Structure maps for hcp metals from first principles calculations

The ability to predict the existence and crystal type of ordered structures of materials from their components is a major challenge of current materials research. Empirical methods use experimental data to construct structure maps and make predictions based on clustering of simple physical parameters. Their usefulness depends on the availability of reliable data over the entire parameter space. Recent development of high throughput methods opens the possibility to enhance these empirical structure maps by {\it ab initio} calculations in regions of the parameter space where the experimental evidence is lacking or not well characterized. In this paper we construct enhanced maps for the binary alloys of hcp metals, where the experimental data leaves large regions of poorly characterized systems believed to be phase-separating. In these enhanced maps, the clusters of non-compound forming systems are much smaller than indicated by the empirical results alone.Comment: 7 pages, 4 figures, 1 tabl

Thermodynamic stabilities of ternary metal borides: An ab initio guide for synthesizing layered superconductors

Density functional theory calculations have been used to identify stable layered Li-$M$-B crystal structure phases derived from a recently proposed binary metal-sandwich (MS) lithium monoboride superconductor. We show that the MS lithium monoboride gains in stability when alloyed with electron-rich metal diborides; the resulting ordered Li$_{2(1-x)}M_x$B$_2$ ternary phases may form under normal synthesis conditions in a wide concentration range of $x$ for a number of group-III-V metals $M$. In an effort to pre-select compounds with the strongest electron-phonon coupling we examine the softening of the in-plane boron phonon mode at $\Gamma$ in a large class of metal borides. Our results reveal interesting general trends for the frequency of the in-plane boron phonon modes as a function of the boron-boron bond length and the valence of the metal. One of the candidates with a promise to be an MgB$_2$-type superconductor, Li$_2$AlB$_4$, has been examined in more detail: according to our {\it ab initio} calculations of the phonon dispersion and the electron-phonon coupling $\lambda$, the compound should have a critical temperature of $\sim4$ K.Comment: 10 pages, 9 figures, submitted to PR

Optical properties of the Ce and La di-telluride charge density wave compounds

The La and Ce di-tellurides LaTe$_2$ and CeTe$_2$ are deep in the charge-density-wave (CDW) ground state even at 300 K. We have collected their electrodynamic response over a broad spectral range from the far infrared up to the ultraviolet. We establish the energy scale of the single particle excitation across the CDW gap. Moreover, we find that the CDW collective state gaps a very large portion of the Fermi surface. Similarly to the related rare earth tri-tellurides, we envisage that interactions and Umklapp processes play a role in the onset of the CDW broken symmetry ground state

Chemical pressure and hidden one-dimensional behavior in rare earth tri-telluride charge density wave compounds

We report on the first optical measurements of the rare-earth tri-telluride charge-density-wave systems. Our data, collected over an extremely broad spectral range, allow us to observe both the Drude component and the single-particle peak, ascribed to the contributions due to the free charge carriers and to the charge-density-wave gap excitation, respectively. The data analysis displays a diminishing impact of the charge-density-wave condensate on the electronic properties with decreasing lattice constant across the rare-earth series. We propose a possible mechanism describing this behavior and we suggest the presence of a one-dimensional character in these two-dimensional compounds. We also envisage that interactions and umklapp processes might play a relevant role in the formation of the charge-density-wave state in these compounds.Comment: 8 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

Pressure dependence of the charge-density-wave gap in rare-earth tri-tellurides

We investigate the pressure dependence of the optical properties of CeTe$_3$, which exhibits an incommensurate charge-density-wave (CDW) state already at 300 K. Our data are collected in the mid-infrared spectral range at room temperature and at pressures between 0 and 9 GPa. The energy for the single particle excitation across the CDW gap decreases upon increasing the applied pressure, similarly to the chemical pressure by rare-earth substitution. The broadening of the bands upon lattice compression removes the perfect nesting condition of the Fermi surface and therefore diminishes the impact of the CDW transition on the electronic properties of $R$Te$_3$.Comment: 5 pages, 4 figure

Nonlocal extension of the dispersive-optical-model to describe data below the Fermi energy

Present applications of the dispersive-optical-model analysis are restricted by the use of a local but energy-dependent version of the generalized Hartree-Fock potential. This restriction is lifted by the introduction of a corresponding nonlocal potential without explicit energy dependence. Such a strategy allows for a complete determination of the nucleon propagator below the Fermi energy with access to the expectation value of one-body operators (like the charge density), the one-body density matrix with associated natural orbits, and complete spectral functions for removal strength. The present formulation of the dispersive optical model (DOM) therefore allows the use of elastic electron-scattering data in determining its parameters. Application to ${}^{40}$Ca demonstrates that a fit to the charge radius leads to too much charge near the origin using the conventional assumptions of the functional form of the DOM. A corresponding incomplete description of high-momentum components is identified, suggesting that the DOM formulation must be extended in the future to accommodate such correlations properly. Unlike the local version, the present nonlocal DOM limits the location of the deeply-bound hole states to energies that are consistent with (\textit{e,e}$^{\prime}$\textit{p}) and (\textit{p,2p}) data.Comment: 14 pages, 10 figures, submitted to Physical Review

Evidence for coupling between collective state and phonons in two-dimensional charge-density-wave systems

We report on a Raman scattering investigation of the charge-density-wave (CDW), quasi two-dimensional rare-earth tri-tellurides $R$Te$_3$ ($R$= La, Ce, Pr, Nd, Sm, Gd and Dy) at ambient pressure, and of LaTe$_3$ and CeTe$_3$ under externally applied pressure. The observed phonon peaks can be ascribed to the Raman active modes for both the undistorted as well as the distorted lattice in the CDW state by means of a first principles calculation. The latter also predicts the Kohn anomaly in the phonon dispersion, driving the CDW transition. The integrated intensity of the two most prominent modes scales as a characteristic power of the CDW-gap amplitude upon compressing the lattice, which provides clear evidence for the tight coupling between the CDW condensate and the vibrational modes

First principles modelling of magnesium titanium hydrides

Mixing Mg with Ti leads to a hydride Mg(x)Ti(1-x)H2 with markedly improved (de)hydrogenation properties for x < 0.8, as compared to MgH2. Optically, thin films of Mg(x)Ti(1-x)H2 have a black appearance, which is remarkable for a hydride material. In this paper we study the structure and stability of Mg(x)Ti(1-x)H2, x= 0-1 by first-principles calculations at the level of density functional theory. We give evidence for a fluorite to rutile phase transition at a critical composition x(c)= 0.8-0.9, which correlates with the experimentally observed sharp decrease in (de)hydrogenation rates at this composition. The densities of states of Mg(x)Ti(1-x)H2 have a peak at the Fermi level, composed of Ti d states. Disorder in the positions of the Ti atoms easily destroys the metallic plasma, however, which suppresses the optical reflection. Interband transitions result in a featureless optical absorption over a large energy range, causing the black appearance of Mg(x)Ti(1-x)H2.Comment: 22 pages, 9 figures, 4 table

Surface-peaked medium effects in the interaction of nucleons with finite nuclei

We investigate the asymptotic separation of the optical model potential for nucleon-nucleus scattering in momentum space, where the potential is split into a medium-independent term and another depending exclusively on the gradient of the density-dependent g matrix. This decomposition confines the medium sensitivity of the nucleon-nucleus coupling to the surface of the nucleus. We examine this feature in the context of proton-nucleus scattering at beam energies between 30 and 100 MeV and find that the pn coupling accounts for most of this sensitivity. Additionally, based on this general structure of the optical potential we are able to treat both, the medium dependence of the effective interaction and the full mixed density as described by single-particle shell models. The calculated scattering observables agree within 10% with those obtained by Arellano, Brieva and Love in their momentum-space g-folding approach.Comment: 16 pages, 8 figures, submitted to PR