Abstract
Normal coordinate calculations have been carried out on partially polymerized simple silicate crystals, including Li and Na di- and metasilicates, Li and Gd pyrosilicates, thortveitite and rankinite. In the antisymmetric Si-O stretching modes which are active at 800–1200 cm−1 in infrared spectra, Si-Obr vibrations occur at higher frequencies than Si-Onb vibrations if the bonds have equivalent strengths. However, this relationship is usually reversed when bridging oxygens are overbonded and non-bridging oxygens are underbonded in terms of Pauling bond strengths, a situation which is generally more common in crystals. An observed bimodality of the high-frequency envelope in infrared spectra of glasses in the alkali oxide-silica systems may be somewhat fortuitous, with the high frequency component (ca. 1100 cm−1) representing underbonded non-bridging oxygens and saturated bridging oxygens, and the lower-frequency component (ca. 1000 cm−1) mainly oversaturated bridging oxygens. Significant differences between crystals and glasses in the number and location of the main high-frequency infrared peaks suggest that there are short-range bonding rearrangements in the glasses, and that crystallite models are not applicable. Mid-frequency (600–800 cm−1) infrared modes in silicates more polymerized than the pyrosilicate (Si2O7) appear to be mostly antisymmetric modes in which Si rattles against bridging oxygens, rather than symmetric stretching modes.
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Dowty, E. Vibrational interactions of tetrahedra in silicate glasses and crystals. Phys Chem Minerals 14, 542–552 (1987). https://doi.org/10.1007/BF00308290
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DOI: https://doi.org/10.1007/BF00308290