FandMcenters in alkali halides: A theoretical study applying self-consistent dielectric-dependent hybrid density functional theory

Abstract

Point defects significantly change electronic properties of alkali halides and thereby enhance their reactivity. However, both the experimental and theoretical description of defects such as the $F$ center and the $M$ center are still far from complete, in particular for the less common bromides. A self-consistent dielectric-dependent global hybrid and plane-wave approach is employed for a comparative theoretical study of the electronic properties of NaCl, KCl, NaBr, and KBr bulk and (100) surface, both perfect and defective. For these systems, a zero-point renormalization was calculated to account for electron-phonon interaction and enhance comparability with the experiment. We focus on anion vacancy defects, the so-called $F$ and $M$ centers. The methodology employed is capable of reproducing measured defect level energies, electronic band gaps, ionization energies, and electron affinities within experimental errors. A general trend of the $F$ center defect level energy with respect to the lattice parameter is found. The results for both the $F$ and the $M$ center of KCl agree with findings from magnetic resonance experiments. The defect orbitals are analyzed and virtual states of the defect electron are identified.