Modelling charge self-trapping in wide-gap dielectrics: Localization problem in local density functionals

We discuss the adiabatic self-trapping of small polarons within the density functional theory (DFT). In particular, we carried out plane-wave pseudo-potential calculations of the triplet exciton in NaCl and found no energy minimum corresponding to the self-trapped exciton (STE) contrary to the experimental evidence and previous calculations. To explore the origin of this problem we modelled the self-trapped hole in NaCl using hybrid density functionals and an embedded cluster method. Calculations show that the stability of the self-trapped state of the hole drastically depends on the amount of the exact exchange in the density functional: at less than 30% of the Hartree-Fock exchange, only delocalized hole is stable, at 50% - both delocalized and self-trapped states are stable, while further increase of exact exchange results in only the self-trapped state being stable. We argue that the main contributions to the self-trapping energy such as the kinetic energy of the localizing charge, the chemical bond formation of the di-halogen quasi molecule, and the lattice polarization, are represented incorrectly within the Kohn-Sham (KS) based approaches.Comment: 6 figures, 1 tabl

Interconversion of intrinsic defects in SrTiO3(001)SrTiO_3(001)

Photoemission features associated with states deep in the band gap of n−SrTiO₃ (001) are found to be ubiquitous in bulk crystals and epitaxial films. These features are present even when there is little signal near the Fermi level. Analysis reveals that these states are deep-level traps associated with defects. The commonly investigated defects—O vacancies, Sr vacancies, and aliovalent impurity cations on the Ti sites—cannot account for these features. Rather, ab initio modeling points to these states resulting from interstitial oxygen and its interaction with donor electrons