Ozone Ultraviolet Photolysis. III. Disposition of Vibrational Energy

摘要

Absorption by the Schumannmdash;RungeB3Sgr;uminus;larr;X3Sgr;gminus;system of O2was measured in order to identify the products of theO(1D)+O3reaction.O3+O(1D)rarr; 2O(3P)+O2,O3+O(1D)rarr;2O2dagger;withk2aprime;gsim;10k2aprime; prime;. TheO2dagger;product is observed in statesvprime; prime;le; 30and is apparently formed in all levels up to the dissociation limit. The formation and disappearance of vibrationally excitedO2dagger;are correlated with measurements of changes in ozone absorbance that are usually attributed to vibrational excitation. Under marginally isothermal and nonisothermal conditions ozone is excited to a nonequilibrium energy distribution, probably by vibrationrarr;vibration energy transfer fromO2dagger;. The rates of all processes having an activation energy are enhanced by this excitation.