Kinetic and mechanistic studies of the recombination of OH with NO2: vibrational deactivation, isotopic scrambling and product isomer branching ratios

Faraday Discuss. 2005;130:111-23; discussion 125-51, 519-24. doi: 10.1039/b417458p.


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) x 10(-11) cm3 molecule 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 x 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.