Crossed-beams and theoretical studies of hyperthermal reactions of O( 3P) with HCl

Jianming Zhang, Amy L. Brunsvold, Hari P. Upadhyaya, Timothy K. Minton, Jon P. Camden, Sophya Garashchuk, George C Schatz

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Abstract

The reaction of O(3P) 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(3P) + HCl collisions.

Original languageEnglish
Pages (from-to)4905-4916
Number of pages12
JournalJournal of Physical Chemistry A
Volume114
Issue number14
DOIs
Publication statusPublished - Apr 15 2010

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Atoms
atoms
collisions
elimination
reagents
products
energy
internal energy
Trajectories
trajectories
collision parameters
Molecular beams
thresholds
Angular distribution
stripping
molecular beams
angular distribution
dissociation
Molecules
Geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Zhang, J., Brunsvold, A. L., Upadhyaya, H. P., Minton, T. K., Camden, J. P., Garashchuk, S., & Schatz, G. C. (2010). Crossed-beams and theoretical studies of hyperthermal reactions of O( 3P) with HCl. Journal of Physical Chemistry A, 114(14), 4905-4916. https://doi.org/10.1021/jp101023y

Crossed-beams and theoretical studies of hyperthermal reactions of O( 3P) with HCl. / Zhang, Jianming; Brunsvold, Amy L.; Upadhyaya, Hari P.; Minton, Timothy K.; Camden, Jon P.; Garashchuk, Sophya; Schatz, George C.

In: Journal of Physical Chemistry A, Vol. 114, No. 14, 15.04.2010, p. 4905-4916.

Research output: Contribution to journalArticle

Zhang, J, Brunsvold, AL, Upadhyaya, HP, Minton, TK, Camden, JP, Garashchuk, S & Schatz, GC 2010, 'Crossed-beams and theoretical studies of hyperthermal reactions of O( 3P) with HCl', Journal of Physical Chemistry A, vol. 114, no. 14, pp. 4905-4916. https://doi.org/10.1021/jp101023y
Zhang J, Brunsvold AL, Upadhyaya HP, Minton TK, Camden JP, Garashchuk S et al. Crossed-beams and theoretical studies of hyperthermal reactions of O( 3P) with HCl. Journal of Physical Chemistry A. 2010 Apr 15;114(14):4905-4916. https://doi.org/10.1021/jp101023y
Zhang, Jianming ; Brunsvold, Amy L. ; Upadhyaya, Hari P. ; Minton, Timothy K. ; Camden, Jon P. ; Garashchuk, Sophya ; Schatz, George C. / Crossed-beams and theoretical studies of hyperthermal reactions of O( 3P) with HCl. In: Journal of Physical Chemistry A. 2010 ; Vol. 114, No. 14. pp. 4905-4916.
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