ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Vibrational-state-specific total-removal relaxation rate constants, kv(M), for O2(X 3Σ−g, v=15 to 26) by M=CO2, N2O, and N2 have been obtained using the stimulated emission pumping (SEP) method in a pump–dump and probe configuration. Relaxation by O3 was studied using the chemical activation method, where the reaction: O(3P)+O3→O2(v)+O2, was employed to produce highly vibrationally excited O2 in an excess of ozone. Efficient (1%–2% of the gas kinetic limit) near-resonant 2–1 and/or 1–1 vibration-to-vibration (V–V) energy exchange was observed whenever the energy resonant condition was fulfilled and the transition in the quench partner would have been an allowed infrared transition in the isolated molecule. For M=CO2 and N2O, the temperature dependence of the 2–1 near-resonant energy transfer rate constants was found to be inverted. In contrast, the temperature dependence of the V–R, T relaxation rate constants for M=O2 was normal. For M=N2, a weak but positive temperature dependence was found. By extrapolating the temperature dependence to mesospheric temperatures (200 K) the effect of highly vibrationally excited O2 on the thermal budget can be discussed. The rate constant for the reaction of O(3P)+O3 was determined for an elevated collision energy of ∼10 kcal/mol and was found to be 5000 times larger than the room temperature rate constant. © 1996 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.472259
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