NMR Knight shifts and the electronic properties of Rb8Na16Si136 clathrate -: art. no. 125403

A silicon framework clathrate type-II compound was synthesized with rubidium and sodium atoms in cages. A single crystal of this material was characterized by both conventional and synchrotron x-ray diffraction; the structure belongs to the cubic space group Fd-3m, with a cell edge of 14.738(1) Angstrom. The alkali metals are ordered in the structure, with the small cages containing sodium, and the large cages containing rubidium. Variable temperature magic-angle-spinning NMR of all three nuclei show large Knight shifts with a strong temperature dependence, unlike conventional metals. The low conductivity (200 S/cm) and high paramagnetic susceptibility (5 x 10(-6) emu/g indicate that as the temperature is lowered, the electrons become more localized on the alkali atoms, resulting in properties consistent with a correlated narrow band metal system.