The relative quantum yields of O2(a1 deltag from the photolysis of ozone at 227K

Physics

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Absorption Spectra, Abundance, Oxygen Production, Ozone, Photolysis, Temperature Dependence, Wavelengths, Yield, Data Correlation, Experiment Design, Laser Spectroscopy, Spectrum Analysis, Vibrational States

Scientific paper

The relative quantum yields of O2(a1deltag) from the photolysis of ozone have been measured at 227(+/- 2)K over the wavelength range 300nm greater than or = lambda greater than or = 322nm, and are compared to those measured previously at 298K (Ball et al., 1993). The yields at the two temperatures show the same initial wavelength dependence in the fall-off region, in contrast to literature measurements of the O1D yields which show a shift in the fall-of curve to shorter wavelengths at low temperature. For lambda greater than 309nm, the yield at 227K falls more rapidly than that at 298K, confirming that internal energy medicated dissociation of ozone provides the major source of O2(a1deltag) at wavelengths just beyond the 310nm threshold for the spin allowed production of the two singlet products. However, the yields of O2(a1deltag) at 227K and 298K were found to approximately equal for photolysis wavelengths lambda greater than or = 320nm, and substantially larger than O1D yields predicted from modeling currently available for the photolysis of vibrationally excited ozone. These results suggest the existence of a spin forbidden dissociation channel for O2(a1)deltaRg) with a quantum yield of phi approx. = 0.1 at wavelengths near to 320nm.

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