Gas-Phase Peroxyl Radical Recombination Reactions : A Computational Study of Formation and Decomposition of Tetroxides

The recombination ("dimerization") of peroxyl radicals (RO2 center dot) is one of the pathways suggested in the literature for the formation of peroxides (ROOR', often referred to as dimers or accretion products in the literature) in the atmosphere. It is generally accepted that these dimers play a major role in the first steps of the formation of submicron aerosol particles. However, the precise reaction pathways and energetics of RO2 center dot + R'O-2 center dot reactions are still unknown. In this work, we have studied the formation of tetroxide intermediates (RO4R'): their formation from two peroxyl radicals and their decomposition to triplet molecular oxygen (O-3(2)) and a triplet pair of alkoxyl radicals (RO center dot). We demonstrate this mechanism for several atmospherically relevant primary and secondary peroxyl radicals. The potential energy surface corresponds to an overall singlet state. The subsequent reaction channels of the alkoxyl radicals include, but are not limited to, their dimerization into ROOR'. Our work considers the multiconfigurational character of the tetroxides and the intermediate phases of the reaction, leading to reliable mechanistic insights for the formation and decomposition of the tetroxides. Despite substantial uncertainties in the computed energetics, our results demonstrate that the barrier heights along the reaction path are invariably small for these systems. This suggests that the reaction mechanism, previously validated at a multireference level only for methyl peroxyl radicals, is a plausible pathway for the formation of aerosol-relevant larger peroxides in the atmosphere.