Vibrational Energy of Ozone During Photolytic Explosion

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Abstract
Following a short photolysis flash of the proper energy the absorption spectrum in the region of the ozone ultraviolet system, a continuum centered at about 2550 Å, broadens and shifts toward longer wavelength as the reaction proceeds. Kinetic measurements of this shift over a period of 200 μsec following a mild photolysis flash of 12 μsec duration in 0.5 Torr pure ozone are interpreted in terms of population of ozone vibrational energy states by exchange of energy with vibrationally excited oxygen formed during the exothermic decomposition. Considerable O2†–O3† vibrational equilibration occurs within 50 μsec. A semiempirical model which correlates the ozone vibrational temperature and the observed data is discussed in relation to the over‐all energetics of ozone decomposition.

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