Abstract
A study of the photolytically-induced reaction of ozone with vinyl chloride, H2CCHCl, in argon matrixes is described, after either red LED (625 nm) or Hg pen lamp (254 nm) irradiation. Products were observed using infrared spectroscopy and identification was aided by 18O and deuterium labeling experiments. The experimental work was supported by extensive DFT calculations. Three products were formed upon red LED irradiation: chloroacetaldehyde, chlorooxirane and chlorovinyl alcohol (this last assignment being tentative). These results suggest the intermediacy of a triplet biradical H2CO∙-CHCl∙ formed through the initial step of the reaction of O 3P with VC. With 254 nm irradiation, additional products were also observed, specifically chloroketene and the ketene-HCl complex, reflecting the higher energy and O 1D spin state of the initial O atom formed with 254 nm irradiation.
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