Pair-correlated dynamics of the Cl + CHD3(v1=1) reaction: Effects of probe laser frequency

The reaction of C-H stretch-excited CHD3 with Cl atom was studied in a crossed-beam experiment by imaging of the ground vibrational state of CD3 products. he methyl product was interrogated by (2+1) resonance-enhanced multiphoton ionization via the Q-head of the origin band. We found that the observed image appearances depend sensitively on the precise frequency of the probe laser. Weattributed the effects to the slight differences in the subset of N-levels of CD3(v=0) being sampled. The implication of collision dynamics is that, ompared to the ground-state reaction, the CH stretch-excited reaction preferentially yields rotationally warmer CD3(v=0) products. And a negative correlation between the CD3 rotational excitation and the vibrational excitation of the coincidently formed HCl coproducts was demonstrated, which enabled us to uncover a hidden, stereodynamical aspect of the title reaction.