A first principles study of structural and mechanical properties of Ti2AlZr intermetallic

The present work describes the structural and mechanical behaviour of three phases namely B2, D0₁₉ and O phases of Ti₂AlZr intermetallic using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The equilibrium lattice constant values of B2, D0₁₉ and O phases are in good agreement with the experimental and theoretical data, respectively. Formation energy of O phase is minimum followed by D0₁₉ and B2. Bonding characteristics of these phases have been explained based on electronic density of states and charge density. All the three phases satisfy the Born stability criteria in terms of elastic constants and are associated with ductile behaviour based on G/B ratios. The B2 phase exhibits very high anisotropy in comparison to those of the D0₁₉ and O.     

First-principles study of electronic structure and magnetic properties of orthorhombic CrGa2Sb2 and MnGa2Sb2

By the first-principles calculations, we present the results of electronic structure and magnetic properties on bulk CrGa₂Sb₂ and MnGa₂Sb₂ in an orthorhombic structure with the linear chains of transition-metal Cr and Mn atoms, using four different exchange correlation potentials: the local density approximation (LDA), the generalized gradient approximation (GGA), GGA + U, and the Tran-Blaha modified Becke-Johnson functional (mBJ). The electronic structure calculations from four exchange correlation potentials show that CrGa₂Sb₂ is a pseudogap (negative gap) material with very small density of states (DOS) at the Fermi level, while MnGa₂Sb₂ has notably higher DOS at the Fermi level compared to CrGa₂Sb₂, exhibiting stronger metallic conductivity, although the mBJ potential obtains lower DOS at the Fermi level than LDA and GGA for both CrGa₂Sb₂ and MnGa₂Sb₂. The GGA + U method with a small value (1 eV) of the on-site Coulomb interaction parameter U obtains lower DOS at the Fermi level compared to the large value of U. In agreement with the measurement data, the total energy calculations reveal that both CrGa₂Sb₂ and MnGa₂Sb₂ have a stable ferromagnetic ground state with lower energies relative to antiferromagnetic state. Based on the Heisenberg model, the magnetic exchange constants between the nearest-neighbor Cr–Cr and Mn–Mn along transition-metal linear chains are calculated to be 48.6 meV and 27.5 meV for CrGa₂Sb₂ and MnGa₂Sb₂, respectively. By the mean-field approximation method, we calculated the Curie temperature of two compounds to be above room-temperature.     

Effect of the tetragonal distortion on the electronic structure,phonons and superconductivity in the Mo3Sb7 superconductor

Effect of tetragonal distortion on the electronic structure, dynamical properties and superconductivity in Mo₃Sb₇ is analyzed using first principles electronic structure and phonon calculations. Rigid muffin tin approximation (RMTA) and McMillan formulas are used to calculate the electron–phonon coupling constant λ and superconducting critical temperature. Our results show, that tetragonal distortion has small, but beneficial effect on superconductivity, slightly increasing λ, and the conclusion that the electron–phonon mechanism is responsible for the superconductivity in Mo₃Sb₇ is supported. The spin-polarized calculations for the ordered (ferromagnetic or antiferromagnetic), as well as disordered (disordered local moment) magnetic states yielded non-magnetic ground state. We point out that due to its experimentally observed magnetic properties the tetragonal Mo₃Sb₇ might be treated as noncentrosymmetric superconductor, which could have influence for the pairing symmetry. In this context the relativistic band structure is calculated and spin–orbit interaction effects are discussed.     

Structural stability of some CsCl structure HfTM (TM = Co, Rh, Ru, Fe) compounds

In order to investigate Hf-TM (TM = Fe, Co, Rh, Ru) phase diagrams in the region of 50:50% atomic ratio, we performed ab initio Full-Potential Linearized Augmented Plane Waves calculations of the most stable Hf and TM elemental phases and HfTM compounds of the CsCl and CuAu structure types. The obtained electronic structures, cohesive energies and enthalpies of formation are discussed and compared to some of the existing models and available experimental data. The non-existing compound HfFe is found to be at least metastable, and the reason for its absence from the phase diagram is discussed.     

Competition of XA and L21B ordering in Heusler alloys Mn2CoZ (Z = Al,Ga, Si,Ge and Sb) and its influence on electronic structure

Competition between the highly-ordered XA structure and disordered L2₁B structure in Heusler alloys Mn₂CoZ (Z = Al, Ga, Si, Ge, Sb) has been investigated. The relative stability of the two structures strongly depends on the main group element Z. When Z belongs to Al or Ga, the XA structure is stabler, but when Z belongs to Si, Ge or Sb, the L2₁B structure gains stability and is lower in energy. This is related to the different number of valence electrons in main group element Z, which influences the DOS structure near the Fermi level and changes N(E_F). The energy difference ΔE between the XA and L2₁B structures may be used to estimate the tendency to form L2₁B structure in different Heusler alloys qualitatively. A large negative ΔE is preferable to retard the A-C site disorder and retain the highly-ordered XA structure. That is just the case in Mn₂CoAl. A robust half-metallicity is observed in Mn₂CoSi, Mn₂CoGe and Mn₂CoSb, they are always half-metallic under either XA or L2₁B structure. But in Mn₂CoAl and Mn₂CoGa, their spin gapless semiconducting character will be destroyed and replaced by a half-metallic state if L2₁B disorder occurs. Finally, these results suggest that the L2₁B structure should be considered together with XA structure when discussing the electronic structure of “inverse” Heusler alloys.     

Density functional study of the mechanical and phonon properties of Al12X (X = Mo,Tc, Ru,W, Re,and Os) compounds

By means of first principles calculations, we have studied the structural, elastic, and phonon properties of the Al₁₂X (X = Mo, Tc, Ru, W, Re, and Os) compounds in cubic structure. The elastic constants of these compounds are calculated, then bulk modulus, shear modulus, Young's modulus, Possion's ratio, Debye temperature, hardness, and anisotropy value of polycrystalline aggregates are derived and relevant mechanical properties are compared with the available theoretical ones. Furthermore, the phonon dispersion curves, mode Grüneisen parameters, and thermo-dynamical properties such as free energy, entropy and heat capacity are computed and the obtained results are discussed in detail.     

Lattice stability of Ca, Sr and Yb disilicides

In this paper a study of the lattice stability of Ca, Sr and Yb disilicides is reported. The structural stability of six different prototype lattices was investigated by means of density functional theory calculations and pseudopotentials within the generalized-gradient approximation using the VASP code. The high-pressure equilibria for the CaSi₂ and SrSi₂ have been described deriving the transition pressures, the structural properties, the bulk moduli and the heats of formation for the various polymorphs. Results are discussed together with the experimental literature. For the ytterbium disilicide a specific study of the Si vacancies in the hR3 ground state structure was carried out. Six different supercells derived from the primitive hexagonal cell were considered and full atomic and lattice relaxations were performed in order to predict the energetically most favorable structure. The formation of vacancies in the Si-sublattice is driven by the lowering of the density of states at the Fermi energy. A new mP22 lattice is proposed to describe the structure of the defective YbSi_2 − x phase: the resulting stoichiometry is Yb₄Si₇.     

Temperature-dependent mechanical properties of alpha-/beta-Nb5Si3 phases from first-principles calculations

The temperature-dependent structural properties and anisotropic thermal expansion coefficients of α-/β-Nb₅Si₃ phases have been determined by minimizing the non-equilibrium Gibbs free energy as functions of crystallographic deformations. The results indicate that the crystal anisotropy of α-Nb₅Si₃ phase is much more temperature dependence than that of β-Nb₅Si₃ phase. The total/partial density of states of α-/β-Nb₅Si₃ phases are discussed in detail to analyze their electronic hybridizations. It is demonstrated that the bonding of the two phases is mainly contributed from the hybridization between Nb-4d and Si-3p electronic states. The temperature-dependent mechanical properties of α-/β-Nb₅Si₃ phases are further investigated via the quasi-harmonic approximation method in coupling with continuum elasticity theory. The calculated single-crystalline and polycrystalline elasticity shows that both phases are mechanically stable and exhibit the intrinsic brittleness. The results also suggest that α-Nb₅Si₃ phase possesses a superior ability of compression resistance but an inferior ability of high-temperature resistance of mechanical properties than those of β-Nb₅Si₃ phase. The bonding features of α-/β-Nb₅Si₃ phases are discussed by means of charge density difference analysis in order to explain the difference of the temperature-dependent mechanical properties between the two phases.     

First principles study of electronic structure of CeNi4Cu

The results of the electronic structure investigation of CeNi₄Cu with the hexagonal CaCu₅-type structure have been presented. The results show domination of the 3d electronic states of Ni below the Fermi energy as well as the participation of 3d electronic states of Cu in the density of states in the energy region from −5 eV to −1 eV. The itinerant electrons of Ni and Cu are found to play a significant role in increase of the degree of hybridisation of Ce 4f with Ni 3d bands at the Fermi level. The hybridisation effects in valence band of CeNi₄Cu are discussed. The calculated value of electronic specific-heat coefficient does not suggest a heavy-fermion behaviour in the studied system.     

Half-metallic ferromagnetism in the RbX (X = Sb,Te) compounds with the rock salt and zinc-blende structures: A first-principles calculation

The first-principles density functional theory (DFT) calculations have been employed to investigate the electronic structures, magnetic properties and half-metallicity of the RbX (X = Sb, Te) compounds with the rocksalt and zinc-blende structures. The RbSb and RbTe compounds with both structures are half-metallic ferromagnet although these compounds do not include transition metal atoms. The compounds with the rock salt structure are found to be more stable energetically than the compounds with the zinc-blende structure. Magnetic moments, independent of crystal structure, are evaluated to be 2 μ_B/f.u. for RbSb and 1 μ_B/f.u. for RbTe. The half-metallic band gaps are 2.94 and 3.61 eV for the RbSb and RbTe compounds with the rock salt structure, respectively, while the RbSb and RbTe compounds with the zinc-blende structure have the half-metallic gaps of 3.00 and 3.25 eV, respectively. The lattice distortion does not affect the half-metallic properties of the RbX (X = Sb, Te) compounds with both structures.     

Structural,electronic, elastic,mechanical and thermal behavior of RESn3(RE = Y,La and Ce) compounds: A first principles study

The structural, electronic, elastic, mechanical and thermal properties of the isostructural and isoelectronic nonmagnetic RESn₃ (RE = Y, La and Ce) compounds, which crystallize in AuCu₃-type structure, are studied using first principles density functional theory based on full potential linearized augmented plane wave (FP-LAPW) method. The calculations are carried out within PBE-GGA, WC-GGA and PBE-sol GGA for the exchange correlation potential. Our calculated ground state properties such as lattice constant (a₀), bulk modulus (B) and its pressure derivative (B′) are in good agreement with the experimental and other available theoretical results. We first time predict the elastic constants for these compounds using different approximations of GGA. All these RESn₃ compounds are found to be ductile in nature in accordance with Pugh's criteria. The computed electronic band structures and density of states show metallic character of these compounds. The elastic properties including Poisson's ratio (σ), Young's modulus (E), shear modulus (G_H) and anisotropy factor (A) are also determined using the Voigt–Reuss–Hill (VRH) averaging scheme. The average sound velocities (v_m), density (ρ) and Debye temperature (θ_D) of these RESn₃ compounds are also estimated from the elastic constants. We first time report the variation of elastic constants, elastic moduli, Cauchy's pressure, sound velocities and Debye temperatures of these compounds as a function of pressure.     

Electronic and magnetic structures and bonding properties of Ce2T2X (T = nd element; X = Mg,Cd, Pb or Sn) intermetallics from first principles

The electronic structure and chemical bonding properties of four families of Ce₂T₂X (T = nd element; X = Mg, Cd, Pb or Sn) intermetallics crystallizing in an ordered U₃Si₂ type structure are shown from density functional theory (DFT) calculations to present electronic and magnetic structure properties arising from their peculiar valence electron count (VEC). Trends of the magnetism are discussed in terms of the characteristics of the Ce(4f) states as well as the energetic position of the transition metal element d states.     

First-principle calculations of the electronic,elastic and thermoelectric properties of Ag doped CuGaTe2

To improve the performance of a thermoelectric material CuGaTe₂, element Ag is doped to replace element Ga and we investigate the electronic structure, phase stability, elastic and thermoelectric properties of CuGa_1−xAg_xTe₂ (x = 0, 0.25 and 0.5) via first-principles method. The phase stability of CuGa_1−xAg_xTe₂ is discussed by analyzing the formation energy, cohesive energy and elastic constants. The calculated sound velocities decrease with the increase of Ag content, which is favorable for reducing the lattice thermal conductivity. The analysis of band structures shows that the replacement of Ga by Ag makes CuGaTe₂ undergo a direct-indirect semiconductor transition. The Ag doping induces steep density of states in valence band edge, which is beneficial for increasing the carrier concentration and improving thermoelectric performance of CuGaTe₂.     

Structural and magnetic properties of Ni2CoSi: First-principles calculation and experimental realization

BCC Heusler phase Ni₂CoSi has been predicted to be a promising candidate to realize magnetic field induced martensitic transformation. We tried to prepare Ni₂CoSi single phase using different methods. Single phase Ni₂CoSi cannot be synthesized by arc-melting and annealing. Then we used mechanical alloying method to synthesize Ni₂CoSi. But a FCC phase rather than BCC was obtained after ball-milling. The lattice constant of FCC Ni₂CoSi is 3.52 Å and the Curie temperature is around 900 K. The saturation magnetization at 5 K is 2.44μ_B/f.u. This FCC phase is stable and no transition is observed when heating to 1173 K. The electronic structure and phase stability of the FCC and BCC Heusler phase have been investigated by first-principles calculations. The FCC Ni₂CoSi has lower total energy compared with BCC, agreeing with the experimental observation. But the calculated total moment is much smaller than the M_s at 5 K. This difference is related to the atomic disorder and was discussed by KKR-CPA calculation.     

Electronic structure of non-centrosymmetric superconductor LaPdSi3 and its reference compound LaPdGe3

Electronic structures of a superconductor without inversion symmetry, LaPdSi₃, and its non-superconducting counterpart, LaPdGe₃, have been calculated employing the full-potential local-orbital method within the density functional theory. The investigations were focused on analyses of densities of states at the Fermi level in comparison with previous experimental heat capacity data and an influence of the antisymmetric spin–orbit coupling on the band structures and Fermi surfaces (FSs) being very similar for both considered here compounds. Their FSs sheets originate from four bands and have a holelike character, but exhibiting pronounced nesting features only for superconducting LaPdSi₃. It may explain a relatively strong electron–phonon coupling in the latter system and its lack in non-superconducting LaPdGe₃.     

第一性原理研究Al-Y合金在压力作用下的晶胞结构、力学性质、热力学性质和电子结构

The influence of structural, elastic properties, thermodynamics and electronic properties Al-Y alloy were investigated by using first-principles. The equilibrium lattice constant, elastic constants, and elastic modulus as calculated here agree with results of previous studies. Calculated results of bulk modulus B, shear modulus G, Young’s modulus E, Poisson’s ratio v and Debye temperature all increase as pressure increase, but the opposite is true for heat capacity cp. In addition, the Debye temperature for the phases reduces gradually as follows: Al2Y > Al3Y> AlY. Additionally, the G/B ratio indicates that AlY and Al3Y are ductile materials, while Al2Y is a brittle material, and that the ductility of AlY and Al3Y can be improved with increased pressure, while the brittleness of Al2Y does not improve with increased pressure. Finally, the paper presents and discusses calculations of density of states and charge populations as they are affected by pressure.     

The structural,elastic, electronic and thermodynamic properties of hexagonal η-Cu6−xNixSn5 (x = 0, 0.5, 1, 1.5 and 2) intermetallic compounds

Based on first-principles calculations, the effects of various Ni concentrations on the structural, elastic, electronic and thermodynamic properties of hexagonal η-Cu₆Sn₅ compound have been systematically investigated. The results demonstrate that higher Ni concentration in the η-Cu_6−xNi_xSn₅ (x = 0, 0.5, 1, 1.5 and 2) leads to thermodynamically stable compounds, and Ni atoms preferentially occupy Cu₂ + Cu_1c sites forming the η-Cu₄Ni₂Sn₅ compound. It is also found that the unit cell volume and lattice parameter of the ‘a’ axis decrease with increasing Ni concentration, which are consistent with the other experimental results. Furthermore, the polycrystalline elastic properties are obtained from single-crystal elastic constants. Our results indicate that the addition of Ni enhances the mechanical stability, brittleness, modulus and Debye temperatures of η-Cu₆Sn₅ compound. Analyzing the electronic structure and charge density distribution provides the explanation that Ni develops distinct bonding energy to Cu and Sn in the structure.     

Electronic and transport properties of Mg2Si under isotropic strains

Density functional theory and Boltzmann theory calculations of the electronic and thermoelectric properties of Mg₂Si subjected to isotropic strains have been performed. The electrical conductivity, the Seebeck coefficient and the power factor have been evaluated at two temperatures (300 K and 900 K) and two charge carrier concentrations (10¹⁸ cm⁻³ and 1.2 × 10²⁰ cm⁻³ electrons and holes). Up to 3% of both compressive and tensile strains have been applied to the material. From our results, we can highlight that a significant improvement of both the Seebeck coefficient (S) and the power factor (PF) is obtained at low temperature and moderate n-doping. The increase in S and PF amounts to 40% and 100%, respectively, compared to the unstrained Mg₂Si.     

Coexistence of localized magnetism and itinerant ferromagnetism in a Gd5Y2Pd3 single crystal

Experimental results of the single-crystal X-ray diffraction, XPS, ac-magnetic susceptibility (ac-χ), dc-magnetization M(T), and electrical resistivity (ρ) measurements for the hexagonal Th₇Fe₃-type Gd₅Y₂Pd₃ single crystal are presented. Anomalies in (ac-χ), (T) and M(T)-curves have allowed to establish that Gd₅Y₂Pd₃ undergoes a long-range ferromagnetic-type ordering at T_C = 263 K, followed by a spin-reorientation below 190 K. The magnetization data indicate that there is an excess of the magnetic moment for the Gd³⁺ ions. The observed XPS, magnetic and electrical resistivity behaviour points to the coexistence of localized magnetism from the magnetic Gd³⁺ ions and itinerant ferromagnetism from 4d- and 5d-electron bands. We discuss the magnetic behaviour of the Gd_7−xY_xPd₃ solid solutions in terms of three competitive mechanisms: RKKY-interaction, magnetic frustration and spin-fluctuation.