Isomer-specific detection in the UV photodissociation of the propargyl radical by chirped-pulse mm-wave spectroscopy in a pulsed quasi-uniform flow

Abstract

Isomer-specific detection and product branching fractions in the UV photodissociation of the propargyl radical is achieved through the use of chirped-pulse Fourier-transform mm-wave spectroscopy in a pulsed quasi-uniform flow (CPUF). Propargyl radicals are produced in the 193 nm photodissociation of 1,2-butadiene. Absorption of a second photon leads to H atom elimination giving three possible C₃H₂ isomers: singlets cyclopropenylidene (c-C₃H₂) and propadienylidene (l-C₃H₂), and triplet propargylene (³HCCCH). The singlet products and their appearance kinetics in the flow are directly determined by rotational spectroscopy, but due to the negligible dipole moment of propargylene, it is not directly monitored. However, we exploit the time-dependent kinetics of H-atom catalyzed isomerization to infer the branching to propargylene as well. We obtain the overall branching among H loss channels to be 2.9% (+1.1/−0.5) l-C₃H₂ + H, 16.8% (+3.2/−1.3) c-C₃H₂ + H, and 80.2 (+1.8/−4.2) ³HCCCH + H. Our findings are qualitatively consistent with earlier RRKM calculations in that the major channel in the photodissociation of the propargyl radical at 193 nm is to ³HCCCH + H; however, a greater contribution to the energetically most favorable isomer, c-C₃H₂ + H is observed in this work. We do not detect the predicted HCCC + H₂ channel, but place an upper bound on its yield of 1%.