Energetics and mechanisms for the acetonyl radical + O2 reaction: An important system for atmospheric and combustion chemistry.

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The acetonyl radical (•CH2COCH3) is relevant to atmospheric and combustion chemistry due to its prevalence in many important reaction mechanisms. One such reaction mechanism is the decomposition of Criegee intermediates in the atmosphere that can produce acetonyl radical and OH. In order to understand the fate of the acetonyl radical in these environments and to create more accurate kinetics models, we have examined the reaction system of the acetonyl radical with O2 using highly reliable theoretical methods. Structures were optimized using coupled cluster theory with singles, doubles, and perturbative triples [CCSD(T)] with an atomic natural orbital (ANO0) basis set. Energetics were computed to chemical accuracy using the focal point approach involving perturbative treatment of quadruple excitations [CCSDT(Q)] and basis sets as large as cc-pV5Z. The addition of O2 to the acetonyl radical produces the acetonylperoxy radical, and multireference computations on this reaction suggest it to be barrierless. No submerged pathways were found for the unimolecular isomerization of the acetonylperoxy radical. Besides dissociation to reactants, the lowest energy pathway available for the acetonylperoxy radical is a 1-5 H shift from the methyl group to the peroxy group through a transition state that is 3.3 kcal mol-1 higher in energy than acetonyl radical + O2. The ultimate products from this pathway are the enol tautomer of the acetonyl radical along with O2. Multiple pathways that lead to OH formation are considered; however, all of these pathways are predicted to be energetically inaccessible, except at high temperatures.