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Determination of v = 0 Rate Constants for the Reaction: D + F2,
IOWA UNIV IOWA CITY DEPT OF CHEMISTRY
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Various chemiluminescence techniques Measured Relaxation, Arrested Relaxation, and Chemiluminescence Mapping provide a powerful tool for obtaining detailed rate constants and energy disposal information for exoergic chemical reactions. These techniques rely on observing emission of vibrationally excited products so that steady state populations of these excited states can be deconvoluted into the microscopic rate constants of the formation reaction. The inherent weakness of these techniques is that the rate constants into the ground vibrational state can not be obtained. Nonetheless, ground state vibrational populations are often reported the upper level populations are extrapolated to v 0 by an information theory approach. Obvious deviations can result if the reaction dynamics are not well behaved. Author
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