Experiments concerning the laser-enhanced reaction between vibrationally excited O3 and NO
- 1 February 1978
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 68 (3) , 1022-1037
- https://doi.org/10.1063/1.435793
Abstract
The reaction of vibrationally excited O3 with NO has been studied for the temperature range 138–410 ° K. Observations were made of chemiluminescence of vibrationally excited NO†2(2A1) and electronically excited NO*2(2B1,2) reaction products immediately following laser excitation of O3(001) molecules. The present results, combined with previous rate constant measurements, permit a determination of the separate rates for formation of NO2†(2A1) molecules and collisional deactivation of vibrationally excited O3 by NO. This latter rate constant exhibits a minimum value at 230 °K. It is shown that the stretching and bending modes of O3 make comparable contributions to reaction rate enhancement. Excitation of either the coupled stretching modes or the bending mode results in a lowering of the activation energies for reactions leading to NO*2(2B1,2) and NO†2(2A1) products of 31% (1.3 kcal/mole) and 56% (1.3 kcal/mole), respectively. The intermode coupling of vibrational energy from the stretching modes to the bending mode of O3 in collisions with NO occurs with a rate constant of (1.2±0.6) ×104 sec−1 Torr−1 at 308±3 °K.Keywords
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