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- W2022715984 abstract "The IR and Raman spectra of the isotypic alkaline earth halide monohydrates, MX2 · 1H2O, with M = Sr, Ba and X = Cl, Br, I, and of deuterated samples are presented for the range 200–700 cm−1 and discussed in terms of normal modes, assignment, coupling, correlation with structure data, and temperature dependence of both the H2O (D2O) and the HDO librational modes. The normal modes of the out-of-plane librations of HDO molecules are of the wagging and twisting type rather than H and D out-of-plane vibrations [4], at least for water molecules with C2v or nearly C2v symmetry. Thus the observed H2O/HDO isotopic shifts can be used as a criterion for assigning the H2O librations. The librational modes of the halide monohydrates (with tetrahedrally coordinated water oxygen atoms) are found in the order νRγ ⪢ νRt ⪢ νRr. The intensities of the IR and Raman spectra are in the order Rγ ⪢ Rr ⪢ Rt (or ∼ Rt in the case of strongly distorted H2O molecules) and Rt ⪢ Rr ⪢ Rγ, respectively. Correlations of the H2O librational modes with structural or bonding data are restricted by frequency shifts due to vibrational coupling and by the fact that the oxygen and the hydrogen atoms of the water molecules are generally affected in a different manner by bond interactions. However, in the case of the twisting vibrations, there are clear correlations with both the size of the metal ions, i.e. increase of νRt with decreasing size, and the intermolecular bonding of the hydrogen atoms, as shown by the OH stretching frequencies, i.e. increase of νRt with decreasing νOH." @default.
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- W2022715984 date "1983-09-01" @default.
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- W2022715984 title "Librational modes of the water molecules in barium and strontium halide monohydrates, MX2 · 1H2O (M = Ba, Sr; X = Cl, Br, I)" @default.
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- W2022715984 doi "https://doi.org/10.1016/0022-2860(83)85013-3" @default.
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