Water Spectra in the Region 4200-6250 cm −1 , Extended Analysis of ν1 + ν2, ν2 + ν3, and 3ν2 Bands and Confirmation of Highly Excited States from Flame Spectra and from Atmospheric Long-Path Observations
Water Spectra in the Region 4200-6250 cm −1 , Extended Analysis of ν1 + ν2, ν2 + ν3, and 3ν2 Bands and Confirmation of Highly Excited States from Flame Spectra and from Atmospheric Long-Path Observations
复制标题
4200-6250 cm -1 区域的水光谱、ν1 + ν2、ν2 + ν3 和 3ν2 波段的扩展分析以及从火焰光谱和大气长路径观测中确认高度激发态
DOI：
10.1006/jmsp.2002.8558
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发表时间：
2002
影响因子：
1.4
通讯作者：
J. Brault
中科院分区：
文献类型：
--
作者：
S. Mikhailenko;V. Tyuterev;V. I. Starikov;K. K. Albert;B. Winnewisser;M. Winnewisser;G. Mellau;C. Camy‐Peyret;R. Lanquetin;J. Flaud;J. Brault
摘要在室温下，在4200-6250 cm-1范围内，以0.0053和0.0080 cm-1之间的分辨率（FWHM）记录了水蒸气的红外光谱。使用怀特型多重反射池可以获得高达31.27毫巴×288.5米的大气压×光程积。高信噪比使我们能够在T=296 K时观察到强度小至10−26 cm−1/分子cm−2的谱线。在约5100条记录的水线中，约有一半是首次报道，其中2351条被指定为H216 O的第二个三元组（带ν1+ν2，ν2+ν3和3ν2）。这使得线的位置和相应的上振转态的测定有相当大的提高精度。通过对火焰光谱和热发射光谱的分析，确认了某些高激发态的归属。确定了上能级{（110），（030），（011）}的有效哈密顿参量的新值。在数据处理中采用了生成函数模型来解释振转能级和共振相互作用的强烈离心畸变。指定的H2O数据的最小二乘拟合的RMS标准偏差对于线位置为5×10−3 cm−1，对于Jmax=20和Ka（max）=13的能级为7×10−3 cm−1。特别注意透明度窗口4200-5000 cm-1中的水线，现有数据库在这方面是不够的。在该区域已记录到水的4种同位素1395条谱线，并报道了H216 O（ν1，ν3，2ν2，ν1+ν2，ν2+ν3，3ν2，4ν2−ν2，2ν2+ν3−ν2，ν1+2ν2−ν2）9条谱带的900多条精确谱线位置。在这个地区的实验室光谱与长路径大气光谱（20公里的山区倾斜路径）的比较表明，许多线从现有的光谱汇编（或相当大的移动相比，观察）是重要的大气观测的正确解释。从分子电子势能面的最佳预测的观测数据的比较进行了讨论。
Abstract Water vapor infrared spectra have been recorded at room temperature in the range 4200–6250 cm−1 at resolutions (FWHM) between 0.0053 and 0.0080 cm−1. The use of a White-type multireflection cell made large pressure × pathlength products possible up to 31.27 mbar×288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10−26 cm−1/molecule cm−2 at T=296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H216O (bands ν1+ν2, ν2+ν3, and 3ν2). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H2O data was 5×10−3 cm−1 for line positions and 7×10−3 cm−1 for energy levels up to Jmax=20 and Ka(max)=13. Particular attention was paid to water lines in the transparency window 4200–5000 cm−1, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H216O (ν1, ν3, 2ν2, ν1+ν2, ν2+ν3, 3ν2, 4ν2−ν2, 2ν2+ν3−ν2, ν1+2ν2−ν2) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.