Temperature dependence of the HO{sub 2} + ClO reaction. 1. Reaction kinetics by pulsed photolysis-ultraviolet absorption and ab initio studies of the potential surface
The kinetics of the HO{sub 2} + ClO reaction was studied using the flash photolysis/ultraviolet absorption technique over the temperature range 203--364 K and pressure range 50--700 Torr of N{sub 2}. In contrast to previous work, the temperature dependence displayed linear Arrhenius behavior over the entire temperature range. Ab initio calculations of intermediates and transition states have been carried out on the singlet and triplet potential energy surfaces. These calculations show that the reaction proceeds mainly through the ClO-HO{sub 2} complex on the triplet surface; however, collisionally stabilized HOOOCl formed on the singlet surface will possess an appreciable lifetime due to large barriers toward decomposition to HCl and HOCl. Termolecular rate calculations using ab initio parameters lead to a strong collision rate constant for HOOOCl formation. This intermediate may be important under both laboratory and atmospheric conditions.
- Research Organization:
- California State Univ., Los Angeles, CA (US)
- OSTI ID:
- 20017475
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 104, Issue 2; Other Information: PBD: 20 Jan 2000; ISSN 1089-5639
- Country of Publication:
- United States
- Language:
- English
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