Electric field gradients in fluoride crystalline powders: correlation of NMR measurements with ab initio calculations.

Electric field gradients (EFG) of 23Na and 27Al in three model fluoride crystalline powders AlF3, Na3AlF6 and Na5Al3F14 were computed using the density functional based electronic structure code WIEN97 and compared to values derived from nuclear magnetic resonance (NMR). First, results of measurements of 23Na and 27Al quadrupolar parameters in AlF3, Na3AlF6 and Na5Al3F14 were revisited by using high-resolution solid-state NMR. To determine chemical shifts and quadrupolar parameters with a high precision, the experimental procedure involved magic angle spinning, satellite transition spectroscopy and multi-quanta techniques applied to the quadrupolar nuclei together with a computed reconstruction of the NMR spectra. The large discrepancies which appear between previously published results in some cases, justify the use of ab initio calculations of the corresponding EFG using the WIEN97 code based on the known structural data of the crystalline phases. The agreement obtained between these calculations and the experimental results which is better than 10% in almost all cases supports the reliability of the present NMR investigations and of the crystallographic data.