Raman Spectroscopic Study on Hydrogen Bond of Water Molecules in Natural Inclusions under the Conditions of Freezing
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摘要: 水的拉曼图谱实际就是带氢键作用的OH伸缩振动峰(包括对称伸缩振动峰和反对称伸缩振动峰)和不带氢键作用的OH对称伸缩振动峰(包括对称伸缩振动峰和反对称伸缩振动峰)的叠加包络线，通过对流体中水的拉曼图谱的分析可以反映流体中氢键作用的强弱.因此，用Renishaw MK1-1000型显微激光拉曼探针原位分析了冷冻条件下天然的流体包裹体腔内流体水分子的氢键作用.研究表明，在冷冻条件下，水分子运动以带氢键作用的伸缩振动为主，同时还有微弱的非氢键作用的伸缩振动；随着温度的降低，流体中水分子的氢键作用不断地增强；在-130~-180 ℃区间氢键作用增强的趋势明显加大，暗示流体性质在此温度区间可能发生了突变.Abstract: The Raman spectroscopy of water is combined by O-H stretching vibration peaks with hydrogen bond and O-H stretching vibration peaks with no hydrogen bond in 3 100-3 700 cm-1, which all include symmetric and anti-symmetric stretching fundamentals. So the intensity of hydrogen bonding of H2O molecules in fluid can be obtained by studying on the Raman spectroscopy of water. The hydrogen bonding of water in natural fluid inclusions under the condition of freezing is studied by in-site analysis with a Renishaw MK1-1000 type laser Raman microprobe. The results show that the stretching vibration with hydrogen bond between different H2O molecules is the main movement of H2O molecules below 0 ℃, and the weak stretching vibration with no hydrogen bond in the same molecules is also found in the meantime. The hydrogen bonding of water become stronger with the descent of temperature, and the property of fluid might be discontinuous at -130 to -180 ℃.
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Key words:
- condition of freezing /
- fluid inclusion /
- hydrogen bonding /
- Raman spectroscopy /
- homogeneous fluid /
- geochemistry
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图 1 不同测试温度下的流体拉曼拟合曲线
Fig. 1. The fitting curves of Raman spectra of fluid by two peaks under experimental temperatures
图 2 冷冻条件下流体的拉曼位移与测试温度的关系
Fig. 2. Relationship of Raman shift and experimental temperature at the condition of freezing
表 1 不同温度下的流体拉曼图谱特征(以两峰拟合后的特征)
Table 1. Raman spectra of fluid fitted by two peaks under different experimental temperatures
测试温度(℃) 主峰 次峰 拉曼位移(cm-1) 拉曼强度(a.u.) 半高宽(cm-1) 拉曼位移(cm-1) 拉曼强度(a.u.) 半高宽(cm-1) -30 3 106.0 771.70 190.88 3 335.0 367.88 215.20 -80 3 095.2 965.98 161.96 3 315.6 367.16 240.85 -130 3 085.5 1 597.00 145.95 3 298.0 464.57 244.29 -180 3 069.1 2 490.50 57.71 3 136.6 673.61 541.49 
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表 2 不同温度区间的流体拉曼参数变化特征(以两峰拟合后的特征)
Table 2. Raman parameters of fluid in different temperature zones
温度区间(℃) 主峰 次峰 △ひmax(cm-1) △I (a.u.) △FWHH(cm-1) △ひmax(cm-1) △I(a.u.) △FWHH(cm-1) -30~-80 10.80 194.28 28.92 19.40 0.62 25.65 -80~-130 9.70 627.02 16.01 17.60 97.39 3.44 -130~-180 16.40 892.50 88.24 161.40 209.04 297.20 注：△I为与两个端元温度相对应的流体拉曼强度之差；△ひmax为与两个端元温度相对应的流体拉曼位移之差；△FWHH为两个端元温度相对应的流体半高宽之差.
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