Specific rate constants k(E, J) for the dissociation of NO2. I. Time-resolved study of rotational dependencies

2001 | journal article. A publication with affiliation to the University of Göttingen.

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​Abel B, Kirmse B, Troe J, Schwarzer D. ​Specific rate constants k(E, J) for the dissociation of NO2. I. Time-resolved study of rotational dependencies​. ​​The Journal of Chemical Physics. ​2001;​115​(14):​​6522​-6530​. ​doi:10.1063/1.1398305. 

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Authors
Abel, Bernd; Kirmse, B.; Troe, Juergen; Schwarzer, Dirk
Abstract
The effect of rotational excitation on the specific rate constants k(E,J) of the unimolecular decomposion of NO2 has been investigated. Time-resolved pump- and probe experiments with sub-ps time resolution are reported in which NO2 molecules with well-defined rotational and vibrational energy distributions were optically excited near and above the dissociation threshold. The subsequent unimolecular decay of the reacting NO2 molecules was probed by time-resolved laser-induced fluorescence of the disappearing NO2 via excitation to Rydberg states. At constant photolysis wavelength, increasing rotational energy (up to 310 cm(-1)) was found to leave the overall decay rate nearly unaffected. This observation can be rationalized by assuming a compensation of the angular momentum and energy dependences of the specific rate constants when J and E are, changed at the same time. Keeping the total energy E nearly constant and changing J independently, the effect of rotation on the decay rate can be separated and observed more clearly. From the experimental data we conclude that, for sufficiently high J and constant total energy, molecules with larger J dissociate more slowly than molecules with small J, which is in agreement with predictions from statistical unimolecular rate theory. (C) 2001 American Institute of Physics.
Issue Date
2001
Status
published
Publisher
Amer Inst Physics
Journal
The Journal of Chemical Physics 
ISSN
0021-9606

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