Unraveling the reaction mechanism of OH radicals with chloromethyl hydroperoxide

Alkyl hydroperoxides are essential intermediates in the atmospheric oxidation of hydrocarbons and in low-temperature combustion processes. Chlorinated alkyl hydroperoxides play a similar role in the atmospheric oxidation of chlorinated hydrocarbons. It is important to study the thermodynamic parameters for these species to understand and predict the reaction pathways, rate constants, and equilibrium constants. The main objective of this work is to provide reliable kinetic and thermodynamic data for the gas phase reaction of hydroxyl radicals with chloromethyl hydroperoxide (CH₂ClOOH). Several possible reaction pathways could be feasible: H-abstraction, Cl-abstraction, and OH-abstraction. Theoretical calculations were performed with the augmented correlation consistent basis sets aug-cc-pVTZ for C, H, and O atoms and the aug-cc-pV(T+d)Z for Cl atom including tight d polarization functions. The potential energies have been calculated at the DK-CCSD(T)/ANO-RCC (VTZP and VQZP) level of theory on the geometries optimized previously. (authors)