A comprehensive quantum chemical study on the mechanism and kinetics of atmospheric reactions of 3-chloro-2-methyl-1-propene with OH radical

The detailed reaction mechanism of 3-chloro-2-methyl-1-propene (3CMP) with OH radical was investigated by employing highly accurate electronic structure calculations and kinetic modelling. Due to the unsaturated structure of 3CMP, it is highly reactive in the troposphere with OH radical. The fate of the so-formed alkyl radical intermediates and intermediate adducts in the favourable pathways is determined by its reaction with other atmospheric oxidants, such as HO2, NO and NO2 radicals. The rate constants computed within the temperature range of 200–1000 K for the favourable hydrogen atom abstraction and OH radical addition reactions are in reasonable agreement with the available experimental values. The oxidation of 3CMP results in the formation of stable chlorinated products, such as chloroacetone and formyl chloride, which are identified experimentally. These products may be transported to the stratosphere which will affect the ozone layer.