Metavalent or Hypervalent Bonding: Is There a Chance for Reconciliation?

Abstract

AbstractA family of solids including crystalline phase change materials such as GeTe and Sb2Te3, topological insulators like Bi2Se3, and halide perovskites such as CsPbI3 possesses an unconventional property portfolio that seems incompatible with ionic, metallic, or covalent bonding. Instead, evidence is found for a bonding mechanism characterized by half‐filled p‐bands and a competition between electron localization and delocalization. Different bonding concepts have recently been suggested based on quantum chemical bonding descriptors which either define the bonds in these solids as electron‐deficient (metavalent) or electron‐rich (hypervalent). This disagreement raises concerns about the accuracy of quantum–chemical bonding descriptors is showed. Here independent of the approach chosen, electron‐deficient bonds govern the materials mentioned above is showed. A detailed analysis of bonding in electron‐rich XeF2 and electron‐deficient GeTe shows that in both cases p‐electrons govern bonding, while s‐electrons only play a minor role. Yet, the properties of the electron‐deficient crystals are very different from molecular crystals of electron‐rich XeF2 or electron‐deficient B2H6. The unique properties of phase change materials and related solids can be attributed to an extended system of half‐filled bonds, providing further arguments as to why a distinct nomenclature such as metavalent bonding is adequate and appropriate for these solids.