Ab initio calculations of elastic constants and thermodynamic properties of Li2O for high temperatures and pressures

The elastic constants and thermodynamic properties of Li₂O for high temperatures and pressures are calculated by the ab initio unrestricted Hartree-Fock (HF) linear combination of atomic orbital (LCAO) periodic approach. The lattice constant, elastic constants, Debye temperature, and thermal expansion coefficient obtained are in good agreement with the available experimental data and other theoretical results. It is found that at zero pressure the elastic constants C₁₁, C₁₂ and C₄₄, bulk modulus B and Debye temperature Θ_D decrease monotonically over the wide range of temperatures from 0 to 1100 K. When the temperature , C₁₂ approaches zero, consistently with the transition temperature 1200 K. However, with increasing pressure, they all increase monotonically and the anisotropy will weaken.     

Elasticity and thermodynamic properties of RuB2 under pressure

First-principles calculations of the crystal structure and the elastic properties of RuB₂ have been carried out with the plane-wave pseudopotential density functional theory method. The calculated values are in very good agreement with experimental data as well as with some of the existing model calculations. The elastic constants c_ij, the aggregate elastic moduli (B, G, E), Poisson's ratio, and the elastic anisotropy with pressure have been investigated. Through the quasi-harmonic Debye model considering the phonon effects, the isothermal bulk modulus, the thermal expansions, Grüneisen parameters, and Debye temperatures depending on the temperature and pressure are obtained in the whole pressure range from 0 to 60 GPa and temperature range from 0 to 1100 K as well as compared to available data.     

Simulated equation of state of CaF2 with fluorite-type structure at high temperature and high pressure

The pressure-volume-temperature (P-V-T) equation of state (EOS), isothermal bulk modulus, and thermal expansivity of CaF₂ with cubic fluorite-type structure are investigated using the constant temperature and pressure shell model molecular dynamics (MD) method with effective pair potentials which consist of the Coulomb, dispersion, and repulsion interaction. It was shown that MD simulation is very successful in accurately reproducing the measured volumes of the CaF₂ over a wide range of pressures. The simulated P-V data matched X-ray diffraction experimental results up to 9.5 GPa at 300 K. In addition, volume thermal-expansion coefficient and isothermal bulk modulus were also calculated and compared with available experimental data and the latest theoretical results at ambient condition. At extended temperature and pressure ranges, The P-V EOS under different isotherms at selected temperatures, T-V EOS under different isobars at selected pressures, thermal expansivity, and isothermal bulk modulus were predicted up to 1500 K and 10 GPa. The detailed knowledge of thermodynamic behavior and EOS at extreme conditions are of fundamental importance to the understanding of the physical properties of CaF₂.     

First-principles study of the structural and thermodynamic properties of AsNMg3 antiperovskite

The structural and elastic properties of the antiperovskite semiconductor AsNMg₃ are investigated using the full-potential linearized augmented plane wave plus local orbital (FP-LAPW+lo) method within the generalized gradient in the frame of the density functional theory. The ground state properties such as lattice constant, bulk modulus, pressure derivative of the bulk modulus and elastic constants are in good agreement with numerous experimental and theoretical data. Through the quasi-harmonic Debye model, in which the phononic effects are considered, we have obtained successfully the thermodynamic properties such as the thermal expansion coefficient, Debye temperature and specific heats in the whole pressure range from 0 to 30 GPa and temperature range from 0 to 1200 K.     

Comparative investigations of the P-V-T relationship of NaCl at high pressure and temperature

Two different potential models of molecular dynamics (MD) simulations have been applied to investigate the pressure-volume-temperature (P-V-T) relationship and lattice parameter of NaCl under high pressure and temperature. The first one is the shell model (SM) potentials in which due to the short-range interaction pairs of ions are moved together as is the case in polarization of a crystal due to the motion of the positive and negative ions, and the second one is the two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials with full treatment of long-range Coulomb forces. The P-V relationship at 300 K, T-V relationship at zero pressure, and lattice parameter a, have been obtained and compared with the available experimental data and other theoretical results. Compared with SM potentials, the MD simulation with BMHFT potentials is very successful in reproducing accurately the measured volumes of NaCl. At an extended pressure and temperature ranges, P-V relationship under different isotherms at selected temperatures, T-V relationship under different pressures, and lattice parameter a have also been predicted. The properties of NaCl are summarized in the pressure range 0-30 GPa and the temperature up to 2000 K.     

Structural and thermodynamic properties of the cubic perovskite BiAlO3

The structural and elastic properties of the cubic perovskite-type BiAlO₃ are studied using the pseudopotential plane wave method within the local density approximation. The calculated structural parameters are in good agreement with previous calculations. The elastic constants are calculated using the static finite strain technique. Thermal effects on some macroscopic properties of BiAlO₃ are predicted using the quasi-harmonic Debye model, in which the lattice vibrations are taken in account. We have obtained successfully the variations of the lattice constant, volume expansion coefficient, heat capacities and Debye temperature with pressure and temperature in the ranges of 0-30 GPa and 0-1000 K.     

Molecular dynamics simulation of thermodynamic properties of NaCl at high pressures and temperatures

The expansivity, constant-pressure heat capacity, and isothermal bulk modulus of sodium chloride (NaCl) have been obtained by using molecular dynamics method. The calculated thermodynamic parameters are found to be in agreement with the available experimental data. At an extended temperature and pressure ranges, these parameters have also been predicted. The thermodynamic properties of NaCl are summarized in the pressure 0-500 kbar ranges and the temperature up to 1000 K.     

Structural and elastic properties under pressure effect of the cubic antiperovskite compounds ANCa3 (A = P, As, Sb, and Bi)

Using first-principles density functional calculations, the effect of high pressures, up to 40 GPa, on the structural and elastic properties of ANCa₃, with A = P, As, Sb, and Bi, were studied by means of the pseudo-potential plane-waves method. Calculations were performed within the local density approximation and the generalized gradient approximation for exchange-correlation effects. The lattice constants are in good agreement with the available results. The elastic constants and their pressure dependence are calculated using the static finite strain technique. We derived the bulk and shear moduli, Young's modulus, Poisson's ratio and Lamé's constants for ideal polycrystalline ANCa₃ aggregates. By analysing the ratio between the bulk and shear moduli, we conclude that ANCa₃ compounds are brittle in nature. We estimated the Debye temperature of ANCa₃ from the average sound velocity. This is the first quantitative theoretical prediction of the elastic properties of PNCa₃, AsNCa₃, SbNCa₃, and BiNCa₃ compounds, and it still awaits experimental confirmation.     

Molecular dynamics simulation of P-V-T relationship of ZnO with rock-salt structure using pair-wise interactions

Molecular dynamics (MD) method is used to investigate the behavior of the pressure-volume-temperature (P-V-T) relationship, lattice constant and thermal expansivity for ZnO with rock-salt structure at high pressures and temperatures. The interionic potential is taken to be the sum of pair-wise additive Coulomb, van der Waals attraction, and repulsive interactions. The isothermal and isobaric properties are discussed from the corresponding P-V-T relationship, and it is shown that the MD simulation is successful in reproducing the measured volumes of ZnO over a wide range of temperature and pressure. Meanwhile, the equations of state parameters including lattice constant, linear thermal expansion coefficient, and isothermal bulk modulus are calculated and compared with the available experimental data and the latest theoretical results. At an extended pressure and temperature range, P-V-T relationship, lattice constant, and linear thermal expansion coefficient have been predicted. The structural and thermodynamic properties of ZnO with rock-salt structure are summarized in the pressure 0-100 GPa ranges and the temperature up to 3100 K.     

Prediction study of structural and elastic properties under pressure effect of M2SnC (M=Ti, Zr, Nb, Hf)

Using first-principles calculations, we have studied the structural and elastic properties of M₂SnC, with M=Ti, Zr, Nb and Hf. Geometrical optimization of the unit cell is in good agreement with the available experimental data. The effect of high pressures, up to 20 GPa, on the lattice constants shows that the contractions along the a-axis were higher than those along the c-axis. We have observed a quadratic dependence of the lattice parameters versus the applied pressure. The elastic constants and their pressure dependence are calculated using the static finite strain technique. A linear dependence of the elastic stiffnesses on the pressure is found. We derived the bulk and shear moduli, Young's moduli and Poisson's ratio for ideal polycrystalline M₂SnC aggregates. We estimated the Debye temperature of M₂SnC from the average sound velocity. This is the first quantitative theoretical prediction of the elastic properties of Ti₂SnC, Zr₂SnC, Nb₂SnC, and Hf₂SnC compounds.     

High pressure X-ray diffraction study of Fe2B

We report the results of a synchrotron based X-ray diffraction study of bct-Fe₂B under quasi-hydrostatic conditions from 0 to 50 GPa. Over this pressure range, no phase change or disproportionation has been observed. A weighted fit of the data to the Birch-Murnaghan equation of state yields a value of the bulk modulus, K, of 164±14 GPa and the first pressure derivative of the bulk modulus, K′, of 4.4±0.5. The compression is found to be anisotropic, with the a-axis being more incompressible than the c-axis.     

Strength of magnesium oxide under high pressure: evidence for the grain-size dependence

X-ray diffraction patterns from magnesium oxide compressed in a diamond anvil cell up to 55 GPa have been recorded and the differential stress (a measure of compressive strength) and grain-size (crystallite size) determined as a function of pressure from the line-width analysis. The strength agrees well with the uniaxial stress component (another measure of compressive strength) derived earlier from the line-shift data. The strength increases while the crystallite size decreases steeply as the pressure is raised from ambient to ∼10 GPa. The increase in strength is much smaller at higher pressures. The strength-pressure data are explained by combining the grain-size dependence of strength and the shear-modulus scaling law. The dependence of strength on grain-size has not been considered in the past in the discussion of high-pressure strength data.     

Pressure dependence of elastic constants in zinc-blende GaN and InN and their influence on the pressure coefficients of the light emission in cubic InGaN/GaN quantum wells

We have studied the influence of nonlinear elastic effects on the pressure coefficients of light emission, dE_E/dP, in cubic InGaN/GaN quantum wells. By means of ab-initio calculations, we have determined the pressure dependences of the elastic constants, C₁₁, C₁₂ and C₄₄ in zinc-blende InN and GaN. Further, we show that the pressure dependence of the elastic constants results in significant reduction of dE_E/dP in cubic InGaN/GaN quantum wells and essentially improves the agreement between experimental and theoretical values.     

Magnetic properties,electronic structure,and optical properties of the filled skutterudite BaFe4Sb12

The magnetic properties, electronic structure, and optical properties of the filled skutterudite BaFe₄Sb₁₂ are calculated by the first-principles full-potential linearized augmented plane wave (FPLAPW) plus local orbital method. It is found that the local spin density approximation (LSDA) method appears more accurate than the generalized gradient approximation (GGA) method in calculating the electronic structures and optical properties of this compound. Furthermore, our calculated lattice constant and spin magnetic moments with the LSDA method are in overall better agreement with experiment. In contrast with recent experiment, our calculations are in good agreement with experimental reflectivity spectra and optical conductivity spectrum.     

Energetics and electronic properties of Mg7TMH16 (TM=Sc, Ti, V, Y, Zr, Nb): An ab initio study

First-principles calculations have been performed on the face-centered cubic (FCC) magnesium-transition metal (TM) hydrides Mg₇TMH₁₆ (TM=Sc, Ti, V, Y, Zr, Nb). The cohesive energies are calculated to analyze the stability, and the obtained enthalpies of formation for hydrides Mg₇TMH₁₆ have been used to investigate the possible pathways of formation reaction. The calculated enthalpy changes show that the decomposition temperatures of Mg₇TMH₁₆ are lower than that of MgH₂. The electronic densities of states reveal that all the hydrides studied here exhibit metallic characteristics. The bonding nature of Mg₇TMH₁₆ is investigated, showing stronger covalent bonding between TM and H than between Mg and H.     

Electronic structure,chemical bonding and elastic properties of the first thorium‐containing nitride perovskite TaThN3

The full‐potential linearized augmented plane wave method with the generalized gradient approximation for the exchange and correlation potential (LAPW‐GGA) is used to understand the electronic and elastic properties of the first thorium‐containing nitride perovskite TaThN₃. Total and partial density of states, charge distributions as well as the elastic constants, bulk modulus, compressibility, shear modulus, Young modulus and Poisson ratio are obtained for the first time and analyzed in comparison with cubic ThN. The chemical bonding in TaThN₃ is a combination of ionic Th–N and of mixed covalent–ionic Ta–N bonds. The cubic TaThN₃ is semiconducting with the direct gap at about 0.65 eV. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synchrotron X-ray diffraction and absorption studies of CeM2X2 (M=Cu, Ni and X=Si, Ge) at high pressure

The equations of state of CeCu₂Si₂ and CeCu₂Ge₂ to about 60 GPa, as well as that of CeNi₂Ge₂ to 22 GPa and the valence state of Ce in CeCu₂Ge₂ to 20 GPa have been studied at room temperature in a diamond-anvil cell using synchrotron radiation sources. In each compound, the ambient-pressure phase (tetragonal ThCr₂Si₂-type structure) persisted to the highest pressure studied. The unit cell volumes of CeNi₂Ge₂ at ∼5 GPa and CeCu₂Ge₂ at ∼7 GPa, respectively, approached that of CeCu₂Si₂ taken at ambient pressure. From the equation-of-state data, the bulk modulus was derived to be 112.0±5.1 GPa for CeCu₂Si₂, 125.6±4.3 GPa for CeCu₂Ge₂, and 178.4±14.3 GPa for CeNi₂Ge₂. The valence state of Ce in CeCu₂Ge₂ remained trivalent throughout the pressure range investigated.     

Some properties of the phonon spectra of transition metal disilicides VSi2, NbSi2, and TaSi2

The phonon spectra of metallic disilicides VSi₂, NbSi₂, and TaSi₂ have been studied in detail by inelastic neutron scattering at 300 K and specific heat measurements between 10 K and 250 K. The specific heat calculated from the generalised phonon density of states extracted from neutron measurements is in good agreement with the measured lattice contribution to the specific heat. The properties of the phonon spectra are discussed in relation with other data reported for these isostructural and isoelectronic disilicides.     

Equation of state of cubic hafnium(IV) nitride having Th3P4 -type structure

Pressure dependence of the specific volume, V(P), of the recently discovered high-pressure compound Hf₃N₄ having cubic Th₃P₄-type structure (c- Hf₃N₄) has been measured at room temperature up to 43.9 GPa in a diamond anvil cell using energy-dispersive X-ray powder diffraction combined with synchrotron radiation. A least-square fit of the Birch-Murnaghan equation of state to the experimental V(P)-data yielded for c- Hf₃N₄ the bulk modulus of and its first pressure derivative of . For fixed at 4 the bulk modulus of c- Hf₃N₄ was determined to be . The obtained B₀-value is only insignificantly below that estimated in preliminary measurements. Existing theoretical predictions for B₀ scatter around the present experimental data. The observation of a high bulk modulus of c- Hf₃N₄ supports the suggestion that this compound could have high hardness.     

Theoretical investigations on ZnCdO2 and ZnMgO2 alloys: A first principle study

We report on the calculations related to the electronic structure of ZnO, CdO, MgO, ZnMgO₂ and ZnCdO₂ in the wurtzite, rocksalt and chalcopyrite structures. From this study we found that ZnO and MgO are of direct band semiconductor, CdO is of semi metallic in nature. ZnMgO₂ and ZnCdO₂ are direct band semiconductors. From the energy considerations, we found that ZnMgO₂ and ZnCdO₂ are more stable in chalcopyrite structure rather than in rocksalt structure. Using the calculated band gap values, the bowing parameter for ZnMgO₂ and ZnCdO₂ is deduced and found to be in agreement with the reported value.