Abstract
Abstract CH2ClCHCl2 was photolyzed with a focusing geometry using the P(24) line of the 10.6 μm CO2 band (940.6 cm−1). The final products of neat photolysis were cis- and trans-CHCl=CHCl, CH2=CCl2, CH2=CHCl, CH≡CCl, CH≡CH, and C4H2. The relative yield of CH2=CCl2 in particular was strongly dependent on CH2ClCHCl2 pressure and sensitive to the addition of H atom containing molecules. A series of diagnostic experiments shows that the dichloroethene isomers are formed by three different processes, i.e., infrared multiphoton decomposition, collision-induced decomposition, and radical chain reaction. Infrared mulitiphoton decomposition and collision-induced decomposition give rise to cis- and trans-CHCl=CHCl predominantly, while the radical chain reaction generates the dichloroethene isomers in comparable amounts at high reactant pressures, the most probable initiation step being the C–Cl bond-scission reaction of the parent molecule. Formation mechanisms for other minor products are also discussed.
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