Electronic Structure of the Chevrel-Phase Compounds Snx_{x}Mo6_{6}Se7.5_{7.5}: Photoemission Spectroscopy and Band-structure Calculations

We have studied the electronic structure of two Chevrel-phase compounds, Mo$_6$Se$_{7.5}$ and Sn$_{1.2}$Mo$_6$Se$_{7.5}$, by combining photoemission spectroscopy and band-structure calculations. Core-level spectra taken with x-ray photoemission spectroscopy show systematic core-level shifts, which do not obey a simple rigid-band model. The inverse photoemission spectra imply the existence of an energy gap located $\sim 1$ eV above the Fermi level, which is a characteristic feature of the electronic structure of the Chevrel compounds. Quantitative comparison between the photoemission spectra and the band-structure calculations have been made. While good agreement between theory and experiment in the wide energy range was obtained as already reported in previous studies, we found that the high density of states near the Fermi level predicted theoretically due to the Van Hove singularity is considerably reduced in the experimental spectra taken with higher energy resolution than in the previous reports. Possible origins are proposed to explain this observation.Comment: 8 pages, 5 figure

Insights from ARPES for an undoped, four-layered, two-gap high-T_c superconductor

An undoped cuprate with apical fluorine and inner (i) and outer (o) CuO2-layers is a 60 K superconductor whose Fermi surface (FS) has large n- and p-doped sheets with the SC gap on the n-sheet twice that on the p -sheet (Y. Chen et al.). The Fermi surface is not reproduced by the LDA, but the screening must be substantially reduced due to electronic correlations, and oxygen in the o-layers must be allowed to dimple outwards. This charges the i-layers by 0.01|e|, causes an 0.4 eV Madelung-potential difference between the i and o -layers, quenches the i-o hopping, and localizes the n-sheets onto the i-layers, thus protecting their d-wave pairs from being broken by scattering on impurities in the BaF layers. The correlation-reduced screening strengthens the coupling to z-axis phonons.Comment: 4 pages, 3 figure

Developing the MTO Formalism

We review the simple linear muffin-tin orbital method in the atomic-spheres approximation and a tight-binding representation (TB-LMTO-ASA method), and show how it can be generalized to an accurate and robust Nth order muffin-tin orbital (NMTO) method without increasing the size of the basis set and without complicating the formalism. On the contrary, downfolding is now more efficient and the formalism is simpler and closer to that of screened multiple-scattering theory. The NMTO method allows one to solve the single-electron Schroedinger equation for a MT-potential -in which the MT-wells may overlap- using basis sets which are arbitrarily minimal. The substantial increase in accuracy over the LMTO-ASA method is achieved by substitution of the energy-dependent partial waves by so-called kinked partial waves, which have tails attached to them, and by using these kinked partial waves at N+1 arbitrary energies to construct the set of NMTOs. For N=1 and the two energies chosen infinitesimally close, the NMTOs are simply the 3rd-generation LMTOs. Increasing N, widens the energy window, inside which accurate results are obtained, and increases the range of the orbitals, but it does not increase the size of the basis set and therefore does not change the number of bands obtained. The price for reducing the size of the basis set through downfolding, is a reduction in the number of bands accounted for and -unless N is increased- a narrowing of the energy window inside which these bands are accurate. A method for obtaining orthonormal NMTO sets is given and several applications are presented.Comment: 85 pages, Latex2e, Springer style, to be published in: Lecture notes in Physics, edited by H. Dreysse, (Springer Verlag

Anisotropies in insulating La2−x_{2-x}Srx_xCuO4_4: angular resolved photoemission and optical absorption

Due to the orthorhombic distortion of the lattice, the electronic hopping integrals along the $a$ and $b$ diagonals, the orthorhombic directions, are slightly different. We calculate their difference in the LDA and find $t_{a}^{\prime}-t_{b}^{\prime}\approx 8$meV. We argue that electron correlations in the insulating phase of La$_{2-x}$Sr$_{x}$CuO$_{4}$, i. e. at doping $x\leq 0.055,$ dramatically enhance the $(t_{a}^{\prime}-t_{b}^{\prime})$-splitting between the $a$- and $b$-hole valleys. In particular, we predict that the intensity of both angle-resolved photoemission and of optical absorption is very different for the $a$ and $b$ nodal points

Third-Generation TB-LMTO

We describe the screened Korringa-Kohn-Rostoker (KKR) method and the third-generation linear muffin-tin orbital (LMTO) method for solving the single-particle Schroedinger equation for a MT potential. The simple and popular formalism which previously resulted from the atomic-spheres approximation (ASA) now holds in general, that is, it includes downfolding and the combined correction. Downfolding to few-orbital, possibly short-ranged, low-energy, and possibly orthonormal Hamiltonians now works exceedingly well, as is demonstrated for a high-temperature superconductor. First-principles sp3 and sp3d5 TB Hamiltonians for the valence and lowest conduction bands of silicon are derived. Finally, we prove that the new method treats overlap of the potential wells correctly to leading order and we demonstrate how this can be exploited to get rid of the empty spheres in the diamond structure.Comment: latex2e, 32 printed pages, Postscript figs, to be published in: Tight-Binding Approach to Computational Materials Science, MRS Symposia Proceedings No. 491 (MRS, Pittsburgh, 1998

The Structure of Barium in the hcp Phase Under High Pressure

Recent experimental results on two hcp phases of barium under high pressure show interesting variation of the lattice parameters. They are here interpreted in terms of electronic structure calculation by using the LMTO method and generalized pseudopotential theory (GPT) with a NFE-TBB approach. In phase II the dramatic drop in c/a is an instability analogous to that in the group II metals but with the transfer of s to d electrons playing a crucial role in Ba. Meanwhile in phase V, the instability decrease a lot due to the core repulsion at very high pressure. PACS numbers: 62.50+p, 61.66Bi, 71.15.Ap, 71.15Hx, 71.15LaComment: 29 pages, 8 figure

Coulomb-Enhanced Spin-Orbit Splitting: The Missing Piece in the Sr2RhO4 Puzzle

The outstanding discrepancy between the measured and calculated (local-density approximation) Fermi surfaces in the well-characterized, paramagnetic Fermi liquid Sr2RhO4 is resolved by including the spin-orbit coupling and Coulomb repulsion. This results in an effective spin-orbit coupling constant enhanced 2.15 times over the bare value. A simple formalism allows discussion of other systems. For Sr2RhO4, the experimental specific-heat and mass enhancements are found to be 2.2.Comment: 4 pages, 2 figure

Comment on "First-principles calculation of the superconducting transition in MgB2 within the anisotropic Eliashberg formalism"

Choi et al. [Phys. Rev. B 66, 020513 (2002)] recently presented first principles calculations of the electron-phonon coupling and superconductivity in MgB2, emphasizing the importance of anisotropy and anharmonicity. We point out that (1) variation of the superconducting gap inside the sigma- or the pi-bands can hardly be observed in real samples, and (2) taking the anisotropy of the Coulomb repulsion into account influences the size of the small gap, Delta_pi.Comment: 3 pages, 2 color figure

Lattice vibrations and structural instability in Cesium near the cubic to tetragonal transition

Under pressure cesium undergoes a transition from a high-pressure fcc phase (Cs-II) to a collapsed fcc phase (Cs-III) near 4.2GPa. At 4.4GPa there follows a transition to the tetragonal Cs-IV phase. In order to investigate the lattice vibrations in the fcc phase and seek a possible dynamical instability of the lattice, the phonon spectra of fcc-Cs at volumes near the III-IV transition are calculated using Savrasov's density functional linear-response LMTO method. Compared with quasiharmonic model calculations including non-central interatomic forces up to second neighbours, at the volume $V/V_0= 0.44$ ($V_0$ is the experimental volume of bcc-Cs with $a_0$=6.048{\AA}), the linear-response calculations show soft intermediate wavelength $T_{[1\bar{1}0]}[{\xi}{\xi}0]$ phonons. Similar softening is also observed for short wavelength $L[\xi\xi\xi]$ and $L[00\xi]$ phonons and intermediate wavelength $L[\xi\xi\xi]$ phonons. The Born-von K\'{a}rm\'{a}n analysis of dispersion curves indicates that the interplanar force constants exhibit oscillating behaviours against plane spacing $n$ and the large softening of intermediate wavelength $T_{[1\bar{1}0]}[{\xi}{\xi}0]$ phonons results from a negative (110)-interplanar force-constant $\Phi_{n=2}$. The frequencies of the $T_{[1\bar{1}0]}[{\xi}{\xi}0]$ phonons with $\xi$ around 1/3 become imaginary and the fcc structure becomes dynamically unstable for volumes below $0.41V_0$. It is suggested that superstructures corresponding to the $\mathbf{q}{\neq}0$ soft mode should be present as a precursor of tetragonal Cs-IV structure.Comment: 12 pages, 5 figure

Covalent bonding and the nature of band gaps in some half-Heusler compounds

Half-Heusler compounds \textit{XYZ}, also called semi-Heusler compounds, crystallize in the MgAgAs structure, in the space group $F\bar43m$. We report a systematic examination of band gaps and the nature (covalent or ionic) of bonding in semiconducting 8- and 18- electron half-Heusler compounds through first-principles density functional calculations. We find the most appropriate description of these compounds from the viewpoint of electronic structures is one of a \textit{YZ} zinc blende lattice stuffed by the \textit{X} ion. Simple valence rules are obeyed for bonding in the 8-electron compound. For example, LiMgN can be written Li$^+$ + (MgN)$^-$, and (MgN)$^-$, which is isoelectronic with (SiSi), forms a zinc blende lattice. The 18-electron compounds can similarly be considered as obeying valence rules. A semiconductor such as TiCoSb can be written Ti$^{4+}$ + (CoSb)$^{4-}$; the latter unit is isoelectronic and isostructural with zinc-blende GaSb. For both the 8- and 18-electron compounds, when \textit{X} is fixed as some electropositive cation, the computed band gap varies approximately as the difference in Pauling electronegativities of \textit{Y} and \textit{Z}. What is particularly exciting is that this simple idea of a covalently bonded \textit{YZ} lattice can also be extended to the very important \textit{magnetic} half-Heusler phases; we describe these as valence compounds \textit{ie.} possessing a band gap at the Fermi energy albeit only in one spin direction. The \textit{local} moment in these magnetic compounds resides on the \textit{X} site.Comment: 18 pages and 14 figures (many in color