Infrared intensities of liquids .20. The intensity of the OH stretching band of liquid water revisited, and the best current values of the optical constants of H2O(1) at 25 degrees C between 15,000 and 1 cm(-1)
Infrared intensities of liquids .20. The intensity of the OH stretching band of liquid water revisited, and the best current values of the optical constants of H2O(1) at 25 degrees C between 15,000 and 1 cm(-1)
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DOI：
10.1366/0003702963905385
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发表时间：
1996-08-01
影响因子：
3.5
通讯作者：
Lan, ZD
中科院分区：
文献类型：
--
作者：
Bertie, JE;Lan, ZD
对先前报道的液态水OH伸缩带强度不可重现性进行了探究。发现通过确保ATR棒与玻璃液体容器同轴，在使用Circle®多重ATR池进行测量时，这种不可重现性可以消除。还发现实验室正常的几度温度变化会使强度改变小于或等于峰高的约1%。在4000至700 cm⁻¹之间确定了一个新的水的虚折射率光谱，它是我们实验室四位工作人员在过去七年中记录的ATR光谱计算所得光谱的平均值。它是在优于先前使用的实验和计算条件下获得的，但与1989年报道的光谱仅有微小差异。特别是，基频的积分强度与1989年报道的相比没有显著变化。对15000至1 cm⁻¹之间现有的虚折射率k值进行了比较。被判定为最可靠的值被组合成一个25℃下15000至1 cm⁻¹之间的H₂O(l)的推荐k光谱，通过克拉默斯 - 克勒尼希变换从该光谱计算出了实折射率光谱。以图表形式给出了25±1℃下液态水的实折射率和虚折射率以及摩尔吸收系数的推荐值。在此波数范围内的实介电常数和虚介电常数以及实摩尔极化率和虚摩尔极化率可从这些表格中计算得出。给出了推荐k值的保守估计可能误差。一个实验室中测量这些值的精度以及不同区域之间的相对误差当然远小于这些可能误差。推荐的k值作为液态水的临时标准强度应该具有相当大的价值，这将有助于实验室之间强度的传递。
The previously reported nonreproducibility of the intensity of the OH stretching band of liquid water has been explored. It was found that it can be eliminated in measurements with the Circle(R) multiple ATR cell by ensuring that the ATR rod is coaxial with the glass liquid holder. It was also found that normal laboratory temperature variations of a few degrees change the intensity by less than or equal to similar to 1% of the peak height. A new imaginary refractive index spectrum of water has been determined between 4000 and 700 cm(-1) as the average of spectra calculated from ATR spectra recorded by four workers in our laboratory over the past seven years. It was obtained under experimental and computational conditions superior to those used previously, but is only marginally different from the spectra reported in 1989. In particular, the integrated intensities of the fundamentals are not changed significantly from those reported in 1989. The available imaginary refractive index, k, values between 15,000 and 1 cm(-1) have been compared. The values that are judged to be the most reliable have been combined into a recommended k spectrum of H2O(l) at 25 degrees C between 15,000 and 1 cm(-1), from which the real refractive index spectrum has been calculated by Kramers-Kronig transformation. The recommended values of the real and imaginary refractive indices and molar absorption coefficients of liquid water at 25 +/- 1 degrees C are presented in graphs and tables. The real and imaginary dielectric constants and the real and imaginary molar polarizabilities in this wavenumber range can be calculated from the tables. Conservatively estimated probable errors of the recommended k values are given. The precision with which the values can be measured in one laboratory and the relative errors between regions are, of course, far smaller than these probable errors. The recommended k values should be of considerable value as interim standard intensities of liquid water, which will facilitate the transfer of intensities between laboratories.