Dynamics of the 193 nm photodissociation of dichlorocarbene

Journal Article · Sat Oct 07 04:00:00 EDT 2006 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2212416· OSTI ID:20864307

Shin, Seung Keun; Dagdigian, Paul J ^[1]

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1. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218-2685 (United States)

The dynamics of the 193 nm photodissociation of the CCl{sub 2} molecule have been investigated in a molecular beam experiment. The CCl{sub 2} parent molecule was generated in a molecular beam by pyrolysis of CHCl{sub 3}, and both CCl{sub 2} and the CCl photofragment were detected by laser fluorescence excitation. The 193 nm attenuation cross section was estimated from the reduction of the CCl{sub 2} signal as a function of the photolysis laser fluence. The internal state distribution of the CCl photofragment was derived from analysis of laser fluorescence excitation spectra in the A {sup 2}{delta}-X {sup 2}{pi} band system. Most of the energy available to the CCl(X {sup 2}{pi})+Cl fragments appears as translational energy. The CCl fragment rotational energy is much less than predicted in an impulsive model. The excited electronic state appears to dissociate indirectly, through coupling with a repulsive state arising from the ground-state CCl(X {sup 2}{pi})+Cl asymptote. The identity of the initially excited electronic state is discussed on the basis of what is known about the CCl{sub 2} electronic states.

• OSTI ID: 20864307
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 125; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CHLOROFORM
COUPLING
CROSS SECTIONS
DISSOCIATION
EXCITATION
EXCITED STATES
FLUORESCENCE
GROUND STATES
MOLECULAR BEAMS
PHOTOLYSIS
PHOTON-MOLECULE COLLISIONS
PYROLYSIS
SPECTRA