Dynamical bottleneck in the reaction H+O/sub 2//r arrow/OH+O at high collision energies
The nascent rotational and /lambda/-doublet state distributions of OH produced in the reaction H+O/sub 2//r arrow/OH(/ital N/,/ital v/,/ital f/ )+O were probed by fast atom--laser induced fluorescence experiments at average collision energies /ital E/=100, 183, 200, 220, and 243 kJ/mol. With increasing /ital E/, the rotational product distributions become increasingly nonstatistical with a narrow peak at high rotational states, in good agreement with quasiclassical trajectory calculations on an /ital ab/ /ital initio/ potential energy surface. The calculations show the narrow product rotational peak to be due to an increasing specifity of the initial H--O/sub 2/ configurations leading to reactions. At high /ital E/ the impact parameters and initial polar angles are confined to a rather small range allowing reaction only for an optimal approach. The OH /lambda/-doublet distributions show preference for the /Pi/(/ital A//prime/) component probed by /ital R/ lines at all collision energies investigated. This suggests a planar reaction path and little importance of out of plane rotation of the HO/sub 2/ complex at the high collision energies of the experiment. The experimental /lambda/-doublet distributions are quantitatively compared with the degree of in-plane scattering obtained from the trajectory calculations.
- Research Organization:
- Physikalisch-Chemisches Institut der Ruprecht-Karls-Universitat, D-6900 Heidelberg, Federal Republic of Germany(DE)
- OSTI ID:
- 6006936
- Journal Information:
- J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 91:4; ISSN JCPSA
- Country of Publication:
- United States
- Language:
- English
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CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMBUSTION
COMBUSTION PRODUCTS
ELEMENTS
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ENERGY LEVELS
EXCITED STATES
HYDROGEN
HYDROXYL RADICALS
KINETIC ENERGY
NONMETALS
OXIDATION
OXYGEN
RADICALS
ROTATIONAL STATES
THERMOCHEMICAL PROCESSES
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