Microporous materials containing hydrated silanol groups Si–OH as well as hydrated proton complexes, H_2n+1O_n⁺, including hydronium (n = 1), Zundel (n = 2), and Eigen (n = 4) cations, are of practical importance as potential ion exchangers and ion conductors. In this paper, we provide data on crystal-chemical features, hydrogen bonding and Raman spectra of alkaline microporous titano-, niobo-, zircono-, and aluminosilicate minerals belonging to the labuntsovite, lovozerite, eudialyte, and sodalite groups in which a part of sodium was substituted by hydrated proton complexes under low-temperature hydrothermal or supergene conditions. Most minerals studied in this work do not have synthetic analogues and are considered as possible natural prototypes of microporous materials with technologically important properties. The obtained experimental data and their comparison with the results of ab initio theoretical calculations published elsewhere show that Raman spectroscopy is an effective tool for the precise identification of hydrated proton complexes with extremely strong hydrogen bonds and estimation of corresponding O···O distances in the range of 2.37–2.68 Å. The presence of hydrated proton complexes in microporous silicates is a clear and sensitive geological indicator showing that a rock underwent the low-temperature alteration.

中文翻译：

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微孔硅酸盐矿物中具有极强氢键的骨架外水合质子配合物的光谱表征

含有水合硅烷醇基团 Si–OH 以及水合质子络合物 H _{2 n +1} O _n ⁺的微孔材料，包括水合氢离子 ( n  = 1)、Zundel ( n  = 2) 和 Eigen ( n  = 4) 阳离子作为潜在的离子交换剂和离子导体具有实际重要性。在本文中，我们提供了碱性微孔钛矿、铌矿、锆矿和铝硅酸盐矿物的晶体化学特征、氢键和拉曼光谱数据，这些矿物属于拉本钠石、洛伏泽石、真钠石和方钠石族，其中一部分在低温水热或表生条件下，钠被水合质子配合物取代。这项工作中研究的大多数矿物没有合成类似物，被认为是具有重要技术特性的微孔材料的可能天然原型。获得的实验数据以及与其他地方发表的从头算理论计算结果的比较表明，拉曼光谱是精确识别具有极强氢键的水合质子配合物以及估计相应的O·O距离的有效工具。范围为 2.37–2.68 Å。微孔硅酸盐中水合质子络合物的存在是一个清晰而敏感的地质指标，表明岩石经历了低温蚀变。