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Internal state distribution of the CF fragment from the 193 nm photodissociation of CFCl and CFBr

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2713398· OSTI ID:20991239
;  [1]
  1. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218-2685 (United States)

The dynamics of the 193 nm photodissociation of the CFCl and CFBr molecules have been investigated in a molecular beam experiment. The CFCl and CFBr parent molecules were generated by pyrolysis of CHFCl{sub 2} and CFBr{sub 3}, respectively, and the CFCl and the CF photofragment were detected by laser fluorescence excitation. The 193 nm attenuation cross section of CFCl was determined from the reduction of the CF photofragment signal as a function of the photolysis laser fluence. The internal state distribution was derived from the analysis of laser fluorescence excitation spectra in the A {sup 2}{sigma}{sup +}-X {sup 2}{pi} band system. A very low degree of rotational excitation, with essentially equal A{sup '} and A{sup ''} {lambda}-doublet populations, and no vibrational excitation were found in the CF photofragment. The energy available to the photofragments is hence predominantly released as translational energy. The CF internal state distribution is consistent with the dissociation of a linear intermediate state. Considerations of CFCl electronic states suggest that a bent Rydberg state is initially excited.

OSTI ID:
20991239
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 126; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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