Study of the quantum-yields of the products in the photolysis of ozone

臭氧在紫外光区光解产生0（1D）的量子产率作为波长和温度的函数，是大气化学模拟计算的关键输入。臭氧分子在230 - 308 nm的Hartley带的强光吸收带内发生光解，并在130 nm附近用激光诱导荧光技术直接检测到O（3 Pj）光碎片。以308 nm处的0（1D）量子产额绝对值0.79为参考，测定了297 ± 2K下臭氧光解生成0（1D）量子产额随光解波长的变化。在Hartley带内，0（1D）量子产额几乎与波长无关（λ = 0.91）。结果进行了比较，与以前测量的值与各种实验技术。计算结果还与大气模拟中使用的推荐值进行了比较。对平流层中O3光解产生的O（1D）的相对生成率进行了评估。我们已经表明，在15，25和40公里的高度，在这项研究中获得的0（1D）量子产额值计算的0（1D）的生产率分别小于1.9%，3.5%和4.8%的最新NASA/喷气推进实验室的建议计算。另一方面，用我们的0（1D）量子产额数据计算的0（1D）产生率在15和25 km处分别比IUPAC推荐值小4.0%和5.7%，在40 km处大0.2%。

The quantum yield for 0(1D) production in the photolysis of ozone in the ultraviolet region as a function of wavelength and temperature is a key input for modeling calculations in the atmospheric chemistry. Ozone molecules have been photolysed in its strong photoabsorption band of the Hartley band at 230 - 308 nm and the 0(3Pj) photo fragments have been detected directly by a technique of laser-induced fluorescence around 130 nm. The quantum yield values for 0(1D) formation in the photolysis of ozone at 297 ± 2 K have been determined as a function of the photolysis wavelength, using the absolute 0(1D) quantum yield value of 0.79 at 308 nm as a reference. The 0(1D) quantum yield values obtained are found to be almost independent of the wavelength over the Hartley band (〜0.91). The results are compared with the values measured previously with various experimental techniques. The results are also compared with the recommendation values for use in atmospheric modeling. The relative production rates of 0(1D) from 03 photolysis in the stratosphere have been evaluated. We have shown that the 0(1D) production rates calculated with the 0(1D) quantum yield values obtained in this study are smaller than those calculated with the latest NASA/JPL recommendation by 1.9, 3.5 and 4.8 % , at the altitudes of 15, 25 and 40 km, respectively. On the other hand, the the 0(1D) production rates calculated with our 0(1D) quantum yield data are smaller than those with the IUPAC recommendation by 4.0 and 5.7 % at 15 and 25 km, respectively, and larger by 0.2 % at 40 km.