Unimolecular β-Hydroxyperoxy Radical Decomposition with OH Recycling in the Photochemical Oxidation of Isoprene

A novel process in the photochemical oxidation of isoprene that recycles hydroxyl(OH) radicals has been identified using first-principles computational chemistry. Isoprene is the dominant biogenic volatile organic compound (VOC), and its oxidation controls chemistry in the forest boundary layer and is also thought to contribute to cloud formation in marine environments. The mechanism described here involves rapid unimolecular decomposition of the two major peroxy radicals (beta-hydroxyperoxy radicals) produced by OH-initiated isoprene oxidation. Peroxy radicals are well-known as key intermediates in VOC oxidation but up to now were only thought to be destroyed in bimolecular reactions. The process described here leads to OH recycling with up to around 60% efficiency in environments with low levels of peroxy radicals and NOx. In forested environments reaction of the beta-hydroxyperoxy radicals with HO2 is expected to dominate, with a small contribution from the mechanism described here. Peroxy radical decomposition will be more important in the unpolluted marine boundary layer, where lower levels of NO and HO2 are encountered.