Resonant vibration-vibration energy transfer between highly vibrationally excited O-2(X (3)Sigma(g)(-),v=15-26) and CO2, N2O, N-2, and O-3

Vibrational-state-specific total-removal relaxation rate constants, k(v)(M), for O-2(X (3) Sigma(g)(-), v = 15 to 26) by M=CO2, N2O, and N-2 have been obtained using the stimulated emission pumping (SEP) method in a pump-dump and probe configuration. Relaxation by O-3 was Studied using the chemical activation method, where the reaction: O(P-3)+O-3-->O-2(v)+O-2, was employed to produce highly vibrationally excited O-2 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=O-2 was normal. For M=N-2, a weak but positive temperature dependence was found. By extrapolating the temperature dependence to mesospheric temperatures (200 K) the effect of highly vibrationally excited O-2 On the thermal budget can be discussed. The rate constant for the reaction of O(P-3)+O-3 was determined for an elevated collision energy of similar to 10 kcal/mol and was found to be 5000 times larger than the room temperature rate constant. (C) 1996 American Institute of Physics.