Photodissociation dynamics of CO[sub 2]at 157.6 nm by photofragment-translational spectroscopy

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DOIResolve DOI: http://doi.org/10.1063/1.464238
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TypeArticle
Journal titleThe Journal Of Chemical Physics
Volume98
Issue3
Pages20662076; # of pages: 11
SubjectCARBON DIOXIDE; CENTEROFMASS SYSTEM; ENERGY SPECTRA; FAR ULTRAVIOLET RADIATION; PHOTODISSOCIATION; TIMEOFFLIGHT METHOD
AbstractThe photodissociation of CO2 at 157 nm was studied by the photofragment-translational spectroscopy technique. Product time-of-flight spectra were recorded and center-of-mass translational energy distributions were determined. Two electronic channels were observed�one forming O(1D) and the other O(3P). With previously determined anisotropy parameters of beta=2 for the O(3P) channel and beta=0 for the O(1D) channel, an electronic branching ratio of 6%�2%O(3P) was obtained, consistent with previous results. The translational energy distribution for the CO(v)+O(3P) channel was very broad (over 30 kcal/mol) and appeared to peak near CO(v=0). The value of beta=2 for the O(3P) channel was confirmed by comparing Doppler profiles, derived from our measured translational energy distribution, with previously measured Doppler profiles. This suggests that the O(3P) channel arises from a direct transition to an excited triplet state. The O(1D) channel had a structured time-of-flight which related to rovibrational distributions of the CO product. The influence of the excitation of the CO2(nu2) bending mode was investigated and shown to have a small but not negligible contribution. Based upon a comparison of our data with a previous vacuum-ultraviolet (VUV) laser induced fluorescence study, we obtain as our best estimate of the vibrational branching ratio, CO(v=0)/CO(v=1)=1.9, for the CO(v)+O(1D) channel.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
NPARC number12337939
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Record identifier475173a0-f1c0-4956-9738-ef031ca15a06
Record created2009-09-10
Record modified2017-03-23
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