Synthesis of the intermetallic clathrate Na2Ba6Si46 by oxidation of Na2BaSi4 with HCl

A new preparation route to the intermetallic clathrate-I compound Na₂Ba₆Si₄₆ is introduced, which allows one to make large amounts of product with standard laboratory equipment. The precursor Na₂BaSi₄ is oxidized with gaseous HCl at 673 K to Na₂Ba₆Si₄₆, NaCl and BaCl₂. Full-profile refinement of the crystal structure from the X-ray powder diffraction data revealed a composition close to Na₂Ba₆Si₄₆ (Na_1.94(1)Ba_6.06(1)Si₄₆, space group , a=10.281(1) Å). Differential scanning calorimetry showed an exothermic effect at 874 K, indicating that Na₂Ba₆Si₄₆ is metastable. The product was additionally characterized by scanning electron microscopy. The electronic structure of Na₂Ba₆Si₄₆ was investigated by a first-principles, all-electron full-potential method, predicting metallic conductivity. Na₂Ba₆Si₄₆ obtained by oxidation with HCl shows Pauli paramagnetism; no bulk superconductivity was found down to 1.8 K in a magnetic field of 20 Oe.