The Myth of “Metavalency” in Phase‐Change Materials

Abstract Phase‐change memory materials (PCMs) have unusual properties and important applications, and recent efforts to find improved materials have focused on their bonding mechanisms. “Metavalent bonding” or “metavalency,” intermediate between “metallic” and “covalent” bonding and comprising single‐electron bonds, has been proposed as a fundamentally new mechanism that is relevant both here and for halide perovskite materials. However, it is shown that PCMs, which violate the octet rule, have two types of covalent bond: two‐center, two‐electron (2c‐2e) bonds, and electron‐rich, multicenter bonds (3c‐4e bonds, hyperbonds) involving lone‐pair electrons. The latter have bond orders less than one and are examples of the century‐old concept of “partial” bonds.