VIBRATIONAL AND ROTATIONAL PROPENSITY RULES FOR THE VIBRATIONAL PREDISSOCIATION OF $Ar--CO_{2}$
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Date
1991
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Publisher
Ohio State University
Abstract
Vibrational predissociation in $Ar--CO_{2}$ has been studied at the state-to-state level in order to determine both the vibrational and rotational propensity rules associated with this process. The technique used in this study involves the direct measurement of the angular distribution of the photofragments using an apparatus based on the optothermal technique. Dissociation is found to proceed via the highest available photofragment vibrational channel. An interesting even/odd rotational propensity is observed, which is consistent with the results of collisionally based calculations for this system. The dissociation energy is also determined from these experiments, and combined with the results already available in the literature, is used to refine previously reported two dimensional $Ar--CO_{2}$ potential energy surfaces. The adjusted potentials which differ from the previous ones primarily in the steepness of the surface with respect to angular displacements from equilibrium, are used to predict the van der Waals stretching frequency and the energy of other excited vibrational states.
Description
Author Institution: Department of Chemistry, University of North Carolina; Department of Chemistry, University of North Carolina; Department of Chemistry, Amherst College