Correlated energy disposal and scattering dynamics of the Cl CD4(ν3 = 2) reaction

Molecular chlorine, methane and helium are co-expanded into the extraction region of a Wiley-McLaren time-of-flight spectrometer. After preparing the first overtone of the antisymmetric stretch (ν3 = 2) with direct IR excitation, the reaction is initiated by photolysing Cl2 with 355 nm light to produce mono-energetic Cl atoms with a translational energy of 0.18 eV. The CD3 and DCl products are state-selectively detected via resonance enhanced multiphoton ionization (REMPI) and analysed with the core-extraction technique. Unusual structure in the 3pz CD3 REMPI spectrum suggests the presence of a previously unobserved transition, which we assign to the stretch-bend combination ( image omitted) band. The product correlated energy disposal and the scattering distributions are compared with the same quantities for the Cl + CH4(ν3 = 2) reaction and found to be similar, although subtle differences are observed. The results for the Cl + CD4(ν3 = 2) reaction support a localized chemistry model in which the Cl atom interacts with a single C-D oscillator and leaves the CD3 methyl radical as a spectator.