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Type: Journal article
Title: The Cl + H₂ → HCl + H Reaction Induced by IR + UV Irradiation of Cl₂ in Solid para-H₂: experiment
Other Titles: The Cl + H(2) -> HCl + H Reaction Induced by IR + UV Irradiation of Cl(2) in Solid para-H(2): experiment
Author: Kettwich, S.
Raston, P.
Anderson, D.
Citation: The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2009; 113(26):7621-7629
Publisher: American Chemical Society
Issue Date: 2009
ISSN: 1089-5639
Statement of
Sharon C. Kettwich, Paul L. Raston, and David T. Anderson
Abstract: We report IR + UV coirradiation photolysis experiments conducted on Cl2-doped para-hydrogen (p-H2) crystals at 1.8 K, using pulsed 355 nm UV radiation and cw broad-band near-IR light from a FTIR tungsten source. The amount of HCl photoproduct is monitored using FTIR spectroscopy as a function of the IR + UV exposure time. Detailed analysis of the HCl growth kinetics reveals that the reaction Cl + H2(v=1,J=0) → HCl + H is playing a significant (15%) role in the in situ photochemistry. In contrast, UV-only photolysis experiments conducted under similar conditions produce almost exclusively (99%) isolated Cl atom photofragments, indicating the reaction Cl + H2(v=0,J=0) → HCl + H is not readily occurring. This combination of photolysis experiments confirms that under these conditions, the Cl + H2 reaction probability increases by a factor greater than 25 for Cl atom reactions with H2(v=1) versus H2(v=0). These results are therefore consistent with the expectation that vibrational excitation of the H2 reagent lowers the reaction threshold and increases the reaction cross section for the Cl + H2 reaction. These experimental studies were motivated by and are compared to the quantum model simulations reported by Korolkov, Manz, and Schild in the accompanying paper.
Rights: © 2009 American Chemical Society
DOI: 10.1021/jp811206a
Appears in Collections:Aurora harvest 7
Chemistry and Physics publications

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