Photodissociation Dynamics of Vinyl Chloride via Mass-Selected Multiphoton Ionization Spectroscopy.

A time-of-flight molecular beam machine was designed and built to measure reaction dynamics in the collisionless time regime. The apparatus design is discussed in detail. The apparatus also has the capability to carry out bimolecular dynamics measurements using the same methodology in future experiments. Resonant enhanced multiphoton ionization (REMPI) measurements were made of the HCl product from the 193 nm photolysis of vinyl chloride. Room temperature HCl REMPI measurements were also made in the same instrument and used to calibrate the rotational line strengths of transitions from the ground electronic state X ^1Sigma^+ (v = 0, 1 and 2) to the F^1Delta (v = 0 and 1) states. HCl product state distributions were then determined from the vinyl chloride data. Perturbations of the F^1Delta electronic state of HCl and their effect on transition line strengths are discussed in detail. An analysis of the unimolecular decay mechanisms of the 193 nm photolysis of vinyl chloride is also presented.