Due to the high degree of improvement and prediction success of ab initio calculations, the advance in Materials Science has been partially shifted from the empirical chemical quest of new compounds to the systematic calculation of putative structures that can yield compounds with promising properties. In particular, two dimensional (2D) materials are at present a central target, as many potential devices rely on particular characteristics of a single layer of atoms or low dimensional electronic active sheets in bulk materials. Several works have focused on this paradigm, yielding a large list of new interesting 2D candidates. Here, we introduce a technique based on an algorithmic filter for searching prospective candidates in very large electronic structure databases. It is designed to detect electronic bands with low energy dispersion along particular directions in reciprocal space, i.e. those perpendicular to certain plane or surface. We propose it as an absolute criterion for obtaining all possible two dimensional compounds. With it we show that previous explorations have missed out a whole group of possible two dimensional materials, namely only electronically 2D.

It was recently discovered that a conductive, metallic state is formed on the surface of some insulating oxides. First observed on SrTiO3 (001), it was then found in other compounds as diverse as anatase TiO2, KTaO3, BaTiO3, ZnO, and also on different surfaces of SrTiO3 (or other oxides) with different symmetries. The spatial extension of the wave function of this electronic state is of only a few atomic layers. Experiments indicate its existence is related to the presence of oxygen vacancies induced at or near the surface of the oxide. We present a simplified model aimed at describing the effect of its small spatial extension on measurements of its threedimensional (3D) electronic structure by angular resolved photoemission spectroscopy. For the sake of clarity, we base our discussion on a simple tight-binding scheme plus a confining potential that is assumed to be induced by the oxygen vacancies. Our model parameters are, nevertheless, obtained from density functional calculations. With this methodology, we can explain, from a very simple concept of selective interference, the "wobbling," i.e., the photoemission intensity modulation and/or apparent dispersion of the Fermi surface and spectra along the out-of-plane (k(z)) direction, and the "mixed 2D/3D" characteristics observed in some experiments. We conclude that the critical model parameters for such an effect are the relative strength of the electronic hopping of each band and the height/width aspect ratio of the surface confining potential. By considering recent photoemission measurements, in light of our findings, we can get relevant information on the electronic wave functions and the nature of the confining potential.

We have performed neutron diffraction measurements of tetragonal Sr2CrO4 to study the crystallographic structure as a function of temperature and the magnetic properties developed below . We have measured the precise positions of the oxygen atoms of the CrO6 octahedra and observed that, with decreasing temperature, the octahedra pass from elongated to almost ideal, contradicting the intuitive idea of a Jahn-Teller effect. DFT calculations explain this apparent anomalous behaviour by establishing that energy level degeneracy only exists in a highly elongated octahedra. Our study agrees with the idea of a weak orbital ordering transition around 150 K followed by an itinerant antiferromagnetic ordering at 110 K with a wave vector determined both from neutron powder diffraction and theory.

We perform an extensive study of Sr_{3}Cr_{2}O_{7}, the n=2 member of the Ruddlesden-Popper Sr_{n+1}Cr_{n}O_{3n+1} system. An antiferromagnetic ordering is clearly visible in the magnetization and the specific heat, which yields a huge transition entropy, Rln(6). By neutron diffraction as a function of temperature we have determined the antiferromagnetic structure that coincides with the one obtained from density functional theory calculations. It is accompanied by anomalous asymmetric distortions of the CrO_{6} octahedra. Strong coupling and Lanczos calculations on a derived Kugel-Khomskii Hamiltonian yield a simultaneous orbital and moment ordering. Our results favor an exotic ordered phase of orbital singlets not originated by frustration.

We perform an extensive study of Sr3Cr2O7, the n = 2 member of the Ruddlesden-Popper Srn+1CrnO3n+1 system. An antiferromagnetic ordering is clearly visible in the magnetization and the specific heat, which yields a huge transition entropy, R ln(6). By neutron diffraction as a function of temperature we have determined the antiferromagnetic structure that coincides with the one obtained from density functional theory calculations. It is accompanied by anomalous asymmetric distortions of the CrO6 octahedra. Strong coupling and Lanczos calculations on a derived Kugel-Khomskii Hamiltonian yield a simultaneous orbital and moment ordering. Our results favor an exotic ordered phase of orbital singlets not originated by frustration.

We report the existence of a two-dimensional electron system (2DES) at the (001) surface of CaTiO3. Using angle-resolved photoemission spectroscopy, we find a hybridization between the d_xz and d_yz orbitals, not observed in the 2DESs at the surfaces of other ATiO3 perovskites, e.g. SrTiO3 or BaTiO3. Based on a comparison of the 2DES properties in these three materials, we show how the electronic structure of the 2DES (bandwidth, orbital order and electron density) is coupled to different typical lattice distortions in perovskites. The orbital hybridization in orthorhombic CaTiO3 results from the rotation of the oxygen octahedra, which can also occur at the interface of oxide heterostructures to compensate strain. More generally, the control of the orbital order in 2DES by choosing different A-site cations in perovskites offers a new gateway towards 2DESs in oxide heterostructures beyond SrTiO3.

We have synthesized for the first time the metastable compound 1T-CrTe2. We have done its complete structural characterization and measured its magnetization, specific heat and electrical resistivity between 4 and 330 K. We have also performed detailed band structure calculations. We have found that it crystallizes in the CdI2 structure type and that its electrical resistance follows a metallic behaviour below room temperature. Its magnetization and specific heat curves show that the compound has a transition to a ferromagnetic state at TC = 310 K, with the magnetic moments ordered parallel to the basal plane. From the specific heat measurements and the ferromagnetic solutions obtained from our DFT calculations, we conclude that the ferromagnetism is of itinerant nature.

We determine the pressure phase diagram of the 1111 compounds CaFeAsF and SrFeAsF, up to 20 GPa and down to 4 K by electrical resistivity measurements and the change of structure up to 40 GPa at room temperature. The antiferromagnetic transition temperature, as determined by the derivative peak, shows a minimum at ~5 GPa (10 GPa) for the Ca (Sr) compound. For CaFeAsF, superconductivity appears at this minimum, coincident with the development of a previously reported monoclinic phase. For SrFeAsF, where the orthorhombic and the monoclinic phase were reported to coexist, superconductivity exists above P≥1 GPa. Both phase diagrams can be scaled by a shift of ~10 GPa pressure at which the volume of SrFeAsF and that of CaFeAsF at ambient pressure coincide. The difference of our phase diagram with that of electron-doped 1111 samples is accounted for by hole doping under pressure, which we verified through electron band structure calculations.

The nature of the Mott transition in the absence of any symmetry breaking remains a matter of debate. We study the correlation-driven insulator-to-metal transition in the prototypical 3D Mott system GaTa(4)Se(8), as a function of temperature and applied pressure. We report novel experiments on single crystals, which demonstrate that the transition is of first order and follows from the coexistence of two states, one insulating and one metallic, that we toggle with a small bias current. We provide support for our findings by contrasting the experimental data with calculations that combine local density approximation with dynamical mean-field theory, which are in very good agreement.

We have studied the effect of substitution of Cr in metastable 1T -CrSe2 by Ti and V on its structural and magnetic properties. The structural transitions observed between 165-180 K in the pure material are stomped by the doping. The pure compound has a magnetization corresponding to an antiferromagnetic (AF) ground state. On Ti substitution, we observe an increase of the lattice constants and a gradual passage towards a ferromagnetic state, while V replacement maintains AF order up to our highest doping, xV = 0.5.With our experimental results and the help of first-principles calculations, we construct the phase diagram of the system.

We study the electronic properties of GaV4S8 (GVS) and GaTa4Se8 (GTS), two distant members within the large family of chalcogenides AM4X8, with A = {Ga, Ge}, M = {V, Nb, Ta, Mo} and X = {S, Se}. While all these compounds are Mott insulators, their ground states show many types of magnetic order, with GVS being ferromagnetic and GTS non-magnetic. Based on their band structures, calculated with density functional theory methods, we compute an effective tight-binding Hamiltonian in a localised Wannier basis set, for each of the two compounds. The localised orbitals provide a very accurate representation of the band structure, with hopping amplitudes that rapidly decrease with distance. We estimate the superexchange interactions and show that the Coulomb repulsion with Hund's coupling may account the for the different ground states observed in GVS and GTS. Our localised Wannier basis provides a starting point for realistic dynamical mean-field theory studies of strong-correlation effects in this family compounds.

Resistive switching (RS) phenomena in transition-metal oxides have been intensively studied in recent years, because of the potential for non-volatile memory application, i.e. resistance random access memory (ReRAM). This chapter explores the RS phenomenon in a multiferroic BiFeO3. It presents that on single crystal SrTiO3:Nb a native surface layer exists that can be switched from semiconducting to metallic behavior by external gradients. The chapter examines the physical mechanism of oxygen vacancy migration in Pt/Nb:SrTiO3 interfaces, which shows the bipolar RS (BRS) phenomena. Resistive RAM (RRAM or ReRAM) composed of a transtition metal oxide dielectric in a capacitor-like structure is a candidate technology for next generation non-volatile memory devices. The chapter uses the resonant photoemission spectroscopy to study the valence and conduction band partial density of states in TiO2 films and single crystals. Controlled Vocabulary Terms conduction bands; ferroelectric materials; switching; transition metal compounds; valence bands

It is well known that transport in lightly n-doped SrTiO(3) involves light and heavy electron bands. We have found that upon application of moderate quasi-isotropic pressures, the relative positions of these subbands are changed by a few meV and, eventually, a band inversion occurs at ~1 kbar. Such effects are, however, suppressed in the closely related KTaO(3) perovskite. We show that the extremely subtle electronic reconfiguration in SrTiO(3) is triggered by strain-induced structural transformations that are accompanied by remarkable mobility enhancements up to about Δμ/μ≈300%. Our results provide a microscopic rationale for the recently discovered transport enhancement under strain and underscore the role of the internal structural degrees of freedom in the modulation of the perovskite electronic properties.

The electrical resistivity, crystalline structure, and electronic properties calculated from the experimentally measured atomic positions of the compound SmFeAsO0.81F0.19 have been studied up to pressures ∼20 GPa. The correlation between the pressure dependence of the superconducting transition temperature (Tc) and crystallographic parameters on the same sample shows clearly that a regular FeAs4 tetrahedron maximizes Tc through optimization of carrier transfer to the FeAs planes as indicated by the evolution of the electronic band structures.

Ab initio calculations using the local spin-density approximation plus Hubbard U (LSDA+U) method have been performed for the three reported phases of Ti4O7. Using the experimental structural parameters, we find that the electronic and magnetic properties are qualitatively different for each phase. The low-temperature structure is an antiferromagnetic semiconductor, with bipolarons arranged symmetrically in chains, separated by other nonmagnetic ion chains. The intermediate-temperature structure also contains bipolarons, but in a much more complicated order, in addition to unpaired magnetic Ti3+ ions and nonmagnetic Ti4+ ions. It has a smaller band gap than the low-temperature one. The high-temperature structure is metallic, and different distributions of Ti3+ and Ti4+ ions can be found that are almost degenerate.

The electrical resistivity, crystalline structure, and electronic properties calculated from the experimentally measured atomic positions of the compound SmFeAsO0.81F0.19 have been studied up to pressures similar to 20 GPa. The correlation between the pressure dependence of the superconducting transition temperature (T-c) and crystallographic parameters on the same sample shows clearly that a regular FeAs4 tetrahedron maximizes T-c through optimization of carrier transfer to the FeAs planes as indicated by the evolution of the electronic band structures.

Two perovskite-derived materials, CaCu3Mn4O12 and CaCu3Ti4O12, have drawn much recent interest due to their magnetoresistive, dielectric, and magnetoelectronic characteristics. Here we present initial theoretical insights into each of these points, based on first principles, density functional based calculations. Our results predict CCMO to have a spin-asymmetric energy gap, which leads to distinct temperature- and magnetic field-dependent changes in properties, and helps to account for its observed negative magnetoresistivity. We have studied CCTO primarily to gain insight into the exchange coupling in both these compounds, where the conventional superexchange coupling vanishes by symmetry for both nearest and next nearest Cu-Cu neighbors, a consequence of the structure. In CCTO, it is necessary to go to 5th Cu-Cu neighbors to obtain a (superexchange) coupling that can provide the coupling necessary to give three dimensional order. Non-superexchange mechanisms may be necessary to describe the magnetic coupling in this structural class.

We measure the pressure dependence of the electrical resistivity and the crystal structure of iron superconductor Sr2VO3FeAs. Below similar to 10GPa the structure compresses but remains undeformed, with regular FeAs4 tetrahedrons, and a constant T-c. Beyond 10GPa, the tetrahedron strongly distorts, while T-c goes gradually to zero. Band structure calculations of the undistorted structure show multiple-nesting features that hinder the development of an antiferromagnetic (AF) ground state, allowing the appearance of superconductivity. The deformation of the tetrahedra that breaks band degeneracy degrades multiple nesting, thus favouring one particular AF state at the expense of T-c. Copyright (C) EPLA, 2011