Clathrate Structure of Silicon Na 8 Si 46 and Na x Si 136 ( x < 11)

Abstract

The crystal structure of two new cubic phases in the silicon-sodium system have been solved from their x-ray diffraction patterns. Both structures are of the clathrate type found for gas hydrates, consisting of tetrahedral networks which are combinations of pentagonal dodecahedra with 14-face polyhedra in one case and with 16-face polyhedra in the other case. There is strict correspondence between the silicon positions and the oxygen positions of the hydrate structures. For one compound, Na₈Si₄₆, the centers of all polyhedra are occupied by sodium atoms. For the other compound, there occurs only partial occupancy of the polyhedral cages.