reactivity, ab initio, transition state, bromoiodomethane

We report the calculation of the H-, Br-, and I-abstraction channels in the reaction of OH radicals with bromoiodomethane CH2IBr. The resulting energy profiles at 0 K were obtained by high-level all-electron ab initio methods including valence and core-valence electron correlation, scalar relativistic effects, spin-orbit coupling, spin-adaptation, vibration contributions, and tunneling corrections. In terms of activation enthalpy at 0 K, the energy profile for the Br-abstraction showed that this reaction pathway is not energetically favorable in contrast to the two other channels (H- and I-abstractions), which are competitive. The H-abstraction was strongly exothermic (-84.4 kJmol(-1)), while the I-abstraction was modestly endothermic (16.5 kJmol(-1)). On the basis of our calculations, we predicted the rate constants using canonical transition state theory over the temperature range 250-500 K for each abstraction pathway. The overall rate constant at 298 K was estimated to be 3.40x10(-14) and 4.22x10(-1)4 cm(3) molecule(-1) s(-1) for complex and direct abstraction mechanisms, respectively. In addition, the overall rate constant computed at 277K was used in the estimation of the atmospheric lifetime for CH2IBr. On the basis of our theoretical calculations, the atmospheric lifetime for the OH removal process is predicted to be close to 1 year. In terms of atmospheric lifetime, the OH reaction is not competitive with the Cl reaction and photolysis processes.