Synthesis,structural characterization,and electronic structure of the novel Zintl phase Ba2ZnP2

The novel Zintl phase dibarium zinc diphosphide (Ba₂ZnP₂) was synthesized for the first time. This was accomplished using the Pb flux technique, which allowed for the growth of crystals of adequate size for structural determination via single‐crystal X‐ray diffraction methods. The Ba₂ZnP₂ compound was determined to crystallize in a body‐centered orthorhombic space group, Ibam (No. 72). Formally, this crystallographic arrangement belongs to the K₂SiP₂ structure type. Therefore, the structure can be best described as infinite [ZnP₂]^4? polyanionic chains with divalent Ba²⁺ cations located between the chains. All valence electrons are partitioned, which conforms to the Zintl–Klemm concept and suggests that Ba₂ZnP₂ is a valence‐precise composition. The electronic band structure of this new compound, computed with the aid of the TB–LMTO–ASA code, shows that Ba₂ZnP₂ is an intrinsic semiconductor with a band gap of ca 0.6 eV.