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Absolute photoionization cross-section of the propargyl radical

Savee, John D.; Soorkia, Satchin; Welz, Oliver W.; Selby, Talitha M.; Taatjes, Craig A.; Osborn, David L.

Using synchrotron-generated vacuum-ultraviolet radiation and multiplexed time-resolved photoionization mass spectrometry we have measured the absolute photoionization cross-section for the propargyl (C 3H 3) radical, σ propargyl ion (E), relative to the known absolute cross-section of the methyl (CH 3) radical. We generated a stoichiometric 1:1 ratio of C 3H 3 : CH 3 from 193 nm photolysis of two different C 4H 6 isomers (1-butyne and 1,3-butadiene). Photolysis of 1-butyne yielded values of σ propargyl ion (10.213 eV)=(26.1±4.2) Mb and σ propargyl ion (10.413 eV)=(23.4±3.2) Mb, whereas photolysis of 1,3-butadiene yielded values of σ propargyl ion (10.213 eV)=(23.6±3.6) Mb and σ propargyl ion (10.413 eV)=(25.1±3.5) Mb. These measurements place our relative photoionization cross-section spectrum for propargyl on an absolute scale between 8.6 and 10.5 eV. The cross-section derived from our results is approximately a factor of three larger than previous determinations. © 2012 American Institute of Physics.