Effect of halogenation on the mechanism of the atmospheric reactions between methylperoxy radicals and NO. A computational study.

The mechanism of the reactions between the halogenated methylperoxy radicals, CHX(2)O(2) (X = F, Cl), and NO is investigated by using ab initio and density functional quantum mechanical methods. Comparison is made with the mechanism of the CH(3)O(2) + NO reaction. The most important energy minima in the potential energy surface are found to be the two conformers of the halogenated methyl peroxynitrite association adducts, CHX(2)OONOcp and CHX(2)OONOtp, and the halogenated methyl nitrates, CHX(2)ONO(2). The latter are suggested to be formed through the one-step isomerization of the peroxynitrite adduct and may lead upon decomposition to carbonylated species, CX(2)O + HONO and CHXO + XNO(2). The ambiguous issue of the unimolecular peroxynitrite to nitrate isomerization is reconsidered, and the possibility of a triplet transition state involvement in the ROONOtp <--> RONO(2) rearrangement is examined. The overall calculations and the detailed correlation with the methyl system show the significant effect of the halogenation on the lowering of the entrance potential energy well which corresponds to the formation of the peroxynitrites. The increased attractive character of the potential energy surface found upon halogenation combined with the increased exothermicity of the CHX(2)O(2) + NO --> CHX(2)O + NO(2) reaction are suggested to be the important factors contributing to the enhanced reactivity of the halogenated reactions relative to CH(3)O(2) + NO. The calculated heat of formation values indicate the large stabilization of the fluorinated derivatives.