Quantum chemistry study for the generation of singlet oxygen from the self-reaction of peroxyl radicals

Abstract

Singlet oxygen resulted from the self-reactions of peroxyl radicals were studied using quantum chemistry. We investigated methyl, ethyl, allyl and pentadienyl groups. By comparison, formation of tetraoxides from allyl and pentadienyl peroxyl radicals are more exergonic than those of methyl and ethyl groups. Furthermore, the reactions involving allyl and pentadienyl groups have lower reaction barriers for hydrogen abstraction. The reaction products of allyl and pentadienyl peroxyls are lower in energy. The negligible spin-orbit coupling indicates that intersystem crossing of the intermediate to the triplet state is unlikely. The extent of unpaired electrons of the molecular species were investigated.