Framework contraction in Na-stuffed Si(cF136)

Inorg Chem. 2010 Jun 21;49(12):5338-40. doi: 10.1021/ic1005049.

Abstract

Systematic crystal structure refinements from powder X-ray diffraction data as well as density functional theory calculations demonstrate that the silicon clathrate II Si(cF136) exhibits a lattice contraction as Na is introduced solely into the Si(28) cages. When the Si(20) cages, in addition, begin to be filled with Na, a contrasting lattice expansion results. The nonmonotonic structural response to filling is an indication of markedly dissimilar guest-framework interactions for Na@Si(20) and Na@Si(28).