Representation of electronic structures in crystals in terms of highly localized quasiatomic minimal basis orbitals

Abstract

A method is presented for expressing electronic orbital states of a periodic solid in terms of a minimal basis set of localized quasiatomic orbitals. While spanning exactly the same occupied subspace as the orbitals determined by a fully converged first-principles calculation with a large basis set, the minimal-basis orbitals from this work are highly localized on atoms and exhibit shapes close to orbitals of the isolated atom. They are also shown to be useful for analyzing chemical bonding in periodic systems. All of these features are found for insulating as well as metallic solids.