Vacuum-ultraviolet (147.0 nm and 123.6 nm) photolysis of 1,1-dimethylcyclopropane

Abstract

The gas-phase photolysis of 1,1-dimethylcyclopropane has been investigated using xenon (147.0 nm) and krypton (123.6 nm) resonance radiation. Major products observed in order of decreasing importance were isobutene, ethylene, hydrogen, 1,3-butadiene 2-methyl-1,3-butadiene, propylene, allene, methylacetylene, and acetylene. Radical scavengers, NO and O2, and radical interceptors, H2S/D2S and HI, were used to determine the relative importance of radical and molecular processes. CH3, C2H3, C3H5, and C4H7 radical species were identified and quantified. Ten primary reaction channels were postulated, of which the elimination of methylene was the most predominant, accounting for 34% of the photo-decomposition at 147.0 nm and 39% at 123.6 nm. Although ionization was established at 123.6 nm (η = 0.10) the nature of a charge transfer or other ion-molecule reaction channel leading to the formation of 2-methyl-1-butene and 2-methyl-2-butene could not be determined.