Interplay between hybridisation gaps and unusual magnetic orders in Kondo semiconductors CeT2Al10 (T = Ru and Os)

ABSTRACT

Kondo semiconductors based on rare-earth elements possess a narrow gap in the renormalised density of states near the Fermi level. Their ground states remain nonmagnetic due to strong hybridisation of the 4f state with conduction bands. However, in the orthorhombic compounds CeT₂Al₁₀ (T?=?Ru, Os), opening of a hybridisation gap is followed by an antiferromagnetic (AFM) order at a rather high temperature T_N???28?K. Our systematic studies of the effects of electron/hole doping on the magnetic and transport properties, electron tunnelling, and spin-gap formation revealed that the hybridisation gap is indispensable for the unusual AFM order. Under uniaxial pressure, T_N increases linearly as the orthorhombic b-axis parameter is decreased. Our findings support the model that a kind of charge-density wave developing along the b axis in the presence of the hybridisation gap induces the AFM order in these systems.     

Theoretical predictions of the structural,mechanical and lattice dynamical properties of XW2 (X = Zr,Hf) Laves phases

We have investigated the structural, mechanical and lattice dynamical properties of ZrW₂ and HfW₂ compounds in cubic C15 (space group Fd-3m), hexagonal C14 (space group P6₃/mmc) and C36 (space group P6₃/mmc) phases using generalized gradient approximation within the plane-wave pseudo-potential density functional theory. We have found that ZrW₂ and HfW₂ in cubic C15 phase are the most stable among the considered phases. From calculated elastic constants, it is shown that all phases are mechanically stable according to the elastic stability criteria. The related mechanical properties, such as bulk, shear and Young moduli, Poisson’s ratio, Debye temperature and hardness have been also calculated. The results show that ZrW₂ and HfW₂ compounds are ductile in nature with respect to the B/G and Cauchy pressure analysis. The phonon dispersion curves, phonon density of states and some thermodynamic properties are computed and discussed exhaustively for considered phases.     

First-principles studies of the structural and electronic properties of the C14 Laves phase XCr2 (X = Ti,Zr, Nb,Hf and Ta)

The optimized structures, electronic properties and bonding characteristics of the hexagonal C14 Laves phase XCr₂ (X?=?Ti, Zr, Nb, Hf and Ta) have been investigated using first-principles calculations. Our results reveal that the equilibrium formation enthalpies are not depends entirely on the atomic numbers. The total and the partial density of states and valence charge densities of Laves phases are also calculated and applied to reveal the nature of the bonding character in consideration of the different atomic numbers.     

First-principles investigation of the elastic and electronic properties of the binary intermetallics in the Al–La alloy system

The structural, elastic and electronic properties of Al₂La, AlLa₃ and Al₃La binary intermetallics in the Al–La alloy system were investigated using the first-principles method. The calculated lattice constants were consistent with the experimental values. Formation enthalpy and cohesive energy showed that the studied Al₂La, AlLa₃ and Al₃La all have a higher structural stability, and the alloying ability of Al₂La and Al₃La is stronger than that of AlLa₃. The single-crystal elastic constants (C_ij) as well as polycrystalline elastic parameters (bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio υ and anisotropy value A) were calculated by the Voigt–Reuss–Hill (V–R–H) approximations, and the relationship of these elastic parameters between Al₂La, AlLa₃ and Al₃La phases were discussed in detail. The results showed that Al₂La and Al₃La which are anisotropic materials are absolutely brittle, while the isotropic AlLa₃ is slightly ductile. Finally, the electronic density of states (DOS) was also calculated to reveal the underlying mechanism of structural stability.     

Cohesive properties of (Cu,Ni)–(In,Sn) intermetallics: Database,electron-density correlations and interpretation of bonding trends

This paper presents a systematic and comparative study of the composition and volume dependence of the cohesive properties for a large group of Me–X intermetallic phases (IPs) with Me=Cu,Ni and X=In,Sn, which are of interest in relation with the design of lead-free soldering (LFS) alloys. The work relies upon a database with total-energy versus volume information developed by using projected augmented waves (PAW) calculations. In previous papers by the current authors it was shown that these results account satisfactorily for the direct and indirect experimental data available. In the present work, the database is further expanded to investigate the composition dependence of the volume (V₀), and the composition and volume dependence of the bulk modulus (B₀) and cohesive energy (E_coh). On these bases, an analysis is performed of the systematic effects of replacing Cu by Ni in several Me–X phases (Me=Cu,Ni and X=In,Sn) reported as stable and metastable, as well as various hypothetical compounds involved in the thermodynamic modeling of IPs using the Compound-Energy Formalism. Moreover, it is shown that the cohesion-related quantities (B₀/V₀)^½ and (E_coh^½/V₀) can be correlated with a parameter expressing the number of valence electrons per unit volume. These findings are compared in detail with related relations involving the Miedema empirical electron density at the boundary of the Wigner–Seitz cell. In view of the co-variation of the cohesive properties, E_coh is selected as a key property and its composition and structure dependence is examined in terms of a theoretical view of the bonding which involves the hybridization of the d-states of Cu or Ni with the s and p-states of In or Sn, for this class of compounds. In particular, a comparative analysis is performed of the DOS of various representative, iso-structural Me–X compounds. Various effects of relevance to understand the consequences of replacing Cu by Ni in LFS alloys are highlighted and explained microscopically for the first time.     

Electronic structure and magnetic properties of X2YZ (X = Co,Y = Mn,Z = Ge,Sn) type Heusler compounds: a first principle study

We performed the structure optimization followed by the calculation of electronic structure and magnetic properties on Co₂MnGe and Co₂MnSn. The structure optimization was based on generalized gradient approximation exchange correlation and full potential linearized augmented plane wave (FP-LAPW) method. The calculation of electronic structure was based on FP-LAPW method using local spin density approximation. We have studied the electronic structure and magnetic properties. The calculated density of states and band structures shows the half-metallic ferromagnets character of Co₂MnGe and Co₂MnSn.     

Half-metallicity and onsite Hubbard interaction on d-electronic states: a case study of Fe2NiZ (Z = Al,Ga, Si,Ge) Heusler systems

DFT-based structural optimisations of Fe₂NiZ (Z?=?Al, Ga, Si, Ge) Heusler compounds confirm the stability of these alloys in F-43m phase. While defining the electronic structure, onsite Hubbard approximation scheme for exchange correlations predicted better results than the generalised gradient approximation. Calculated band structure and densities of states together with spin magnetic moments designate the half-metallic character of these alloys. Indirect band gaps, 1.2?eV for Fe₂NiAl, 0.98?eV for Fe₂NiGa, 1.3?eV for Fe₂NiSi and 1.1?eV for Fe₂NiGe in spin-down states are observed. The ferromagnetic spin moments amount to an integral value of 5μB for (Al, Ga) and 6μB for (Si, Ge) systems with a maximum contribution from transition metal atom (Fe). To forecast the possible turnout of the thermopower, Seebeck coefficients, electrical and thermal conductivities are calculated, which directly hints the thermoelectric response of these materials. This study creates a possibility of these alloys in thermoelectrics and spintronics.     

In-plane magnetic penetration depth in FeSe1-xSx (x = 0, 0.04, 0.09) and FeTe1-xSex (x = 0.40) single crystals

The magnetization anomaly of FeSe_1–xS_x(x?=?0, 0.04, 0.09) and FeTe_1–xSe_x(x?=?0.40) single crystals are examined through our Modified Phenomenological Ginzburg–Landau (MPGL) theory applicable to two-band superconducting systems. The theory in the London limit calculates the values of λ_ab(0) as 445.695, 372.058 and 432.957?nm of FeSe_1–xS_x for x?=?0, 0.04, 0.09 which are very close to the experimental values reported by Hafiez et al. [Superconducting properties of sulfur-doped iron selenide. Phys Rev B. 2015;91(16):165109–165120] and as 534?nm for FeTe_1–xSe_x(x?=?0.40) single crystal, which is close to the experimental value reported by Yadav and Paulose [Upper critical field, lower critical field and critical current density of FeTe_0.60Se_0.40 single crystals. New J Phys 2009;11:103046]. In addition, the variation of temperature-dependent in-plane magnetic penetration depth λ_ab(T) with the temperature (T) has been presented, which agrees well as reported by Hafiez et al. [Superconducting properties of sulfur-doped iron selenide. Phys Rev B. 2015;91(16):165109–165120] and Yadav and Paulose [Upper critical field, lower critical field and critical current density of FeTe_0.60Se_0.40 single crystals. New J Phys. 2009;11:103046].     

Structural,electronic, optical and thermodynamic investigations of NaXF3 (X = Ca and Sr): First-principles calculations

The structural, electronic and optical properties for fluoro-perovskite NaXF₃ (X?=?Ca and Sr) compounds have calculated by WIEN2k code based on full potential linearized augmented plane wave (FP-LAPW) approach within density functional theory (DFT). To perform the total energy calculations, exchange-correlation energy/potential functional has been utilized into generalized gradient approximation (GGA) and local density approximation (LDA). Our evaluated results like equilibrium lattice constants, bulk moduli, and their pressure derivatives are in agreement with the available data. The electronic band structure calculation has revealed an indirect band-gap nature of NaCaF₃, while NaSrF₃ has direct band gap. Total and partial densities of states confirm the degree of localized electrons in different bands. The optical transitions in NaCaF₃ and NaSrF₃ compounds were identified by assigning corresponding peaks obtained from the dispersion relation for the imaginary part of the dielectric function. The thermodynamic properties were calculated using quasi-harmonic Debye model to account lattice vibrations. In addition, the influence of temperature and pressure effects was analyzed on bulk modulus, lattice constant, heat capacities and Debye temperature.     

Investigation of half-metallic and magnetic phase transition in Co2TiZ (Z = Al,Ga, In) Heusler alloys

ABSTRACT

The half-metallic and ferromagnetic properties of Co₂TiZ (Z?=?Al, Ga, In) Heusler alloys are investigated. The structural stability is analyzed among the two possible structures, namely, L2₁ (Cu₂MnAl phase) and XA (Hg₂CuTi phase) structures. It is found that these alloys are stable in L2₁ (Cu₂MnAl phase) structure. The electronic structure of Co₂TiZ reveals that these alloys exhibit half-metallic ferromagnetism with small spin-flip gap at the minority spin state. As the pressure is increased, ferromagnetic to non-magnetic phase transition is observed at the pressures of 380.9, 363.0 and 317.8?GPa for Co₂TiAl, Co₂TiGa and Co₂TiIn, respectively. Half-metallic to metallic phase transition occurs in Co₂TiAl, Co₂TiGa and Co₂TiIn at the pressures of 76.5?GPa, 73.1?GPa and 63.9?GPa respectively.     

Ab initio investigation of isomeric and conformeric structures of halogen nitrites,XONO (X = Cl,Br, I)

A comparative study of isomers and conformers of halogen nitrites, XONO (X?=?Cl, Br, I), with particular emphasis on the I derivatives, has been carried out using high levels of electronic structure theory. All isomeric and conformeric structures and cis- to trans- conformational barriers were determined for each family. The nitryl halide isomers, XNO₂, were calculated to be the lowest energy compounds. Interesting variations in the structural parameters, harmonic vibrational frequencies and stabilization energies were obtained on halogen substitution, that are particularly pronounced in the iodine family.     

Structural,Elastic, Electronic Properties and Interatomic Interactions in Metallic Tetraboride Series MB4 (M = Ru,Rh, Pd,Os, Ir,and Pt) Obtained from FLAPW–GGA Calculations

Physics of the Solid State - The report presents the results of systematic first-principle FLAPW–GGA calculations of a series of metallic tetraborides MB4 (where M = Ru, Rh, Pd, Os, Ir, and...     

Probing the structural,bonding, electronic and magnetic properties of transition–metal borazine systems: Co m (borazine) n (m = 1, 2; n = 1–3)

ABSTRACT

The geometrical structures of neutral and anionic Co _m (borazine) _n (m?=?1, 2; n?=?1–3) complexes have been determined by using density functional theory. The results indicate that most of the ground state structures for the complexes are similar to those of Co _m (benzene) _n , which might because borazine is isoelectronic and isostructural to benzene. The frontier molecular orbitals (FMOs) analyses show that their FMOs mainly arise from the 3d/4s electrons of cobalt atoms and the weak π-cloud of borazine molecule. Furthermore, the magnetic moments of complexes were studied and the results revealed that the Co atoms carry most of the magnetic moments. Comparing with the magnetic moment of a free Co atom (3.0μ_B), the magnetic moments of Co atom in most of Co _m (borazine) _n ^0/- complexes are significantly reduced and even quenched except that the Co(borazine) remains unchanged. More importantly, there is a transition FM-to-AFM between neutral and anionic Co₂(borazine)₂. Finally, natural population analyses were performed to insightfully explore the reliable electronic structure properties.     

Effect of A-site cation radius on thermodynamic properties of ARuO3 (A = Ca, Sr, and Ba)

The thermodynamic properties of alkaline earth ruthenate ARuO₃ (A?=?Ca, Sr, and Ba) perovskites have been investigated for the first time by means of a modified rigid ion model at temperature 1 K?≤?T?≤?300 K. As strong electron–phonon interactions are present in these compounds, the lattice contribution to the specific heat deserves proper attention. The values of specific heat calculated by us have shown remarkably good agreement with corresponding experimental data. We have found that in ARuO₃ (A?=?Ca, Sr, and Ba) ruthenate family, Debye temperature increases inversely with the ionic radius of the alkaline earth A cations. In addition, the results on the temperature dependence of thermal expansion coefficient (α), cohesive energy (?), molecular force constant (f), Reststrahlen frequency (υ), Debye temperature (θ _D), and Grüneisen parameter (γ) are also reported.     

Pressure-induced structural phase transition and electronic properties of RESb (RE = Ho,Er and Tm) compounds: ab initio calculations

The structural phase transition and electronic properties at ambient (B ₁-phase) and high pressure (B ₂-phase) of heavy rare earth monoantimonides (RESb; RE?=?Ho, Er, and Tm) have been studied theoretically using the self-consistent tight binding linear muffin tin orbital method. These compounds show metallic behavior under ambient condition and undergo a structural phase transition to the B ₂ phase at high pressure. We predict a structural phase transition from the B ₁ to B ₂ phase in the pressure range 30.0–35.0?GPa. Apart from this, the ground state properties, such as lattice parameter and bulk modulus are calculated and compared with the available theoretical and experimental results.     

Evolution of geometrical structures,stabilities and electronic properties of neutral and anionic Li n Cu λ (n = 1–9, λ = 0, −1) clusters: compare with pure lithium clusters

The structural evolution, stabilities, and electronic properties of copper-doped lithium Li _n Cu^λ (n?=?1–9, λ?=?0, ?1) clusters have been systematically investigated using a density functional method at PW91PW91 level. Extensive searches for ground-state structures were carried out, and the results showed the copper tends to occupy the most highly coordinated position and form the largest probable number of bonds with lithium atoms. By calculating the binding energies per atom, fragmentation energies and the HOMO-LOMO gaps, we found LiCu, Li₇Cu, LiCu^?, Li₂Cu^? and Li₈Cu^? clusters have the stronger relative stability and enhanced chemical stability. The content and pattern of frontier MOs for the most stable doped isomers were analysed to investigate the bond nature of interaction among Li and Cu atoms. The results show some σ-type and π-type bonds are formed among them, and with small admixture of the Cu d characters. To achieve a deep insight into the electron localization and reliable electronic structure information, the natural population analysis and electron localization function were performed and discussed.