Autoxidation in atmospheric chemistry

Long recognized as an important process in the degrdn. of unsatd. fats and oils, wine, and components of biol. organisms, and in low temp. combustion processes, the role of autoxidn. in the conversion of atm. chems. is only just beginning to be understood. Here, recent exptl. and theor. work on the rate limiting step of autoxidn., namely, the H-shift isomerization of peroxy radicals (RO_2 → QOOH), for several systems relevant to atm. chem. will be highlighted. Trends in the peroxy radical isomerization rates with functionalization will be discussed. The potential impact of autoxidn. toward the gas- and condensed-phase org. chem. of the atm. will be hypothesized, and directions for future work to test this hypothesis will be suggested.