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High-pressure single-crystal to 20 GPa and powder diffraction measurements to 50 GPa, show that the structure of Pb2SnO4 strongly distorts on compression with an elongation of one axis. A structural phase transition occurs between 10 GPa and 12 GPa, with a change of space group from Pbam to Pnam. The resistivity decreases by more than six orders of magnitude when pressure is increased from ambient conditions to 50 GPa. This insulator-to-semiconductor transition is accompanied by a reversible appearance change from transparent to opaque. Density functional theory-based calculations show that at ambient conditions the channels in the structure host the stereochemically-active Pb 6s2 lone electron pairs. On compression the lone electron pairs form bonds between Pb2+ ions. Also provided is an assignment of irreducible representations to the experimentally observed Raman bands.
Tailoring of spin state energetics of transition metal complexes and even the correct prediction of the resulting spin state is still a challenging task, both for the experimentalist and the theoretician. Apart from the complexity in the solid state imposed by packing effects, molecular factors of the spin state ordering are required to be identified and quantified on equal rights. In this work we experimentally record the spin states and SCO energies within an eight-member substitution-series of N4O2 ligated iron(II) complexes both in the solid state (SQUID magnetometry and single-crystal X-ray crystallography) and in solution (VT-NMR). The experimental survey is complemented
by exhaustive theoretical modelling of the molecular and electronic structure of the open-chain N4O2 family and its macrocyclic N6 congeners through density-functional theory methods. Ligand topology is identified as the leading factor defining ground-state multiplicity of the corresponding iron(II) complexes. Invariably the low-spin state is sterically trapped in the macrocycles, whereas subtle substitution effects allow for a molecular fine tuning of the spin state in the open-chain ligands. Factorization of computed relative SCO energies holds promise for directed design of future SCO systems.
Oxygen vacancies in strontium titanate surfaces (SrTiO3) have been linked to the presence of a two-dimensional electron gas with unique behavior. We perform a detailed density functional theory study of the lattice and electronic structure of SrTiO3 slabs with multiple oxygen vacancies, with a main focus on two vacancies near a titanium dioxide terminated SrTiO3 surface. We conclude based on total energies that the two vacancies preferably inhabit the first two layers, i.e. they cluster vertically, while in the direction parallel to the surface, the vacancies show a weak tendency towards equal spacing. Analysis of the nonmagnetic electronic structure indicates that oxygen defects in the surface TiO2 layer lead to population of Ti ${{t}_{2g}}$ states and thus itinerancy of the electrons donated by the oxygen vacancy. In contrast, electrons from subsurface oxygen vacancies populate Ti eg states and remain localized on the two Ti ions neighboring the vacancy. We find that both the formation of a bound oxygen-vacancy state composed of hybridized Ti 3eg and 4p states neighboring the oxygen vacancy as well as the elastic deformation after extracting oxygen contribute to the stabilization of the in-gap state.
Far outside the surface of slabs, the exact exchange (EXX) potential vx falls off as −1/z , if z denotes the direction perpendicular to the surface and the slab is localized around z=0 . Similarly, the EXX energy density ex behaves as −n/(2z) , where n is the electron density. Here, an alternative proof of these relations is given, in which the Coulomb singularity in the EXX energy is treated in a particularly careful fashion. This new approach allows the derivation of the next-to-leading order contributions to the asymptotic vx and ex . It turns out that in both cases, the corrections are proportional to 1/z2 in general.