Insulating state of Na clusters and their metallic transition in low-silica X zeolite

Optical and magnetic properties are investigated for low-silica X (LSX) zeolite loaded with Na metals at various loading densities. In LSX, β-cages with the inside diameter of ∼7 Å are arrayed in a diamond structure and the supercages with that of ∼13 Å are formed among them. When the average number of guest Na atoms per β cage, n, is smaller than ∼2, optical reflectance shows a peak at ∼2.5 eV. This corresponds to the 1s-1p transition of the cluster formed in β cage. At n>2, this peak disappears and several strong peaks are seen at 1-3 eV. The oscillator strength increases with n. They can be attributed to surface-plasmon-like excitations of the Na clusters formed in supercages. At n≤10, clear absorption tails with energy gaps are observed at near IR region indicating insulating states. However, when n is increased up to ∼12, a clear Drude reflection suddenly appears in the IR region, indicating that an insulator-to-metal transition abruptly occurs. This dramatic change of the electronic state may be caused by the successive connection between adjacent clusters in supercages due to some special arrangement of Na+ ions as well as the delocalized wave function of electrons at high Na-loading density.