Tyuterev V G, Barbe A, Manceron L, Grouiez B, Tashkun S A, Burgalat J, Rotger M
National Research Tomsk State University, Tomsk, 634050, Russia; V. E. Zuev Institute of Atmospheric Optics, SB Russian Academy of Sciences, Tomsk 634050, Russia.
GSMA UMR 7331 Université de Reims, 51000, France.
Spectrochim Acta A Mol Biomol Spectrosc. 2024 Jan 15;305:123456. doi: 10.1016/j.saa.2023.123456. Epub 2023 Sep 27.
Ozone is one of the important molecules in terms of the impact on the atmospheric chemistry, climate changes, bio- and eco-systems and human health. It has a strong absorption in the microwave, terahertz and far-infrared spectral ranges where a large part of the Earth's outgoing longwave radiation to space is located. In this work, the observations, and analyses of the ozone high-resolution spectra in the THz range recorded using the Synchrotron light source of the SOLEIL CNRS equipment are reported for the first time. Thanks to the exceptional brightness of the Synchrotron radiation and to the signal/noise ratio, it was possible to observe many more ozone transitions of the cold rotational band and the hot ν-ν band in the range 0.9-6 THz compared to the previous works. In addition, we have carried out new measurements and assignments for the ν band. The simultaneous fit of the rotational band GS-GS, the hot band ν-ν and the FIR ν band yielded an overall weighted standard deviation of 0.68 for 13,466 line positions within the experimental accuracy. This includes all previously available MW (with the best uncertainty 0.1 - 10 kHz), FIR data and the original SOLEIL measurements that provided experimental accuracy of 0.00005 - 0.0001 cm for the best lines. Significant deviations in new experimental spectra compared to available spectroscopic databases were evidenced, particularly for the line positions and energy levels at high J, K rotational quantum numbers that are the most pronounced in the 4.5 - 6 THz range. Accurate ab initio calculations of line intensities combined with empirically fitted line positions were used to create new linelists that permit theoretical modelling of the transmittance in a good agreement with the Synchrotron spectra in the entire range of observations for various pressures and optical paths. The region near 100 cm and above appears to be more sensitive to the temperature conditions that should be considered in atmospheric observation for the currently operational and future ground based and space missions.
就对大气化学、气候变化、生物与生态系统以及人类健康的影响而言，臭氧是重要的分子之一。它在微波、太赫兹和远红外光谱范围内有强烈吸收，而地球向太空发射的大部分长波辐射就位于这些波段。在这项工作中，首次报告了使用法国国家科学研究中心（CNRS）的SOLEIL同步辐射光源记录的太赫兹范围内臭氧高分辨率光谱的观测与分析结果。得益于同步辐射的卓越亮度和信噪比，与之前的工作相比，在0.9 - 6太赫兹范围内能够观测到更多冷转动带和热ν-ν带的臭氧跃迁。此外，我们对ν带进行了新的测量和归属。转动带GS - GS、热带ν-ν和远红外ν带的同时拟合在实验精度范围内对13466个谱线位置产生了0.68的总体加权标准偏差。这包括所有先前可用的微波（最佳不确定度为0.1 - 10 kHz）、远红外数据以及原始的SOLEIL测量数据，其中最佳谱线的实验精度为0.00005 - 0.0001 cm⁻¹。新实验光谱与现有光谱数据库相比存在显著偏差，特别是在4.5 - 6太赫兹范围内最明显的高J、K转动量子数的谱线位置和能级方面。结合经验拟合的谱线位置进行的线强度精确从头计算被用于创建新的谱线列表，从而能够对不同压力和光程的整个观测范围内的透射率进行理论建模，且与同步辐射光谱高度吻合。100 cm⁻¹及以上附近区域似乎对温度条件更为敏感，这在当前运行的以及未来的地基和太空任务的大气观测中应予以考虑。
