On the atomistic origin of the polymorphism and the dielectric physical properties of beryllium oxide

Abstract

AbstractPolymorphic beryllium oxide has been theoretically investigated from first principles as regards orbital occupancies, chemical bonding, polarization, as well as dielectric properties. By means of Crystal‐Orbital Bond Index (COBI) analysis, the important role of the 2p orbitals on beryllium has been elucidated, in particular in terms of the correlation between polarization and beryllium‐atom displacement, including the impact of the latter on the covalency of the BeO bond. In addition, several structural possibilities for a BexMg1−xO solid solution have been investigated for a Be content between 6% and 22%; for those, dynamically stable structures have been found, displaying large polarization values, more covalent BeO bonds, and a tendency for tetrahedral Be coordination. The dynamically unstable structures, however, resemble rock‐salt BeO in their local structural properties around the Be atom. High dielectric constants and band gaps indicating insulating behavior have been found for those.