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Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy

机译：偏振红外光谱法测定绿柱通道中水分子与Na +阳离子的配位

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Subtle variations of frequencies in the infrared (IR) absorption spectra of beryl have been predicted based on the coordination between extra-framework cations and water molecules in two orientations (referred to as type I and type II) trapped within the channel. In this study, the polarized IR spectra of hydrated synthetic beryl and natural beryl were measured to clarify the relationships between the frequencies of the absorption bands and the coordination states of type II water. Na+ was assumed to be the predominant cation coordinated to type II water in our samples, as determined by chemical analyses. These measurements revealed a clear quantitative linear relationship in absorbance between bands at 3,602 and 1,619 and at 3,589 and 1,631 cm(-1). On the basis of experimental and theoretical studies, we assigned these pairs of bands to the nu(1) and nu(2) modes of doubly coordinated type II H2O and to singly coordinated type II H2O, respectively. These assignments were supported by IR measurements of annealed natural beryl. We also conducted dehydration studies of natural beryl, in which two observed dehydration peaks, at 600 and 750 degrees C, suggested the dehydration of type I and type II water, respectively.
机译：基于框架内阳离子和水分子在通道内的两个方向（称为I型和II型）的配位关系，可以预测绿柱石的红外（IR）吸收光谱中频率的细微变化。在这项研究中，对水合合成绿柱石和天然绿柱石的偏振红外光谱进行了测量，以阐明吸收谱带的频率与II型水的配位态之间的关系。通过化学分析确定，Na +被认为是我们样品中与II型水配位的主要阳离子。这些测量结果显示，在3,602和1,619以及3,589和1,631 cm（-1）的谱带之间的吸光度存在明显的定量线性关系。在实验和理论研究的基础上，我们分别将这些带对分配给双配型II H2O的nu（1）和nu（2）模式和单配型II H2O。这些分配得到退火的天然绿柱石的红外测量结果的支持。我们还进行了天然绿柱石的脱水研究，其中在600和750摄氏度观察到两个脱水峰，分别表明I型和II型水脱水。

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