Direct Observation of Aliphatic Peroxy Radical Autoxidation and Water Effects: An Experimental and Theoretical Study.

The autoxidation of organic peroxy radicals (RO ) into hydroperoxy-alkyl radicals (QOOH), then hydroperoxy-peroxy radicals (HOOQO ) is now considered to be important in the Earth's atmosphere. To avoid mechanistic uncertainties these reactions are best studied by monitoring the radicals. But for the volatile and aliphatic RO radicals playing key roles in the atmosphere this has long been an instrumental challenge. This work reports the first study of the autoxidation of aliphatic RO radicals and is based on monitoring RO and HOOQO radicals. The rate coefficients, k (s ), were determined both experimentally and theoretically using MC-TST kinetic theory based on CCSD(T)//M06-2X quantum chemical methodologies. The results were in excellent agreement and confirmed that the first H-migration is strongly rate-limiting in the oxidation of non-oxygenated volatile organic compounds (VOCs). At higher relative humidity (2-30 %) water complexes were evidenced for HOOQO radicals, which could be an important fate for HOO-substituted RO radicals in the atmosphere.