Electric field gradients in s-, p- and d-metal diborides and the effect of pressure on the band structure and Tc_c in MgB2_2

Results of FLMTO-GGA (full-potential linear muffin-tin orbital -- generalized gradient approximation) calculations of the band structure and boron electric field gradients (EFG) for the new medium-T$_c$ superconductor (MTSC), MgB$_2$, and related diborides MB$_2$, M=Be, Al, Sc, Ti, V, Cr, Mo and Ta are reported. The boron EFG variations are found to be related to specific features of their band structure and particularly to the M-B hybridization. The strong charge anisotropy at the B site in MgB$_2$ is completely defined by the valence electrons - a property which sets MgB$_2$ apart from other diborides. The boron EFG in MgB$_2$ is weakly dependent of applied pressure: the B p electron anisotropy increases with pressure, but it is partly compensated by the increase of core charge assymetry. The concentration of holes in bonding $\sigma$ bands is found to decrease slightly from 0.067 to 0.062 holes/B under a pressure of 10 GPa. Despite a small decrease of N(E$_F$), the Hopfield parameter increases with pressure and we believe that the main reason for the reduction under pressure of the superconducting transition temperature, T$_c$, is the strong pressure dependence of phonon frequencies, which is sufficient to compensate the electronic effects.Comment: 12 pages, 3 figure

Ab initio probing of the electronic band structure and Fermi surface of fluorine-doped WO3 as a novel low-TC superconductor

First-principles calculations were performed to investigate the electronic structure and the Fermi surface of the newly discovered low-temperature superconductor: fluorine-doped WO3. We find that F doping provides the transition of the insulating tungsten trioxide into a metallic-like phase WO3-xFx, where the near-Fermi states are formed mainly from W 5d with admixture of O 2p orbitals. The cooperative effect of fluorine additives in WO3 consists in change of electronic concentration as well as the lattice constant. At probing their influence on the near-Fermi states separately, the dominant role of the electronic factor for the transition of tungsten oxyfluoride into superconducting state was established. The volume of the Fermi surface gradually increases with the increase of the doping. In the sequence WO3 \rightarrow WO2.5F0.5 the effective atomic charges of W and O ions decrease, but much less, than it is predicted within the idealized ionic model - owing to presence of the covalent interactions W-O and W-F.Comment: 8 pages, 4 figure

Nature of bonding and electronic structure in MgB2, a boron intercalation superconductor

Chemical bonding and electronic structure of MgB2, a boron-based newly discovered superconductor, is studied using self-consistent band structure techniques. Analysis of the transformation of the band structure for the hypothetical series of graphite - primitive graphite - primitive graphite-like boron - intercalated boron, shows that the band structure of MgB2 is graphite-like, with pi-bands falling deeper than in ordinary graphite. These bands possess a typically delocalized and metallic, as opposed to covalent, character. The in-plane sigma-bands retain their 2D covalent character, but exhibit a metallic hole-type conductivity. The coexistence of 2D covalent in-plane and 3D metallic-type interlayer conducting bands is a peculiar feature of MgB2. We analyze the 2D and 3D features of the band structure of MgB2 and related compounds, and their contributions to conductivity.Comment: 4 pages in revtex, 3 figures in 4 separate EPS file

Superconductivity of metallic boron in MgB_2

Boron in MgB_2 forms layers of honeycomb lattices with magnesium as a space filler. Band structure calculations indicate that Mg is substantially ionized, and the bands at the Fermi level derive mainly from B orbitals. Strong bonding with an ionic component and considerable metallic density of states yield a sizeable electron-phonon coupling. Using the rigid atomic sphere approximation and an analogy to Al, we estimate the coupling constant lambda to be of order 1. Together with high phonon frequencies, which we estimate via zone-center frozen phonon calculations to be between 300 and 700 cm^-1, this produces a high critical temperature, consistent with recent experiments reporting Tc=39 K (J. Akimitsu et al., to be published). Thus MgB_2 can be viewed as an analog of the long sought, but still hypothetical, superconducting metallic hydrogen.Comment: several typos corrected, most importantly, units in the tables fixed and a missing zero in the expression for the resistivity restore

Bonding Nature in MgB2

The accurate charge density of MgB2 was observed at room temperature(R.T.) and 15K by the MEM(Maximum Entropy Method)/Rietveld analysis using synchrotron radiation powder data. The obtained charge density clearly revealed the covalent bonding feature of boron forming the 2D honeycomb network in the basal plane, on the other hand, Mg is found to be in divalent state. A subtle but clear charge concentration was found on boron 2D sheets at 15K, which should be relating to superconductivity.Comment: 4 pages, 3 figure

Pair-Hopping Mechanism for Layered Superconductors

We propose a possible charge fluctuation effect expected in layered superconducting materials. In the multireference density functional theory, relevant fluctuation channels for the Josephson coupling between superconducting layers include the interlayer pair hopping derived from the Coulomb repulsion. When interlayer single-electron tunneling processes are irrelevant in the Kohn-Sham electronic band structure calculation, the two-body effective interactions stabilize a superconducting phase. This state is also regarded as a valence-bond solid in a bulk electronic state. The hidden order parameters coexist with the superconducting order parameter when the charging effect of a layer is comparable to the pair hopping. Relevant materials structures favorable for the pair-hopping mechanism are discussed.Comment: 24 pages, 2 figures, to be published in J. Phys. Soc. Jpn. (2009

BN domains included into carbon nanotubes: role of interface

We present a density functional theory study on the shape and arrangement of small BN domains embedded into single-walled carbon nanotubes. We show a strong tendency for the BN hexagons formation at the simultaneous inclusion of B and N atoms within the walls of carbon nanotubes. The work emphasizes the importance of a correct description of the BN-C frontier. We suggest that BN-C interface will be formed preferentially with the participation of N-C bonds. Thus, we propose a new way of stabilizing the small BN inclusions through the formation of nitrogen terminated borders. The comparison between the obtained results and the available experimental data on formation of BN plackets within the single walled carbon nanotubes is presented. The mirror situation of inclusion of carbon plackets within single walled BN nanotubes is considered within the proposed formalism. Finally, we show that the inclusion of small BN plackets inside the CNTs strongly affects the electronic character of the initial systems, opening a band gap. The nitrogen excess in the BN plackets introduces donor states in the band gap and it might thus result in a promising way for n-doping single walled carbon nanotubes

Superconducting properties and c-axis superstructure of Mg1-xAlxB2

The superconducting and structural properties of a series of Mg1-xAlxB2 samples have been investigated. X-ray diffraction results confirmed the existence of a structural transition associated with the significant change in inter-boron layer distance as reported previously by Slusky et al. Moreover,transmission-electron-microscopy observations revealed the existence of a superstructure with doubled lattice constant along the c-axis direction. We propose that this superstructure is essentially related to the structural transition. The modifications of superconducting transition temperature Tc, the normal state resistivity, and the upper critical field Bc2 by Al doping are discussed in terms of Al-substitution induced changes in the electronic structure at the Fermi energy.Comment: 15 pages, 7 figure

Structural, Magnetic and Electronic Properties of the Iron-Chalcogenide Ax_xFe2−y_{2-y}Se2_2 (A=K, Cs, Rb, Tl and etc.) Superconductors

The latest discovery of a new iron-chalcogenide superconductor A$_x$Fe$_{2-y}$Se$_2$(A=K, Cs, Rb, Tl and etc.) has attracted much attention due to a number of its unique characteristics, such as the possible insulating state of the parent compound, the existence of Fe-vacancy and its ordering, a new form of magnetic structure and its interplay with superconductivity, and the peculiar electronic structures that are distinct from other Fe-based superconductors. In this paper, we present a brief review on the structural, magnetic and electronic properties of this new superconductor, with an emphasis on the electronic structure and superconducting gap. Issues and future perspectives are discussed at the end of the paper.Comment: 45 pages, 19 figure

Band structure of SrFeAsF and CaFeAsF as parent phases for a new group of oxygen-free FeAs superconductors

By means of first-principle FLAPW-GGA calculations, we have investigated the electronic properties of the newly discovered layered quaternary systems SrFeAsF and CaFeAsF as parent phases for a new group of oxygen-free FeAs superconductors. The electronic bands, density of states, Fermi surfaces, atomic charges, together with Sommerfeld coefficients and molar Pauli paramagnetic susceptibility have been evaluated and discussed in comparison with oxyarsenide LaFeAsO - a parent phase for a new class of high-temperature (Tc about 26-56K) oxygen-containing FeAs superconductors. Similarity of our data for SrFeAsF and CaFeAsF with the band structure of oxygen-containing FeAs superconducting materials may be considered as theoretical background specifying the possibility of superconductivity in these oxygen-free systems.Comment: 12 pages, 3 figure