer tropospheric lifetime for CHCHOO with respect to solar photolysis. Complementary electronic structure calculations (EOM-CCSD) are carried out for the and potentials of these Criegee intermediates along the O–O coordinate. An intramolecular interaction stabilizes the ground state of the -conformer of CHCHOO relative to -CHCHOO, and indicates that the -conformer will be the more abundant species in the expansion. The excited electronic state of -CHCHOO is also predicted to be destabilized relative to that for -CHCHOO and CHOO, in accord with the shift in the - transition observed experimentally. Hydroxyl radicals produced concurrently with the generation of the Criegee intermediates are detected by 1+1 resonance enhanced multiphoton ionization. The OH yield observed with CHCHOO is 4-fold larger than that from CHOO, consistent with prior studies of OH generation from alkene ozonolysis.


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