An Experimental and Theoretical Study of the Reactions OIO + NO and OIO + OH

Plane, J. M. C., Joseph, D. M., Allan, B. J., Ashworth, Stephen and Francisco, J. S. (2006) An Experimental and Theoretical Study of the Reactions OIO + NO and OIO + OH. The Journal of Physical Chemistry A, 110 (1). pp. 93-100.

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Abstract

The kinetics of the reaction OIO + NO were studied by pulsed laser photolysis/time-resolved cavity ring-down spectroscopy, yielding k(235-320 K) = 7.6+4.0-3.1 × 10-13 exp[(607±128)/T] cm3 molecule-1 s-1. Quantum calculations on the OIO + NO potential-energy surface show that the reactants form a weakly bound OIONO intermediate, which then dissociates to the products IO + NO2. Rice-Ramsberger-Kassel-Markus (RRKM) calculations on this surface are in good accord with the experimental result. The most stable potential product, IONO2, cannot form because of the significant rearrangement of OIONO that would be required. The reaction OIO + OH was then investigated by quantum calculations of the relevant stationary points on its potential-energy surface. The very stable HOIO2 molecule can form by direct recombination, but the bimolecular reaction channels to HO2 + IO and HOI + O2 are closed because of significant energy barriers. RRKM calculations of the HOIO2 recombination rate coefficient yield krec,0 = 1.5 × 10-27 (T/300 K)-3.93 cm6 molecule-2 s-1, krec,8 = 5.5 × 10-10 exp(46/T) cm3 molecule-1 s-1, and Fc = 0.30. The rate coefficients of both reactions are fast enough around 290 K and 1 atm pressure for these reactions to play a potentially important role in the gas phase and aerosol chemistry in the marine boundary layer of the atmosphere.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Rachel Smith
Date Deposited: 10 Feb 2011 16:13
Last Modified: 31 Oct 2019 13:55
URI: https://ueaeprints.uea.ac.uk/id/eprint/21125
DOI: 10.1021/jp055364y

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