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Abstract

The reaction of O(3 P) with HCl at hyperthermal collision energies (45-116 kcal mol-1 ) has been investigated with crossed-molecular beams experiments and direct dynamics quasi-classical trajectory calculations. The reaction may proceed by two primary pathways, (1) H-atom abstraction to produce OH and Cl and (2) H-atom elimination to produce H and ClO. The H-atom abstraction reaction follows a stripping mechanism, in which the reagent O atom approaches the HCl molecule at large impact parameters and the OH product is scattered in the forward direction, defined as the initial direction of the reagent O atoms. The H-atom elimination reaction is highly endoergic and requires low-impact-parameter collisions. The excitation function for ClO increases from a threshold near 45 kcal mol-1 to a maximum around 115 kcal mol-1 and then begins to decrease when the ClO product can be formed with sufficient internal energy to undergo secondary dissociation. At collision energies slightly above threshold for H-atom elimination, the ClO product scatters primarily in the backward direction, but as the collision energy increases, the fraction of these products that scatter in the forward and sideways directions increases. The dependence of the angular distribution of ClO on collision energy is a result of the differences in collision geometry. Collisions where the H atom on HCl is oriented away from the incoming reagent O atom lead to backward-scattered ClO and those where the H atom is oriented toward the incoming O atom lead to forward-scattered ClO. The latter trajectories do not follow the minimum energy path and involve larger translational energy release. Therefore, they become dominant at higher collision energies because they lead to lower internal energies and more stable ClO products. The H-atom abstraction and elimination reactions have comparable cross sections for hyperthermal O(3 P) + HCl collisions.

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