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Initial vibrational level distribution of HCN[{tilde X}thinsp{sup 1}{Sigma}{sup +}(v{sub 1}0v{sub 3})] from the CN(Xthinsp{sup 2}{Sigma}{sup +})+H{sub 2}{r_arrow}HCN+H reaction

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.477028· OSTI ID:641605
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  1. Argonne National Laboratory, Chemistry Division, 9700 South Cass Avenue, Argonne, Illinois 60439 (United States)

The reaction of the cyano radical (CN) with hydrogen was studied by time-resolved infrared absorption spectroscopy of individual rovibrational states of HCN. The initial vibrational level distribution of HCN(v{sub 1}0v{sub 3}) was determined by plotting the time dependence of the fractional population of a vibrational level and extrapolating these curves to the origin of time. The experiments were carried out at two temperatures, 293 and 324 K, with similar results. It was estimated that about 50{percent} of the available reaction exothermicity was deposited as vibrational excitation of the HCN product. Surprisingly, the HCN(101) vibrational level received a significant fraction of the observed vibrational population, implying that the CN vibration was not really a spectator bond in the reaction dynamics. Furthermore, the observed HCN(v{sub 1}0v{sub 3}) vibrations only account for about 27{percent} of the initial HCN population produced in the title reaction. A significant fraction of the product HCN molecules must have been produced with the bending mode excited, likely in combination with the H{endash}C stretch vibrations. {copyright} {ital 1998 American Institute of Physics.}

OSTI ID:
641605
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 11 Vol. 109; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English