Abstract
Ab initio force constants of structural fragments of α-quart, Si-O-Si bridge and SiO4 tetrahedron, are calculated by the gradient (force) method for molecules accessible to spectroscopic investigation, disiloxane and tetramethoxysilane respectively. The comparison of theoretical frequencies with experimental ones enables the empirical scaling of quantum chemical force constants. A generalized approach to the inverse vibrational problem in spectroscopy of solids is outlined. It consists of a joint treatment of vibrational spectra and properties of a crystal related to its homogeneous deformation, namely compressibility and elastic constants. The importance of analyzing the microscopic structure of compressibility for testing the force field model is emphasized. The scaled molecular force constants complemented by the force constants of nonbonded O...O interactions at shortest distances after slight empirical correction are found to be sufficient to reproduce all mechanical properties of α-quartz accessible to experimental determination. A discussion of results in terms of structure and bonding including the analysis of various versions of a force field model is presented. The calculated shapes of normal coordinates and uniform strains are validated by satisfactory reproduction of IR intensities and piezoelectric constants.
Published Version
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