Chloroethylene photochemical lasers: Vibrational energy content of the HCl molecular elimination products

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Abstract
Chemical laser techniques have been used to determine relative photochemical product yields and HCl† (v′ ≤4) photoelimination product vibronic state distributions resulting from chloroethylene (CH2=CHCl, CH2=CDCl, CH2=CCl2, cis- and trans-CHCl=CHCl, and CHCl=CCl2) photolyses at λ ≥ 1550 Å. The observed highly nonstatistical product vibronic state distributions are successfully matched by a bootstrap reaction dynamics model which considers sudden structural distortion and intramolecular relaxation of HCl as it separates from acetylene or haloacetylene products. Chloroethylene vacuum ultraviolet absorption spectra (λ≥ 1400 Å) are also reported. All available spectroscopic, photochemical, and product energy partitioning data are used to formulate a state-to-state photochemical reaction mechanism for HCl photoelimination from the chloroethylenes.