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Formation of the CH fragment in the 193 nm photodissociation of CHCl

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2837664· OSTI ID:21024775
;  [1]
  1. Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218-2685 (United States)

The CH fragment from the 193 nm photodissociation of CHCl is observed in a molecular beam experiment. This fragment is formed in the higher-energy dissociation pathway, the lower pathway involving formation of CCl. Both the CHCl parent molecule and the CH fragment were detected by laser-induced fluorescence. The 193 nm CHCl absorption cross section was estimated from the reduction of the CHCl signal as a function of the photolysis laser fluence. The CH internal state distribution was derived from the analysis of laser-induced fluorescence spectra of the A-X {delta}v=0 sequence. A modest degree of rotational excitation was found in the CH fragment; the most probable rotational level is N=1, but the distribution has a tail extending to N>25. Also observed is a slight preference for formation of {lambda}-doublets of A{sup ''} symmetry, which appears to increase with increasing rotational angular momentum N. Vibrationally excited CH was observed, and the degree of vibrational excitation was found to be low. The energy available to the photofragments is predominantly released as translational excitation. The preferential formation of A{sup ''} {lambda}-doublets suggests that dissociation occurs through a nonlinear excited state.

OSTI ID:
21024775
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 128; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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