Kinetic and mechanistic studies of the recombination of OH with NO 2: Vibrational deactivation, isotopic scrambling and product isomer branching ratios

Luca D'Ottone, Dieter Bauer, Pedro Campuzano-Jost, Melissa Fardy, Anthony J. Hynes

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

The kinetics and mechanism of the three-body recombination of OH with NO2 were studied using a pulsed laser photolysis - pulsed laser induced fluorescence technique. The rate coefficients for deactivation of vibrationally excited OH (v = 1-5) by NO2 were found to be independent of vibrational level with a value of (6.4 ± 0.3) × 10-11 cm3 molecule-1 s-1 at 298 K. The rate coefficient for reaction of 18OH with NO2 was measured and found to be much faster than for unlabeled OH with a "zero pressure" rate of 1 × 10-11 cm3 molecule -1 s-1 at 298 K and 273 K. Observation of temporal profiles of 16OH and 18OH suggest that isotopic scrambling in the initially formed [H18ON16O2] complex is complete on the microsecond time scale of our experiments. The rate coefficient for reaction of unlabeled OH with NO2 was measured at 413 K in 400 Torr of He. Biexponential temporal profiles were obtained and are consistent with a 10 ± 3% yield of the weakly bound HOONO isomer.

Original languageEnglish (US)
Pages (from-to)111-123
Number of pages13
JournalFaraday Discussions
Volume130
DOIs
StatePublished - Sep 8 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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