Thermochemistry and Kinetics of the OH- and Cl-Initiated Degradation Pathways of the HCFC-132b Atmospheric Pollutant

The gas-phase hydrogen abstraction reaction of 1,2-dichloro-1,1-difluoroethane (CH2ClCClF2) with OH and Cl radicals is theoretically investigated by employing density functional theory methods combined with coupled-cluster-based composite schemes. The mechanism and kinetics of the degradation entrance channels of CH2ClCClF2, recently detected with increasing concentration in the atmosphere, is elucidated by using cost-effective ab initio triple-slash dual-level direct dynamics, jChS// B2PLYP-D3(BJ)/jun-cc-pV(T+d)Z///M06-2X-D3/jun-cc-pV(T +d)Z. Thermal rate constants are calculated over the temperature range of 200-1000 K by adopting both canonical-(CVT) and microcanonical (mu VT)-variational transition state theory also including the microcanonically optimized multidimensional tunnel-ing transmission coefficient (mu OMT). The theoretical rate coefficient for the H-abstraction reaction initiated by the OH radical is computed to be kOH CVT/mu OMT = 1.72 x 10-14 cm3 molecule-1 s-1 and kOH mu VT/mu OMT = 1.57 x 10-14 cm3 molecule-1 s-1 at 298 K, in excellent agreement with the available experimental data. The rate constant for the H-abstraction reaction by the Cl atom, here obtained for the first time, is predicted to be kCl CVT/mu OMT = 5.96 x 10-14 cm3 molecule-1 s-1 and kCl mu VT/mu OMT = 5.65 x 10-14 cm3 molecule-1 s-1 at 298.15 K, thus showing increased efficiency with respect to the OH-prompted reaction.

Automated summary

In this study, the gas-phase hydrogen abstraction reaction of 1,2-dichloro-1,1-difluoroethane (CH2ClCClF2) with OH and Cl radicals was investigated using density functional theory methods. The mechanism and kinetics of the degradation entrance channels of CH2ClCClF2 were elucidated using cost-effective ab initio triple-slash dual-level direct dynamics. The calculated rate constants for the H-abstraction reactions by OH and Cl radicals were in excellent agreement with the available experimental data.