K2BaSi4: Zintl Concept in Position Space

Abstract

AbstractThe Zintl phase K2BaSi4 has been synthesized from the mixture of precursors KSi and BaSi2. The crystal structure of K2BaSi4 was elucidated from X‐ray powder diffraction data: Pearson symbol oP28, space group Pbcm, a=9.4950(1), b=9.2392(1), c=9.9025(1) Å. The main building block of the crystal structure are tetrahedral anions Si44–. Analysis of chemical bonding for K2BaSi4 and its chemical analogs – molecular H4Si4 and solid state K4Si4 employing the electron localizability approach reveals the basic agreement with the Zintl model in terms of number of basins for Si−Si bonds and lone pairs at Si atoms, as well as the charge transfer direction. The populations of the bond and ‘lone‐pair’ basins agree with the Zintl count for molecular species and deviate strongly for the solids, in particular, while the ‘lone‐pair’ basins are over‐populated, the bond basins are essentially under‐populated. The topology of the calculated electron density and electron‐localizability indicator is very sensitive toward the interatomic distances and angles in the Si44− anion.