We report the calculation of the H-, Br-, and I-abstraction channels in the reaction of OH radicals with bromoiodomethane CH 2 IBr. 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 kJ mol −1 ), while the I-abstraction was modestly endothermic (16.5 kJ mol −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 3.40 × 10 −14 and 4.22 × 10 −14 cm 3 molecule −1 s −1 for complex and direct abstraction mechanisms, respectively. In addition, the overall rate constant computed at 277 K was used in the estimation of the atmospheric lifetime for CH 2 IBr. 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.

Reactants, weak molecular complexes, transition states, and products for the H-, Cl-, and I-abstraction channels in the reaction of OH radicals with chloroiodomethane CH(2)ICl as well as the energy profiles at 0 K have been determined using high-level all-electron ab initio methods. The results showed that all-electron DK-CCSD(T)/ANO-RCC approach performed very well in predicting the reactivity of iodine. In terms of activation enthalpy at 0 K, the energy profile for the Cl-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 (-87 kJ mol(-1)), while the I-abstraction was modestly endothermic (11.8 kJ mol(-1)). On the basis of our calculations including the following corrections to the potential energies: basis set saturation, valence and core-valence electron correlation, relativistic effects, spin-adaptation, vibration contributions, and tunneling corrections, rate constants were predicted 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 4.29 × 10(-14) and 5.44 × 10(-14) cm(3) molecule(-1) s(-1) for complex and direct abstraction mechanisms, respectively. In addition, the overall rate constant computed at 277 K was used in the estimation of the atmospheric lifetime for CH(2)ICl. 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.

The present study reports temperature dependent rate constantsHighly correlated

We present a systematic study of the thermochemistry for a set of iodine species relevant to atmospheric chemistry. The reactions include H, O and I atoms and H2, OH, HI, I2, iodine monoxide, hypoiodous acid (HOI) and H2O species. The calculations presented were performed using completely renormalized coupled cluster theory including single, double and non-iterative triple substitutions in conjunction with the ANO-RCC basis sets developed for scalar relativistic calculations. The second-order spin-free Douglas–Kroll–Hess Hamiltonian was used to account for the scalar relativistic effects. The calculations also included spin–orbit corrections and semi-core correlation contributions. The resulting reaction enthalpies and Gibbs energies at 298 K have been compared with the experimental data. On the basis of a set of selected reactions we suggest an updated value for Δ f H298K° of HOI based on the set of isogyric reactions: −69.0 ± 3.7 kJ mol−1.

We present a systematic density functional study of central- and surface-doped aluminum cluster anions Al12X- (X=Mg, B, Ga, Si, P, Sc-Zn), their interactions and reactivity with water. Adsorption of water...