Quantum yields of O(¹D) formation in the photolysis of ozone between 230 and 308 nm

Abstract

Ozone molecules are photolyzed in the strong photoabsorption band of the Hartley band at 230–308 nm, and the O(3Pj) photofragments produced by the photolysis are detected directly by a technique of laser‐induced fluorescence around 130 nm. The quantum yield values for O(1D) formation in the photolysis of ozone at 297 ± 2 K are determined as a function of the photolysis wavelength, using the O(1D) quantum yield value of 0.79 at 308 nm as a reference. The O(1D) quantum yield values obtained are found to be almost independent of the photolysis wavelength over the Hartley band (∼0.91). The results are compared with the values measured previously using various experimental techniques and also with the recommendation values for use in atmospheric modeling. The effects of the present yield data on the O(1D) production rates from ozone photolysis in the stratosphere are evaluated. Impact of our new O(1D) quantum yield values on the stratospheric chemistry has also been explored using a one‐dimensional photochemical model. The smaller O(1D) production rates as compared to the latest NASA/JPL recommendation values are followed by changes in the efficiency of the chemical chain reactions involving HOx, NOx, and ClOx and result in the higher O3 concentrations throughout the stratosphere.

Sensitivity studies of the recent new data on O(<sup>1</sup><i>D</i>) quantum yields in O<sub>3</sub> Hartley band photolysis in the stratosphere

“…Talukdar et al (1998) reported that the O( 1 D) quantum yield between 289 and 305 nm was 0.89±0.02, which is in good agreement with results presented by Taniguchi et al (2000) and Takahashi et al (2002). The yield values reported by Trolier and Wiesenfeld (1988) and JPL-2000 recommendations in this wavelength region are larger than values reported by Talukdar et al (1998) , Taniguchi et al (2000), and Takahashi et al (2002). At shorter wavelengths, JPL-2000 panel has recommended a constant value of 0.95 for the O( 1 D) quantum yield in the Hartley band photolysis of O 3 between obtained by Taniguchi et al (2000) and Takahashi et al (2002).…”

“…The yield values reported by Trolier and Wiesenfeld (1988) and JPL-2000 recommendations in this wavelength region are larger than values reported by Talukdar et al (1998) , Taniguchi et al (2000), and Takahashi et al (2002). At shorter wavelengths, JPL-2000 panel has recommended a constant value of 0.95 for the O( 1 D) quantum yield in the Hartley band photolysis of O 3 between obtained by Taniguchi et al (2000) and Takahashi et al (2002). For comparison, the yield values reported by other groups are also shown (Trolier and Wiesenfeld, 1988;Cooper et al, 1993;Talukdar et al, 1997Talukdar et al, , 1998.…”

“…2, the yield values presented by Taniguchi et al (2000) and Takahashi et al (2002) are compared with both values previously reported by other different groups (Trolier and Wiesenfeld, 1988;Cooper et al, 1993;Talukdar et al, 1997Talukdar et al, , 1998 and JPL-2000 recommendations . Talukdar et al (1998) reported that the O( 1 D) quantum yield between 289 and 305 nm was 0.89±0.02, which is in good agreement with results presented by Taniguchi et al (2000) and Takahashi et al (2002). The yield values reported by Trolier and Wiesenfeld (1988) and JPL-2000 recommendations in this wavelength region are larger than values reported by Talukdar et al (1998) , Taniguchi et al (2000), and Takahashi et al (2002).…”

“…The experimental data for the O( 1 D) quantum yields from O 3 photolysis over the Hartley band (200-300 nm) are sparse, which may result in some notable uncertainties in the model calculation. Very recently, Taniguchi et al (2000) and Takahashi et al (2002) The absolute quantum yields of O( 1 D) formation from O 3 photolysis between 306 and 328 nm have been evaluated by Matsumi et al (2002) with the detailed examination of recent experimental measurements as a joint activity of SPARC and IGAC. Very recently, Takahashi et al (2002) have measured the O( 1 D) quantum yields from O 3 photolysis between 230 and 308 nm using a new experimental technique.…”

“…Very recently, Taniguchi et al (2000) and Takahashi et al (2002) The absolute quantum yields of O( 1 D) formation from O 3 photolysis between 306 and 328 nm have been evaluated by Matsumi et al (2002) with the detailed examination of recent experimental measurements as a joint activity of SPARC and IGAC. Very recently, Takahashi et al (2002) have measured the O( 1 D) quantum yields from O 3 photolysis between 230 and 308 nm using a new experimental technique. Using the same technique, Taniguchi et al (2000) have indicated that the O( 1 D) quantum yield in the wavelength range of 297-306 nm is almost independent of the wavelength (∼0.89).…”