盐类晶体结构中占据对称不适当位置的铵的光谱分析

IF 0.8 4区 化学 Q4 SPECTROSCOPY Journal of Applied Spectroscopy Pub Date : 2024-07-06 DOI:10.1007/s10812-024-01753-5
A. V. Sergeeva, L. A. Polevoy, M. B. Golikova, M. A. Nazarova, A. V. Gladyshkina, E. V. Kartasheva, A. A. Kuzmina
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Disorder of the ammonium cation in salt crystals caused by the need to adjust the tetrahedral cation to the symmetry of the position to preserve the crystal symmetry was revealed. If the symmetry group of the position was not a subgroup of the tetrahedral symmetry group, the NH<sub>4</sub> tetrahedron was distorted by the subgroup <i>H</i>ʹ common for <i>T</i><sub><i>d</i></sub> and <i>H</i>, where <i>H</i> is the symmetry group of the position. Then, a polyhedron corresponding to the symmetry of the position was constructed from <i>N</i> = |<i>H</i>|/|<i>H</i>ʹ| (|<i>H</i>| and |<i>H</i>ʹ| are the orders of these groups) distorted tetrahedra. The disordered ammonium cation had several orientations (<i>N</i>), the superposition of which formally gave a polyhedron corresponding to the local symmetry. The maximum common subgroups for the given salts were <i>C</i><sub>3<i>v</i></sub> and <i>C</i><sub>3</sub>. 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引用次数: 0

摘要

天然硫酸铵 tschermigite NH4Al(SO4)2(H2O)12、lonecreekite NH4Fe(SO4)2(H2O)12、氨橄榄石 (NH4)2Fe2+5Fe3+3Al(SO4)12(H2O)18 的振动光谱、氨铝石 NH4Al3(SO4)2(OH)6,以及氨晶石 NH4Fe3(SO4)2(OH)6。研究揭示了铵阳离子在盐晶体中的混乱状态,这是因为需要将四面体阳离子调整到对称位置以保持晶体对称性。如果位置的对称性基团不是四面体对称性基团的子基团,NH4 四面体就会被 Td 和 H 的共同子基团 Hʹ 扭曲,其中 H 是位置的对称性基团。然后,由 N = |H|/|Hʹ|(|H|和|Hʹ|是这些基团的阶)扭曲的四面体构建出与该位置的对称性相对应的多面体。无序的铵阳离子有几种取向(N),它们的叠加形式给出了一个与局部对称性相对应的多面体。给定盐的最大公共亚群为 C3v 和 C3。铵的变形导致红外光谱中 ν1 和 ν2 [NH4+ ] 振动的激活以及 ν3 和 ν4 [NH4+ ] 振动的分裂。不过,对于处于中心对称位置的铵,如氨铝石和氨焦石中的铵,这种影响几乎不明显。在铵矾石、铵沸石和沙比石的光谱中,ν4 [NH4+] 波段明显分裂,ν1 和 ν2 [NH4+ ] 振动清晰可见。
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Spectroscopy of Ammonium Occupying Symmetry-Inappropriate Positions in Crystal Structures of Salts

The vibrational spectra of the natural ammonium sulfates tschermigite NH4Al(SO4)2(H2O)12, lonecreekite NH4Fe(SO4)2(H2O)12, ammoniovoltaite (NH4)2Fe2+5Fe3+3Al(SO4)12(H2O)18, sabieite NH4Fe(SO4)2, ammonioalunite NH4Al3(SO4)2(OH)6, and ammoniojarosite NH4Fe3(SO4)2(OH)6 were studied to determine the behavior of ammonium in symmetry-inappropriate positions. Disorder of the ammonium cation in salt crystals caused by the need to adjust the tetrahedral cation to the symmetry of the position to preserve the crystal symmetry was revealed. If the symmetry group of the position was not a subgroup of the tetrahedral symmetry group, the NH4 tetrahedron was distorted by the subgroup Hʹ common for Td and H, where H is the symmetry group of the position. Then, a polyhedron corresponding to the symmetry of the position was constructed from N = |H|/|Hʹ| (|H| and |Hʹ| are the orders of these groups) distorted tetrahedra. The disordered ammonium cation had several orientations (N), the superposition of which formally gave a polyhedron corresponding to the local symmetry. The maximum common subgroups for the given salts were C3v and C3. Distortion of ammonium led to activation of ν1 and ν2 [NH4+ ] vibrations in the IR spectrum and splitting of ν3 and ν4 [NH4+ ]. However, the effect was barely noticeable for ammonium in a centrosymmetric position, as in ammonioalunite and ammoniojarosite. The ν4 [NH4+] band was noticeably split and ν1 and ν2 [NH4+ ] vibrations were clearly visible in spectra of the ammonium alums, ammoniovoltaite, and sabieite.

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来源期刊
CiteScore
1.30
自引率
14.30%
发文量
145
审稿时长
2.5 months
期刊介绍: Journal of Applied Spectroscopy reports on many key applications of spectroscopy in chemistry, physics, metallurgy, and biology. An increasing number of papers focus on the theory of lasers, as well as the tremendous potential for the practical applications of lasers in numerous fields and industries.
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