The Metallic Zintl Phase Ba₃Si₄ – Synthesis, Crystal Structure, Chemical Bonding, and Physical Properties

Abstract

Abstract The Zintl phase Ba 3 Si 4 has been synthesized from the elements at 1273 K as a single phase. No homogeneity range has been found. The compound decomposes peritectically at 1307(5) K to BaSi 2 and melt. The butterfly‐shaped Si 4 6− Zintl anion in the crystal structure of Ba 3 Si 4 (Pearson symbol tP 28, space group P 4 2 / mnm , a = 8.5233(3) Å, c = 11.8322(6) Å) shows only slightly different Si‐Si bond lengths of d (Si–Si) = 2.4183(6) Å (1×) and 2.4254(3) Å (4×). The compound is diamagnetic with χ ≈ −50 × 10 −6 cm 3 mol −1 . DC resistivity measurements show a high electrical resistivity (ρ(300 K) ≈ 1.2 × 10 −3 Ω m) with positive temperature gradient dρ/d T . The temperature dependence of the isotropic signal shift and the spin‐lattice relaxation times in 29 Si NMR spectroscopy confirms the metallic behavior. The experimental results are in accordance with the calculated electronic band structure, which indicates a metal with a low density of states at the Fermi level. The electron localization function (ELF) is used for analysis of chemical bonding. The reaction of solid Ba 3 Si 4 with gaseous HCl leads to the oxidation of the Si 4 6− Zintl anion and yields nanoporous silicon.