A hybrid density functional view of native vacancies in gallium nitride.

We investigated the transition energy levels of the vacancy defects in gallium nitride by means of a hybrid density functional theory approach (DFT). We show that, in contrast to predictions from a recent study on the level of purely local DFT, the inclusion of screened exchange stabilizes the triply positive charge state of the nitrogen vacancy for Fermi energies close to the valence band. On the other hand, the defect levels associated with the negative charge states of the nitrogen vacancy hybridize with the conduction band and turn out to be energetically unfavorable, except for high n-doping. For the gallium vacancy, the increased magnetic splitting between up-spin and down-spin bands due to stronger exchange interactions in sX-LDA pushes the defect levels deeper into the band gap and significantly increases the associated charge transition levels. Based on these results, we propose the ϵ(0| - 1) transition level as an alternative candidate for the yellow luminescence in GaN.

Electronic and magnetic properties of Ti(2)O(3), Cr(2)O(3), and Fe(2)O(3) calculated by the screened exchange hybrid density functional.

The electronic and magnetic properties of the transition metal sesqui-oxides Cr(2)O(3), Ti(2)O(3), and Fe(2)O(3) have been calculated using the screened exchange (sX) hybrid density functional. This functional is found to give a band structure, bandgap, and magnetic moment in better agreement with experiment than the local density approximation (LDA) or the LDA+U methods. Ti(2)O(3) is found to be a spin-paired insulator with a bandgap of 0.22 eV in the Ti d orbitals. Cr(2)O(3) in its anti-ferromagnetic phase is an intermediate charge transfer Mott-Hubbard insulator with an indirect bandgap of 3.31 eV. Fe(2)O(3), with anti-ferromagnetic order, is found to be a wide bandgap charge transfer semiconductor with a 2.41 eV gap. Interestingly sX outperforms the HSE functional for the bandgaps of these oxides.

Graphite intercalation compounds under pressure

Motivated by recent experimental work, we use first-principles density functional theory methods to conduct an extensive search for low enthalpy structures of C$_6$Ca under pressure. As well as a range of buckled structures, which are energetically competitive over an intermediate range of pressures, we show that the high pressure system ($\gtrsim 18$ GPa) is unstable towards the formation of a novel class of layered structures, with the most stable compound involving carbon sheets containing five- and eight-membered rings. As well as discussing the energetics of the different classes of low enthalpy structures, we comment on the electronic structure of the high pressure compound and its implications for superconductivity.

Channel selective tunnelling through a nanographene assembly.

We report selective tunnelling through a nanographene intermolecular tunnel junction achieved via scanning tunnelling microscope tip functionalization with hexa-peri-hexabenzocoronene (HBC) molecules. This leads to an offset in the alignment between the energy levels of the tip and the molecular assembly, resulting in the imaging of a variety of distinct charge density patterns in the HBC assembly, not attainable using a bare metallic tip. Different tunnelling channels can be selected by the application of an electric field in the tunnelling junction, which changes the condition of the HBC on the tip. Density functional theory-based calculations relate the imaged HBC patterns to the calculated molecular orbitals at certain energy levels. These patterns bear a close resemblance to the π-orbital states of the HBC molecule calculated at the relevant energy levels, mainly below the Fermi energy of HBC. This correlation demonstrates the ability of an HBC functionalized tip as regards accessing an energy range that is restricted to the usual operating bias range around the Fermi energy with a normal metallic tip at room temperature. Apart from relating to molecular orbitals, some patterns could also be described in association with the Clar aromatic sextet formula. Our observations may help pave the way towards the possibility of controlling charge transport between organic interfaces.

Calculation of point defects in rutile TiO 2 by the screened-exchange hybrid functional

The formation energies of the oxygen vacancy and titanium interstitial in rutile TiO 2 were calculated by the screened-exchange (sX) hybrid density functional method, which gives a band gap of 3.1 eV, close to the experimental value. The oxygen vacancy gives rise to a gap state lying 0.7 eV below the conduction band edge, whose charge density is localized around the two of three Ti atoms next to the vacancy. The Ti interstitial (Ti int) generates four defect states in the gap, whose unpaired electrons lie on the interstitial and the adjacent Ti 3d orbitals. The formation energy for the neutral oxygen vacancy is 1.9 eV for the O-poor chemical potential. The neutral Ti interstitial has a lower formation energy than the O vacancy under O-poor conditions. This indicates that both the O vacancy and Ti int are relevant for oxygen deficiency in rutile TiO 2 but the O vacancy will dominate under O-rich conditions. This resolves questions about defect localization and defect predominance in the literature. © 2012 American Physical Society.

Stabilization of a complex perovskite superstructure under ambient conditions: Influence of cation composition and ordering, and evaluation as an SOFC cathode

Ba1.6Ca2.3Y1.1Fe5O13 is an Fe3+ oxide adopting a complex perovskite superstructure, which is an ordered intergrowth between the Ca2Fe2O5 and YBa2Fe3O8 structures featuring octahedral, square pyramidal, and tetrahedral B sites and three distinct A site environments. The distribution of A site cations was evaluated by combined neutron and X-ray powder diffraction. Consistent with the Fe3+ charge state, the material is an antiferromagnetic insulator with a Néel temperature of 480-485 °C and has a relatively low d.c. conductivity of 2.06 S cm-1 at 700 °C. The observed area specific resistance in symmetrical cell cathodes with the samarium-doped ceria electrolyte is 0.87 Ω cm2 at 700 °C, consistent with the square pyramidal Fe3+ layer favoring oxide ion formation and mobility in the oxygen reduction reaction. Density functional theory calculations reveal factors favoring the observed cation ordering and its influence on the electronic structure, in particular the frontier occupied and unoccupied electronic states. © 2010 American Chemical Society.