Abstract
Variations in the 17O nuclear quadrupole coupling constant, NQCC, and the 17O NMR shielding constant, σO, are evaluated for bridging oxygens in H3T-O-T′H3 linkages (with T, T′=Al, Si, P), and for nonbridging O in SiH3O−, SiH3OH and SiH3OMg+ and the 19F NMR shielding constant, σF, is evaluated for bridging F in H3SiFSiH −3 using Hartree-Fock methods with large, flexible Gaussian basis sets. Trends in 17O NQCC as a function of T and T′ identity agree with experiment but the value for the Si-O-Al case is underestimated, indicative of neglected contributions from charge compensating cations. For H3SiOSiH3 the decrease in NQCC over the range from 180° to 140° is substantial but somewhat slower than the variation of -cos<Si-O-Si. The NQCC at bridging oxygen for R(Si-O)=1.607 Å and <Si-O-Si=140° interpolated from the calculations is 5.3 MHz, in good agreement with experiment. The calculated values of σSi and σO decrease as <Si-O-Si decreases, at a rate consistent with experiment. The calculations properly rank the σSi of the nonbridging oxygen of SiH3O− compared to the bridging oxygen of H3SiOSiH3 but the calculated σSi in H3SiOAlH −3 is too large and σO too small, indicative of important contributions from counter ions. By contrast, σO for PH3OAlH3 compared to SiH3OSiH3 is consistent with experiment. In H3SiFSiH +3 (a model for bridging F in amorphous Si:H:F) the value of σSi is smaller and the NQCC at F is considerably larger than for H3SiF, suggesting distinctive 29Si and 19F NMR spectra for this species.
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Tossell, J.A., Lazzeretti, P. Calculation of NMR parameters for bridging oxygens in H3T—O—T′H3 linkages (T, T′=Al, Si, P), for oxygen in SiH3O−, SiH3OH and SiH3OMg+ and for bridging fluorine in H3SiFSiH +3 . Phys Chem Minerals 15, 564–569 (1988). https://doi.org/10.1007/BF00311027
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DOI: https://doi.org/10.1007/BF00311027