Photodissociation rates of ox y gen and ozone molecules in the stratosphere, mesosphere and lower thermosphere were examined to see the uncertainties in treatment of the predissociation of the Schumann-Runge bands, the solar flux and the transmission in the Schumann-Runge bands. The effect of these uncertainties on the calculated distribution of the ozone molecule was estimated.
First were examined the previous studies about the predissociation of the Schumann-Runge bands. It is concluded that the vibrational levels of B
3Σ
u state are predissociated to some extent between υ′=3 and υ′=17. This is confirmed by spectroscopic and photochemical evidences. But some questions remain about the crossing point of the potential curve of
3Π
u state with that of B
3Σ
u state, the contribution of the underlying continuum to the decomposition of the oxygen molecule, the quantum yield of the ozone formation from the decomposition of the excited oxygen molecule in the Schumann-Runge system and so on. The effect of the predissociation on the dissociation rates of the oxygen and ozone molecules was estimated.
Next, we reviewed the estimations of solar ultraviolet radiation outside the atmosphere. Large variations are recognized in the reported solar radiation below 2500 Å. These variations come from several sources. The first of them is the absolute intensity calibration. The second problem is the variability of the sun. The third problem is difference in the detectors.
We applied the band model to the calculations of transmission in the Schumann-Runge bands in order to reduce the labor involved in exact calculations of transmission in the bands. We examined the line broadening effects and adopted the Lorentz line shape for the predissociation line shape. From the line positions and the intensity distributions of the rotational lines, we came to the conclusion that the random model for the inverse first power or the exponential distribution of line intensities is most appropriate.
The dissociation rate of the oxygen molecule excluding the predissociation was compared with that including the predissociation of the Schumann-Runge bands. The remarkable contribution of the predissociation appears above 45 km. The maximum contribution of the predissociation appears at 75 km for sec
z=1.0, at 80 km for sec
z=3.0 and at 85 km for sec
z=6.0. The ratio of the dissociation rate including the predissociation to that excluding the predissociation falls in the range from 8 to 3for sec
z=3.0.
Taking account of the uncertainty in solar ultraviolet radiation due to the difference between the values obtained by photographic technique and those obtained by photoelectric technique, an uncertainty of factor 2to 4 appears in the dissociation rate of the oxygen molecule between 40and 100 km.
The deviations of the dissociation rate of the oxygen molecule due to various causes originating from the band model in the Schumann-Runge bands were estimated. The deviation due to the distribution functions (inverse first power distribution and exponential distribution) is at most about 11% between 40 and 100 km. The deviations due to the band model parameters are: (1) 20% due to the mean line intensity (mean absorption coefficient), (2) 20% due to the mean line spacing, and (3) 5% due to the mean line half-width.
The photodissociation rate of the ozone molecule is hardly affected by the predissociation or by the band model for the Schumann-Runge bands, but has the uncertainty of about 6% between 40 and 100 km due to the ambiguity of solar radiation.
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