title: Multiplexed Photoionization Mass Spectrometry Investigation of the O((3)P) + Propyne Reaction.
abstract: The reaction of O((3)P) + propyne (C3H4) was investigated at 298 K and 4 Torr using time-resolved multiplexed photoionization mass spectrometry and a synchrotron-generated tunable vacuum ultraviolet light source. The time-resolved mass spectra of the observed products suggest five major channels under our conditions: C2H3 + HCO, CH3 + HCCO, H + CH3CCO, C2H4 + CO, and C2H2 + H2 + CO. The relative branching ratios for these channels were found to be 1.00, (0.35 ± 0.11), (0.18 ± 0.10), (0.73 ± 0.27), and (1.31 ± 0.62). In addition, we observed signals consistent with minor production of C3H3 + OH and H2 + CH2CCO, although we cannot conclusively assign them as direct product channels from O((3)P) + propyne. The direct abstraction mechanism plays only a minor role (≤1%), and we estimate that O((3)P) addition to the central carbon of propyne accounts for 10% of products, with addition to the terminal carbon accounting for the remaining 89%. The isotopologues observed in experiments using d1-propyne (CH3CCD) and analysis of product branching in light of previously computed stationary points on the singlet and triplet potential energy surfaces (PESs) relevant to O((3)P) + propyne suggest that, under our conditions, (84 ± 14)% of the observed product channels from O((3)P) + propyne result from intersystem crossing from the initial triplet PES to the lower-lying singlet PES.
authors.affiliation: †Combustion Research Facility, Sandia National Laboratories, Mail Stop 9055, Livermore, California 94551-0969, United States.
authors.forename: John D
authors.initials: JD
authors.lastname: Savee
authors.affiliation: ‡Department of Chemistry, University of the Pacific, Stockton, California 95211, United States.
authors.forename: Sampada
authors.initials: S
authors.lastname: Borkar
authors.affiliation: †Combustion Research Facility, Sandia National Laboratories, Mail Stop 9055, Livermore, California 94551-0969, United States.
authors.forename: Oliver
authors.initials: O
authors.lastname: Welz
authors.affiliation: ‡Department of Chemistry, University of the Pacific, Stockton, California 95211, United States.
authors.forename: Bálint
authors.initials: B
authors.lastname: Sztáray
authors.affiliation: †Combustion Research Facility, Sandia National Laboratories, Mail Stop 9055, Livermore, California 94551-0969, United States.
authors.forename: Craig A
authors.initials: CA
authors.lastname: Taatjes
authors.affiliation: †Combustion Research Facility, Sandia National Laboratories, Mail Stop 9055, Livermore, California 94551-0969, United States.
authors.forename: David L
authors.initials: DL
authors.lastname: Osborn