Photodissociation of propargyl chloride at 193 nm

Laura R. McCunn, Doran I G Bennett, Laurie J. Butler, Haiyan Fan, Fernando Aguirre, Stephen T. Pratt

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The photodissociation of propargyl chloride (C 3H 3Cl) has been studied at 193 nm. Ion imaging experiments with state-selective detection of the Cl atoms and single-photon ionization of the C 3H 3 radicals were performed, along with measurements of the Cl + C 3H 3 and HCl + C 3H 2 recoil kinetic energy distributions, using a scattering apparatus with electron bombardment ionization detection to resolve the competing Cl and HCl elimination channels. The experiments allow the determination of the Cl ( 2P 3/2) and Cl ( 2P 1/2) (hereafter Cl*) branching fractions associated with the C-Cl bond fission, which are determined to be 0.5 ± 0.1 for both channels. Although prior translational spectroscopy studies by others had concluded that the low velocity signal at the Cl+ mass was due to daughter fragments of the HCl elimination products, the present work shows that Cl atoms are produced with a bimodal recoil kinetic energy distribution. The major C-Cl bond fission channel, with a narrow recoil kinetic energy distribution peaking near 40 kcal/mol, produces both Cl and Cl*, whereas the minor (5%) channel, partitioning much less energy to relative kinetic energy, produces only ground spin - orbit state Cl atoms. The maximum internal energy of the radicals produced in the lowrecoil-kinetic-energy channel is consistent with this channel producing electronically excited propargyl radicals. Finally, in contrast to previous studies, the present work determines the HCl recoil kinetic energy distribution and identifies the possible contribution to this spectrum from propargyl radicals cracking to C 3 + ions in the mass spectrometer.

Original languageEnglish
Pages (from-to)843-850
Number of pages8
JournalJournal of Physical Chemistry A
Volume110
Issue number3
DOIs
Publication statusPublished - Feb 26 2006
Externally publishedYes

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Photodissociation
Kinetic energy
photodissociation
Chlorides
kinetic energy
chlorides
energy distribution
Atoms
Ionization
fission
elimination
Ions
atoms
ionization
electron bombardment
Mass spectrometers
internal energy
mass spectrometers
low speed
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

McCunn, L. R., Bennett, D. I. G., Butler, L. J., Fan, H., Aguirre, F., & Pratt, S. T. (2006). Photodissociation of propargyl chloride at 193 nm. Journal of Physical Chemistry A, 110(3), 843-850. https://doi.org/10.1021/jp058148y

Photodissociation of propargyl chloride at 193 nm. / McCunn, Laura R.; Bennett, Doran I G; Butler, Laurie J.; Fan, Haiyan; Aguirre, Fernando; Pratt, Stephen T.

In: Journal of Physical Chemistry A, Vol. 110, No. 3, 26.02.2006, p. 843-850.

Research output: Contribution to journalArticle

McCunn, LR, Bennett, DIG, Butler, LJ, Fan, H, Aguirre, F & Pratt, ST 2006, 'Photodissociation of propargyl chloride at 193 nm', Journal of Physical Chemistry A, vol. 110, no. 3, pp. 843-850. https://doi.org/10.1021/jp058148y
McCunn LR, Bennett DIG, Butler LJ, Fan H, Aguirre F, Pratt ST. Photodissociation of propargyl chloride at 193 nm. Journal of Physical Chemistry A. 2006 Feb 26;110(3):843-850. https://doi.org/10.1021/jp058148y
McCunn, Laura R. ; Bennett, Doran I G ; Butler, Laurie J. ; Fan, Haiyan ; Aguirre, Fernando ; Pratt, Stephen T. / Photodissociation of propargyl chloride at 193 nm. In: Journal of Physical Chemistry A. 2006 ; Vol. 110, No. 3. pp. 843-850.
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