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.     

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.     

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.     

Theoretical investigations of structural, elastic and thermodynamic properties for PtN2 under high pressure

We have investigated structural and elastic properties of PtN₂ under high pressures using norm-conserving pseudopotentials within the local density approximation (LDA) in the frame of density-functional theory. Calculated results of PtN₂ are in agreement with experimental and available theoretical values. The a/a₀, V/V₀, ductility/brittleness, elastic constants C_ij, shear modulus C′, bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio σ and anisotropy factor A as a function of applied pressure are presented. Through the quasi-harmonic Debye model, we also study thermodynamic properties of PtN₂. The thermal expansion versus temperature and pressure, thermodynamic parameters X (X=Debye temperature or specific heat) with varying pressure P, and heat capacity of PtN₂ at various pressures and temperatures are estimated.     

P-V relation for cuprous halides: Pseudopotential approach

Cuprous halides are found to show significantly different behaviour from that of alkali halides. This difference is mainly due to the presence of outermost d-electrons present in Cu⁺ ion. In the present paper, the ab initio pseudopotential formalism incorporating the effect of d-electrons is used to generate the equation of state (EOS) for group I-VII binary compounds from first-principles calculations. The expression for the EOS is derived for the first time within the pseudopotential framework. The computed isothermal compression curves for cuprous halides are compared with compression curves from other EOSs belonging to different classes and categories and have also been tested for the prediction of end point.     

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.     

Observation of chemical reactions between alkaline-earth oxides and tungsten at high pressure and high temperature

The potential chemical reactions of alkaline-earth oxides (AeO with Ae: Mg, Ca, Sr, and Ba) and tungsten are studied at high pressure and high temperature. At pressures ranging from 5 to 10 GPa and temperatures of 2000 K, a noticeable reaction between AeO and powder tungsten (W) was detected. As a product of the reaction, scheelite-structured orthotungstates (AeWO₄) were formed. The reactivity of alkaline-earth oxides with tungsten increases in the order Ca<Sr<Ba, being the reaction not detected for MgO. Possible chemical reactions leading to the formation of alkaline-earth orthotungstates have been considered. Our results support the conclusion that the most probable reaction occurring under high-pressure and high-temperature conditions is AeO+W+3/2 O₂→AeWO₄.     

Two-stage amorphization of scandium molybdate at high pressure

Using Raman spectroscopy and X-ray diffraction we find that at high pressure amorphization of scandium molybdate occurs in two stages. Excessive broadening of molybdate internal modes arising from distortion and disordering of MoO₄ tetrahedra, together with rapid weakening of diffraction from large d-spacings and disappearance of diffraction from small d-spacings suggest gross molybdate ion disorder above 4 GPa. On the other hand, complete amorphization occurs at the significantly higher pressure of 12 GPa, where diffraction disappears completely. The amorphization is also found to be irreversible.     

Influence of high pressure on the ferromagnetic transition temperature of CrO2

The shift of the Curie temperature of CrO₂ with pressure was determined by ac-susceptibility measurements under hydrostatic pressure up to 5 GPa. These experiments show that ferromagnetism of CrO₂ is suppressed at a rate , which is close to recent theoretical estimates.     

Acoustic behaviour of high pressure air-filled porous media

This paper deals with the acoustic behaviour of porous media when the saturating fluid is high pressured. These observations are performed by ultrasonic transmission through a porous sample with variations of the static pressure of the saturating fluid. Previous works have experimentally demonstrated that a high frequency asymptotic equivalent fluid model allows to model the behaviour of such media for low pressure (between 0.2 and 6 bars). In this paper, in order to characterize high damping materials, measurements are performed for higher static pressure (up to 18 bars). It is shown that the behaviour of transmission coefficient and speed with pressure follows Biot’s theory. Moreover, measurements are dependant on temperature variations. Temperature variations have been accounted for in this study, but this does not explain entirely the high sensitivity of the transmission coefficient with static pressure. It remains that the mechanical properties of the porous medium vary strongly with the thermodynamic variables.     

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.     

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.     

Heat capacity of ZnO with cubic structure at high temperatures

The heat capacities at constant pressure and constant volume, and thermal expansivity are calculated for ZnO with rocksalt-type and zinc-blende-type cubic structures over a wide range of temperatures using molecular dynamics simulations with interactions due to effective pair-wise potentials which consist of the Coulomb, dispersion, and repulsion interaction. It is shown that the calculated structural and thermodynamic parameters including lattice constant, thermal-expansion coefficient, isothermal bulk modulus and its pressure derivative at ambient condition are in good agreement with the available experimental data and the latest theoretical results. At extended pressure and temperature ranges, lattice constant and heat capacity have also been predicted. The structural and thermodynamic properties of ZnO with cubic structure are summarized in the 300-1500 K temperature ranges and up to 100 kbar pressure.     

Crystallization of mechanically alloyed amorphous W-Mg alloy under high pressure

Pure metal powder mixtures of W and Mg at the desired composition were milled in conventional high-energy ball mill, and amorphous alloy W₅₀Mg₅₀ was obtained after milling for 20 h. The structure evolution of elemental powder mixtures was studied following milling and subsequent high pressure and high temperature treatment. The amorphous alloy transform into a nanocrystalline material below 1050 °C at 4.0 GPa. On increasing the temperature, it transforms into a mixture of several new crystal phases under high-pressure condition. It also found that both mechanical alloying and high pressure treatment are the two necessary processes to form the nanocrystalline and the new phases.     

Schottky barrier properties of various metal (Zr, Ti, Cr, Pt) contact on p-GaN revealed from I-V-T measurement

Schottky barrier contact using three different metal (Zr, Ti, Cr and Pt) and Ohmic contact using Ni were made on same epitaxial growth layer of p-GaN. Measurements were carried out using current-voltage-temperature (I-V-T) in the range of 27-100°C. Under forward bias and room-temperature (RT), the ideality factors (η) were determined to be 2.38, 1.82, 1.51 and 2.63, respectively, for Zr, Ti, Cr and Pt. The Schottky barrier height (SBH) and effective Richardson coefficient A^** were measured through modified Norde plot as one of the analysis tools. Barrier heights of 0.84, 0.82, 0.77 and 0.41 eV for Zr, Ti, Cr and Pt, respectively, were obtained from the modified Norde plot. Schottky barrier heights of Zr, Ti, or Cr/p-GaN were also measured through activation energy plot, and determined to be in the same range (∼0.87 eV) and Pt at 0.49 eV. These results indicate that the Fermi level seems to be pinned due to the value of slope parameter (S) was very low (S = −0.25).     

New features in the pressure dependence of photoluminescence spectra of C60 at room temperature

We present new results on the pressure dependence of the electronic band gap of molecular C₆₀ measured by photoluminescence spectroscopy up to 10 GPa at room temperature. In agreement with previous results, the energy gap decreases with increasing pressure up to about 6 GPa. For higher pressures, however, we observe an energy gap that is wider than that at 6 GPa.     

Properties of C60 polymerized under high pressure and temperature

60 polymers. Pure and mixed phase polymeric samples were synthesized by simultaneously subjecting microcrystalline C₆₀ powder or pellets to various pressures () and temperatures (). The optical spectra of the orthorhombic, tetragonal, and rhombohedral C₆₀ polymer phases are observed to be quite distinct and rich. These spectra exhibit numerous lines and an overall downshift in frequency relative to C₆₀ is observed, consistent with a loss of double bonds from the fullerene cage. The LDMS spectra of a sample synthesized at under hydrostatic conditions and , exhibited a succession of clear peaks at mass numbers corresponding to , similar to the LDMS data on the C₆₀ photopolymer. This is taken as further evidence for interfullerene bonds in these high-pressure polymers. The XRD pattern of this sample indicates the presence of a strong texture in the sample. Received: 14 November 1996/Accepted: 8 January 1997     

Analysis of P-V-T relationships and thermodynamic properties for some alkali halides

In this paper, Pandey approximation for the volume dependence of Anderson-Grüneisen parameter at fixed pressure, Anderson approximation for the temperature dependence of thermal expansivity, the equations of thermal expansivity along isobars derived by Shanker et al., and the presented approximation for the volume dependence of Anderson-Grüneisen parameter along isobars, have been used to study and predict the pressure-volume-temperature (P-V-T) data and the variations of the volume expansion coefficient and isothermal bulk modulus with temperature and pressure for NaCl, CsCl, LiF, NaF crystals, up to 30 GPa and in the temperature range 298-1073 K. The calculated values are compared with each other. It is found that these equations-of-state are valid and present good agreement with the available experimental data.     

On the phase-transition in anthracene induced by high pressure

The crystallographic structure of anthracene is studied under high pressure up to 27 GPa using diamond anvil cells. Different pressure-transmitting media (helium, a methanol-ethanol mixture, a normal- and iso-pentane mixture and no medium) were used up to specific critical pressures where the hydrostatic conditions are lost. It is clearly observed that the loss of hydrostaticity is associated with a crystallographic phase-transition in anthracene. The phase-transition is observed as reversible, and it is accompanied by a large hysteresis. These observations clarify conflicting reports in the literature on the high-pressure phase-transition of anthracene.