Polymorphic 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 BeO bond. In addition, several structural possibilities for a Bex Mg1-x O 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 BeO 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.
© 2023 The Authors. Journal of Computational Chemistry published by Wiley Periodicals LLC.