Reaction mechanism and kinetics of the atmospheric oxidation of 1,4-thioxane by NO3 — A theoretical study

Volatile organic compounds (VOCs) are emitted as pollutants into the atmosphere from many natural and artificial sources. The oxidation of VOCs by atmospheric species plays a key role in the degradation of VOCs. In the present investigation, the atmospheric degradation of a cyclic organosulfur compound, 1,4-thioxane, by an NO3• radical is studied. Pathways for the reaction of 1,4-thioxane with the NO3• radical were modeled through electronic structure calculations using density functional theory methods B3LYP, M06-2X, and MP2 with the 6–31G(d,p) basis set. The NO3•-initiated reaction of 1,4-thioxane was found to proceed in three ways: by single-hydrogen atom abstraction, by direct transfer of the O atom of NO3• to the S atom moiety of 1,4-thioxane, or by two-hydrogen atom transfer reactions leading to the formation of a peroxy radical intermediate, which further undergoes secondary reactions with other atmospheric species. Structures, energies, and vibrational frequencies obtained from M06-2X/6–31G(d,p) electronic structure calculations were subsequently used to perform canonical variational transition-state theory calculations to determine the rate constants over the temperature range of 278–350 K and to study the lifetime of 1,4-thioxane in the atmosphere. The rate constant calculated for the reaction of 1,4-thioxane with the NO3• radical is in good agreement with the available experimental data.