Raman spectroscopic study of dilute HOD in liquid H2O in the temperature range − 31.5 to 160 °C
Raman spectroscopic study of dilute HOD in liquid H2O in the temperature range − 31.5 to 160 °C
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− 31.5 至 160 °C 温度范围内液态 H2O 中稀 HOD 的拉曼光谱研究
DOI：
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发表时间：
1990
期刊：
影响因子：
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通讯作者：
C. Sorensen
中科院分区：
文献类型：
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作者：
D. Hare;C. Sorensen
我们给出了在−31.5-160 °C范围内，10mol%HOD在H2O中的OD伸展模的拉曼数据。我们发现，准确的等温线并不成立，而是等温线的交叉点缓慢而均匀地随温度变化。基于玻尔兹曼统计的分析结果表明，在固态冰和无定形固相中，在频率(2440 cm−1)附近，具有最小能量的重氢氢键强度分布是有证据的。这一分析还给出了2630厘米−1以上的频率带的证据，这是由于OD振子相对于最强的氢键基本上处于相同的高能，我们将该带解释为氢键断裂。这使得我们可以计算氢键几率，我们发现这个几率随着温度的降低而增加，并且接近于过冷水异常的奇异温度ts≂−45 °C附近的四键渗流阈值。最高频率和最高频率...
We present Raman data for the OD stretch mode of 10 mol % HOD in H2O for the liquid phase from −31.5 to 160 °C. We find that an exact isosbestic does not hold, but rather the crossing of isotherms slowly but uniformly changes with temperature. We present an analysis based on Boltzmann statistics which gives evidence for a distribution of deuterium hydrogen bond strengths with minimum energy near the frequency (2440 cm−1) also found in the solid ice and amorphous solid phases. This analysis also gives evidence for a band of frequencies above 2630 cm−1 due to OD oscillators all at essentially the same high energy relative to the strongest hydrogen bonds, and we interpret this band as due to broken hydrogen bonds. This allows us to calculate hydrogen bond probabilities, and we find this probability increases with decreasing temperature and approaches a value equal to the four bonded percolation threshold near the singular temperature Ts ≂−45 °C for the anomalies of supercooled water. Peak frequency and full ...