Computational study of the stability of α-hydroperoxyl- or α-alkylperoxyl substituted alkyl radicals

Degradation mechanisms of peroxide-containing compounds, either stable or transients in the degradation of volatile organic compounds, are still poorly understood, despite their importance in atmospheric chemistry. A theoretical DFT and Coupled Cluster theory analysis of the stability of alkyl radicals with hydroperoxyl- (HOO–) or alkylperoxyl (ROO–) substituents on the radical carbon atom revealed that such radicals are unstable, dissociating by O–O scission to a carbonyl compound and a hydroxy or alkoxy radical even for multiple substituted compounds. This dissociation occurs sequentially after completion of the reaction forming the α-peroxyl-substituted radicals, such that the latter is independent of the O–O scission.