Pressure-Temperature Phase Diagram of Vanadium Dioxide.

The complexity of strongly correlated electron physics in vanadium dioxide is exemplified as its rich phase diagrams of all kinds, which in turn shed light on the mechanisms behind its various phase transitions. In this work, we map out the hydrostatic pressure-temperature phase diagram of vanadium dioxide nanobeams by independently varying pressure and temperature with a diamond anvil cell. In addition to the well-known insulating M1 (monoclinic) and metallic R (tetragonal) phases, the diagram identifies the existence at high pressures of the insulating M1' (monoclinic, more conductive than M1) phase and two metallic phases of X (monoclinic) and O (orthorhombic, at high temperature only). Systematic optical and electrical measurements combined with density functional calculations allow us to delineate their phase boundaries as well as reveal some basic features of the transitions.

Unconventional aspects of electronic transport in delafossite oxides.

The electronic transport properties of the delafossite oxides [Formula: see text] are usually understood in terms of two well-separated entities, namely the triangular [Formula: see text] and ([Formula: see text] layers. Here, we review several cases among this extensive family of materials where the transport depends on the interlayer coupling and displays unconventional properties. We review the doped thermoelectrics based on [Formula: see text] and [Formula: see text], which show a high-temperature recovery of Fermi-liquid transport exponents, as well as the highly anisotropic metals [Formula: see text], [Formula: see text], and [Formula: see text], where the sheer simplicity of the Fermi surface leads to unconventional transport. We present some of the theoretical tools that have been used to investigate these transport properties and review what can and cannot be learned from the extensive set of electronic structure calculations that have been performed.

High- and low-temperature modifications of Sc3RuC4 and Sc3OsC4--relativistic effects, structure, and chemical bonding.

Sc(3)RuC(4) and Sc(3)OsC(4) were synthesized by arc-melting and subsequent annealing. At room temperature, they crystallize with the Sc(3)CoC(4) structure, space group Immm. At 223 and 255 K, Sc(3)RuC(4) and Sc(3)OsC(4), respectively, show a monoclinic distortion caused by a pair-wise displacement of the one-dimensional [Ru(C(2))(2)](delta-) and [Os(C(2))(2)](delta-) polyanions, which are embedded in a scandium matrix. Superstructure formation leads to shorter Ru-Ru and Os-Os distances of 316 pm between adjacent [Ru(C(2))(2)](delta-) and [Os(C(2))(2)](delta-) polyanions. Each ruthenium (osmium) atom is covalently bonded to four C(2) pairs with Ru-C (Os-C) distances of 220-222 pm. A comparison of the C-C bond distances at room temperature in Sc(3)TC(4) with T representing a group 8 transition metal (Fe, Ru, Os) reveals a minimum in the case of the 4d metal Ru: 144.98(11) pm (Fe), 142.8(7) pm (Ru), and 144.6(4) pm (Os). Analysis of the local electronic structure of the [T(C(2))(2)] moieties hints at a complex interplay between chemical bonding and relativistic effects, which is responsible for the V-shaped pattern of the C-C bond distances (long, short, and long for T = Fe, Ru, and Os, respectively). Relativistic effects lead to a strengthening of covalent T-C bonding. This is shown on the basis of periodic DFT calculations by a significant increase of the charge density at the T-C bond critical points (0.55 < 0.57 < 0.64 eA(-3)) down the row of group 8 elements. These structural characteristics and topological features do not change in the corresponding low-temperature phases of Sc(3)RuC(4) and Sc(3)OsC(4). However, topological analyses of theoretical charge density distributions reveal distinct changes of the valence shell charge concentrations at the transition metal centers due to the monoclinic distortions. Presumably, the local electronic situation at the transition metals reflects the origin and extent of these monoclinic distortions.

Experimental electron density of the complex carbides Sc3[Fe(C2)(2)] and Sc3[Co(C2)(2)].

The nature of chemical bonding in the complex carbides Sc3[Fe(C2)2] (1) and Sc3[Co(C2)2] (2) has been explored by combined experimental and theoretical charge density studies. The structures of these organometallic carbides contain one-dimensional infinite TC4 (T = Fe, Co) ribbons embedded in a scandium matrix. Bonding in 1 and 2 was studied experimentally by multipolar refinements based on high-resolution X-ray data and compared to scalar-relativistic electronic structure calculations using the augmented spherical wave method. Besides substantial covalent T-C bonding within the TC4 ribbons, one also observes discrete Sc-C bonds of noticeable covalent character. Furthermore, our study highlights that even tiny differences in the electronic band structure of solids might be faithfully recovered in the properties of the Laplacian of the experimental electron density. In our case, the increase of the Fermi level in the organometallic Co(d9) carbide 2 relative to its isotypic Fe(d8) species 1 is reflected in the charge density picture by a significant change in the polarization pattern displayed by valence shell charge concentrations of the transition metal centers in the TC4 units. Hence, precise high-resolution X-ray diffraction data provide a reliable tool to discriminate and analyze the local electronic structures of isotypic solids, even in the presence of a severe coloring problem (Z(Fe)/Z(Co) = 26/27).