Institute of Applied Physics of the Russian Academy of Sciences, Nizhny Novgorod, Russia.
J Chem Phys. 2011 Feb 28;134(8):084306. doi: 10.1063/1.3556606.
It is shown that the evolution of water vapor spectra in the 2500-5000 cm(-1) range recorded at 650 K and pressures up to 130 atms after subtraction of monomer contribution may be interpreted qualitatively well on the basis of experimental data on water dimer and trimer obtained from cold molecular beams and in He droplets. The proposed spectroscopic model considers water vapor as a mixture of nonideal monomers, dimers, and trimers at chemical equilibrium. The effect of line mixing is taken into account in the monomer spectrum modeling. Decomposition of the high temperature spectra allowed determining a dimer equilibrium constant that was compared with the previously known values. The contribution of water trimer is assessed. The performed analysis indicates that the number of bound dimers in water vapor is quite large, even at such a high temperature.
研究表明，在 650K 和高达 130 大气压的条件下，扣除单体贡献后，在 2500-5000cm^(-1) 范围内记录的水蒸气光谱的演化，可以很好地根据从冷分子束和氦滴中获得的关于水二聚体和三聚体的实验数据进行定性解释。所提出的光谱模型将水蒸气视为处于化学平衡的非理想单体、二聚体和三聚体混合物。在单体光谱建模中考虑了谱线混合的影响。对高温光谱的分解允许确定二聚体平衡常数，并将其与以前已知的值进行比较。评估了水三聚体的贡献。所进行的分析表明，即使在如此高的温度下，水蒸气中结合的二聚体数量也相当大。
