Does Infrared Multiphoton Dissociation of Vinyl Chloride Yield Cold Vinylidene?

Velocity map imaging of the infrared multiphoton dissociation of vinyl chloride shows the formation of HCl in rotational levels below J = 10 that are associated with the three-center elimination pathway. The total translational energy release is observed to peak at 3-5 kcal/mol, which is consistent with the low reverse barrier predicted for the formation of HCl with vinylidene coproducts. Direct dynamics trajectory studies from the three-center transition state reproduce the observed distributions and show that the associated vinylidene is formed with only modest rotational excitation, precluding Coriolis-induced mixing among the excited vibrational levels of acetylene that would lead to distribution of vinylidene character into many vibrationally mixed acetylene vibrational levels. The results suggest that infrared multiphoton dissociation of vinyl chloride is an efficient route to synthesis of stable, cold vinylidene.