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The photodissociation reaction dynamics of CF{sub 3}I at 304 nm ({sup 3}Q{sub 0+}, {sup 1}Q{sub 1}<-{sup 3}Q{sub 0+}, and {sup 3}Q{sub 1})

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2402173· OSTI ID:20864351
; ;  [1]
  1. Department of Chemistry, University of Southern California, Los Angeles, California 90089 (United States)
The photodissociation of CF{sub 3}I at 304 nm has been studied using long time-delayed core-sampling photofragment translational spectroscopy. Due to its capability of detecting the kinetic energy distribution of iodine fragments with high resolution, it is able to directly assign the vibrational state distribution of CF{sub 3} fragments. The vibrational state distributions of CF{sub 3} fragments in the I*({sup 2}P{sub 1/2}) channel, i.e., {sup 3}Q{sub 0+} state, have a propensity of the {nu}{sub 2}{sup '} umbrella mode with a maximum distribution at the vibrational ground state. For the I({sup 2}P{sub 3/2}) channel, i.e., {sup 1}Q{sub 1}<-{sup 3}Q{sub 0+}, the excitation of the {nu}{sub 2}{sup '} umbrella mode accounts for the majority of the vibrational excitation of the CF{sub 3} fragments. The 1 {nu}{sub 1}{sup '} (symmetric CF stretch) +n{nu}{sub 2}{sup '} combination modes, which are associated with the major progression of the {nu}{sub 2}{sup '} umbrella mode, are observed for the photodissociation of CF{sub 3}I at the I channel, i.e., {sup 3}Q{sub 1} state. The bond dissociation energy of the CI bond of CF{sub 3}I is determined to be D{sub 0}(CF{sub 3}-I){<=}53.62{+-}0.5 kcal/mol (18 754{+-}175 cm{sup -1}) by applying the energy conservation law to the photodissociation process.
OSTI ID:
20864351
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 21 Vol. 125; ISSN JCPSA6; ISSN 0021-9606
Country of Publication:
United States
Language:
English