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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Abel, Bernd; Kirmse, B.; Troe, Juergen; Schwarzer, Dirk
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.
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Amer Inst Physics
The Journal of Chemical Physics 



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