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We studied quantitatively the photochemistry of solid O3 and O2 films at 193nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pureozone destroyed O3, but a small amount of ozone remained in the film at highfluence. Photolysis of pure O2 produced O3 in an amount that increased withphoton fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratioat saturation is 0.03, nearly 10-30 times larger than those obtained in gasphase photolysis. This enhancement is attributed to the increasedphotodissociation of O2 due to photoabsorption by O2 dimers, a processsignificant at solid state densities. We obtain initial quantum yield for ozonesynthesis from solid oxygen, {\Phi} (O3) = 0.18 and for destruction of ozoneand oxygen in their parent solids, {\Phi} (- O3) = 1.7 and {\Phi} (-O2) = 0.28.Combined with known photoabsorption cross sections, we estimate probabilitiesfor germinate recombination of 0.15 for O3 fragments and 0.90 for oxygen atomsfrom O2 dissociation. Using a two-parameter kinetic model, we deduce theaverage probabilities for the reaction of an O atom with O2 and O3 to be 0.10and 1, respectively. These probabilities are the same for both O2 and O3 films,even though the distribution of kinetic and internal energy of thephotofragments is very different in both cases. This finding suggests efficientenergy relaxation of photofragments in the solid occur prior to their reactionswith other species.

Photolysis of pure solid O3 and O2 films at 193 nm