The structure and vibrational spectroscopy of cryolite, Na(3)AlF(6)

Cryolite, Na(3)[AlF(6)], is essential to commercial aluminium production because alumina is readily soluble in molten cryolite. While the liquid state has been extensively investigated, the spectroscopy of the solid state has been largely ignored. In this paper, we show that the structure at 5 K is the same as that at room temperature. We use a combination of infrared and Raman spectroscopies together with inelastic neutron scattering (INS) spectroscopy. The use of INS enables access to all of the modes of Na(3)[AlF(6)], including those that are forbidden to the optical spectroscopies. Our spectral assignments are supported by density functional theory calculations of the complete unit cell.