Photofragment Translational Spectroscopy of Propargyl Radicals at 248 nm

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The photodissociation of propargyl radical, C{sub 3}H{sub 3}, and its perdeuterated isotopolog was investigated using photofragment translational spectroscopy. Propargyl radicals were produced by 193 nm photolysis of allene entrained in a molecular beam expansion, and then photodissociated at 248 nm. photofragment time-of-flight spectra were measured at a series of laboratory angles using electron impact ionization coupled to a mass spectrometer. Data for ion masses corresponding to C{sub 3}H{sub 2}{sup +}, C{sub 3}H{sup +}, C{sub 3}{sup +}, and the analogous deuterated species show that both H and H{sub 2} loss occur. The translational energy distributions for these processes have average values ... continued below

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Goncher, S.J.; Moore, D.T.; Sveum, N.E. & Neumark, D.M. December 21, 2007.

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The photodissociation of propargyl radical, C{sub 3}H{sub 3}, and its perdeuterated isotopolog was investigated using photofragment translational spectroscopy. Propargyl radicals were produced by 193 nm photolysis of allene entrained in a molecular beam expansion, and then photodissociated at 248 nm. photofragment time-of-flight spectra were measured at a series of laboratory angles using electron impact ionization coupled to a mass spectrometer. Data for ion masses corresponding to C{sub 3}H{sub 2}{sup +}, C{sub 3}H{sup +}, C{sub 3}{sup +}, and the analogous deuterated species show that both H and H{sub 2} loss occur. The translational energy distributions for these processes have average values <E{sub T}> = 5.7 and 15.9 kcal/mol, respectively, and are consistent with dissociation on the ground state following internal conversion, with no exit barrier for H loss but a tight transition state for H{sub 2} loss. The translational energy distribution for H atom loss is similar to that in previous work on propargyl in which the H atom, rather than the heavy fragment, was detected. The branching ratio for H loss/H{sub 2} loss was determined to be 97.6/2.4 {+-} 1.2, in good agreement with RRKM results.

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  • Journal Name: The Journal of Chemical Physics

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  • Report No.: LBNL-1495E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 948440
  • Archival Resource Key: ark:/67531/metadc901851

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Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

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  • December 21, 2007

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  • Sept. 27, 2016, 1:39 a.m.

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  • Sept. 30, 2016, 6:55 p.m.

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Goncher, S.J.; Moore, D.T.; Sveum, N.E. & Neumark, D.M. Photofragment Translational Spectroscopy of Propargyl Radicals at 248 nm, article, December 21, 2007; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc901851/: accessed October 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.