Abstract
The photoproducts of 1,1-dichloroethene (DCE) in Xe matrix at 12 K differ from those observed in Kr. With 239-nm photolysis, chlorine is eliminated from 1,1-DCE in solid Xe, but not in Kr, although HCl elimination and DCE isomerization occur in both matrices. Just as in the 1,2-dichloroethenes, Cl{sub 2} elimination proceeds in the heavy Xe matrix via spin-orbit-enhanced intersystem crossing to a triplet reaction surface. At higher photolysis energies, a novel products appears in Xe and is identified with the aid of isotopic substitution as a second HCl{center dot}C{sub 2}HCl isomer, {sigma}-hydrogen-bonded through the acetylenic proton. The product dependence on wavelength, parent, and matrix indicates that it is formed through a triplet-surface process under geometric constraints specific to the 1,1 isomer. Loss of Cl from a dissociative triplet state to form an excited chlorovinyl radical, with further cage reaction of the energetic fragments, is postulated.
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