Unimolecular dissociation of the propargyl radical intermediate of the CH+C2H2 and C+C2H3 reactions

Abstract

This paper examines the unimolecular dissociation of propargyl (HCCCH2) radicals over a range of internal energies to probe the CH+HCCH and C+C2H3 bimolecular reactions from the radical intermediate to products. The propargyl radical was produced by 157 nm photolysis of propargyl chloride in crossed laser-molecular beam scattering experiments. The H-loss and H2 elimination channels of the nascent propargyl radicals were observed. Detection of stable propargyl radicals gave an experimental determination of 71.5 (+5-10) kcal/mol as the lowest barrier to dissociation of the radical. This barrier is significantly lower than predictions for the lowest barrier to the radical's dissociation and also lower than calculated overall reaction enthalpies. Products from both H2+HCCC and H+C3H2 channels were detected at energies lower than what has been theoretically predicted. An HCl elimination channel and a minor C-H fission channel were also observed in the photolysis of propargyl chloride.