Non-linear pressure dependence of phonon frequencies in RbI

The frequencies of a representative sample of phonons with negative Grueneisen parameters, in RbI, were measured at several pressures up to, and slightly above, the thermodynamic equilibrium pressure between the NaCl and CsCl structure phases (3.56 kbar). In general the frequency-pressure curves are linear up to about 3 kbar but show a tendency to saturate around 3.5 kbar.     

New states in SmS ?

Quasihydrostatic pressure resistivity experiments on a single crystal of SmS are reported up to 27.5 kbar. At low temperature, a regime change occurs at P ～ 20 kbar, between a “quasiinsulating” behavior (P < 20 kbar) and a metallic ground state (P 20 kbar). Striking similarities appear with TmSe and TmS cases.     

Use of smoke samples in diamond-anvil cells to measure pressure dependence of optical spectra: Application to the ZnO exciton

We present measurements of ZnO exciton peak energies, E₀, at pressures up to 107.3 kbar. Smoke samples consisting of randomly oriented single crystal particles were prepared by oxidizing metallic zinc in air and were collected on one diamond face of a Merrill-Bassett pressure cell. Pressures were measured by the ruby fluorescence technique. In the pressure range between 5 and 90 kbar, our results indicate a consistent linear dependence with dE₀/dP = 2.33 × 10^?3 eV kbar^?1 for both increasing and decreasing pressures. A mixed phase structure is suggested by the observed irregular peak shapes and measured pressure dependence for the sample that had been taken beyond ? 90 kbar where the transformation to the NaCl structure has been reported.     

High temperature equation of state of metallic hydrogen

The equation of state of liquid metallic hydrogen is solved numerically. Investigations are carried out at temperatures from 3000 to 20 000 K and densities from 0.2 to 3 mol/cm³, which correspond both to the experimental conditions under which metallic hydrogen is produced on earth and the conditions in the cores of giant planets of the solar system such as Jupiter and Saturn. It is assumed that hydrogen is in an atomic state and all its electrons are collectivized. Perturbation theory in the electron-proton interaction is applied to determine the thermodynamic potentials of metallic hydrogen. The electron subsystem is considered in the randomphase approximation with regard to the exchange interaction and the correlation of electrons in the local-field approximation. The proton-proton interaction is taken into account in the hard-spheres approximation. The thermodynamic characteristics of metallic hydrogen are calculated with regard to the zero-, second-, and third-order perturbation theory terms. The third-order term proves to be rather essential at moderately high temperatures and densities, although it is much smaller than the second-order term. The thermodynamic potentials of metallic hydrogen are monotonically increasing functions of density and temperature. The values of pressure for the temperatures and pressures that are characteristic of the conditions under which metallic hydrogen is produced on earth coincide with the corresponding values reported by the discoverers of metallic hydrogen to a high degree of accuracy. The temperature and density ranges are found in which there exists a liquid phase of metallic hydrogen.     

Pressure effect on the resistance of InS

The effect of pressure on the resistance of InS was studied to pressure higher than to 150 kbar for single crystal and to ca. 300 kbar for powdered samples. The resistance exhibits a sharp maximum at 47 kbar, which is explainable by the change of band structure due to pressure increase. Under higher pressure, the resistance decreased gradually with increasing pressure. A marked change in slope, however, was observed at 108 kbar, suggesting a phase transition possibly to a metallic phase.     

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.     

Equation of state of sodium chloride up to 32 kbar and 500°C2

The length change of a 25mm long single crystal of NaCl has been determined as a function of hydrostatic pressure up to 32 kbar and temperatures up to 500°C using an electrical contact piezometer with tungsten carbide as a standard. The measurements were carried out in an end loaded piston cylinder apparatus. The length change of the tungsten carbide standard is small compared to that of NaCl and therefore reliable data are obtained. Compression data by Bridgman[1] and thermal expansion data by Kennametal Inc. were used for the equation of state of tungsten carbide. We estimated an absolute uncertainty in the length change measurement of NaCl of ±0.7%. The temperature was accurate within 0.3°C. The uncertainty in pressure is ±0.4%. The results are compared with Decker's [2] equation of state which is frequently used when NaCl is taken as a standard in high pressure work. At room temperature we find a smaller compression of NaCl than Decker and find excellent agreement with Bridgman's[3] data. At higher temperatures we find very good agreement between our data and Decker's equation of state.     

A search for mechanoluminophors capable of pressure-induced thermal population of excited states

During the process of deforming a crystal, a high pressure is developed near the tip of mobile cracks, which may in turn produce a new ground state by thermal electron transfer. Upon sudden release of pressure, the electron can either relax to one atmosphere ground state or remain in the excited state potential well long enough to relax to one atmosphere and radiatively transfer back to the ground state. For analysing the pressure induced thermal population of the excited state, the mechanoluminescence(ML) and high pressure photoluminescence(PL) of several organic and inorganic crystals were measured. The study indicated that usual pressure coefficient of energy shift of the order of 50–100 cm⁻¹/kbar and the stress at the crack-tip of the order of 5–10 kbar, are not sufficient to cause the thermal population of the excited state. If by any means the product of pressure coefficient and stress at the mobile crack-tip can be increased by 50 to 100 times, then the thermal population of the excited states may take place. Using the pressure coefficient of energy shift and the difference in ML and PL spectra, and using independently the change in relative intensities of the vibronic peaks, the pressure at the emitting mechanoluminescent crystal sites is evaluated and it is found to be of the order of several kbar which varies from crystal to crystal.     

Antiferromagnetic metallic state of NiS2

The neutron diffraction experiment we have made on NiS_1.91 single crystal under increasing pressure (0<P<30 kbar) indicates a constant increase of the Néel temperature of the sample. For high pressures (P>20 kbar) and low temperatures the sample is in an antiferromagnetic metallic state as suggested by theoretical considerations for a Mott-Hubbard insulator. The pressure dependence of the second magnetic transition in NiS₂ (T = 31 K for P = 0) is also reported.     

The effect of pressure on lattice parameter,magnetic susceptibility and reflectivity of SmS

The lattice parameter of SmS single crystals has been measured under hydrostatic pressure up to 70 kbar. The fit for the metallic phase by means of the Birch equation gives an unusually large pressure derivative of the bulk modulus B' = 11 and hence a large pressure dependence of B. No change in the nonmagnetic intermediate valence state of Sm is observed up to 24 kbar as concluded from our magnetic susceptibility measurements. Reflectivity measurements under hydrostatic pressure p > 6.5 kbar show a small plasma edge shift (～0.08 eV) towards lower energy upon cooling from 77 to 4.2 K. Hence the low temperature resistivity anomaly is attributed to an enhanced conduction electron scattering.     

High pressure lattice dynamics, dielectric and thermodynamic properties of SrO

Using density functional theory and density functional perturbation theory we have studied the effects of hydrostatic pressure on lattice dynamics, dielectric and thermodynamic properties of the rocksalt (NaCl) and CsCl phases of SrO. The stability of the NiAs type structure, experimentally confirmed to be stable in BaO, is also investigated. Studying the lattice dynamics of the NaCl and CsCl phases at various pressures, in the range of the phase stability, we have found the lattice dynamical instabilities which govern the phase transitions between NaCl and CsCl phases with increasing and decreasing pressure. By monitoring the behaviour of the found soft modes, we have calculated the transition pressures upon compression and decompression of SrO crystal. Lattice dynamics calculations reveal that the rocksalt and CsCl structures are unstable with respect to the soft transversal acoustic modes at single points of the Brillouin zone, which points to the fact that the transitions are of displacive type. Responses to electric fields and thermodynamic properties at high pressures are also given and discussed. All our results are in a good agreement with experimental data where applicable.     

Exciton condensation in intermediate valent Sm0.90La0.10S

Sm_1−xLa_xS for x more than a few percents are metals at ambient conditions. At low temperature and high pressure they develop a small gap in the order of some meV and become semiconductors or insulators. This has been interpreted as a manifestation of the excitonic insulator. In this Letter we will concentrate on Sm_0.90La_0.10S, which is the only composition showing a first order transition. Measurements of the volume change with pressure at ambient temperature show this first order volume collapse at 5 kbar with hysteresis. The resistivity is measured in function of temperature and pressure and exhibits also at 5 kbar and ambient temperature a first order phase transition to a more metallic state. At low temperatures and in function of pressure the resistivity exhibits a peak. The optical reflectivity at 300 K has been measured at low and high pressure and transforms with pressure above 5 kbar into the golden metallic phase.     

Hydrostatic pressure effect on the commensurate—incommensurate phase transition of NiBr2

Pressure effects on the magnetic properties of NiBr₂ have been determined. While the Néel temperature is practically independent of pressure, the temperature of the transition between the incommensurate and the commensurate phases decreases strongly with pressure (9.5% per kbar) and above 10.6 kbar the stability range of the helical state disappears. The susceptibility in the antiferromagnetic phase is depressed by pressure (4.5% per kbar) whereas it remains unchanged in the helical state.     

Superconductivity and phase stability of selenium at high pressures

Hexagonal Se shows no indication of a transformation to a metallic, superconducting phase up to 160 kbar. Amorphous Se transforms at about 130 kbar to an unstable metallic, superconducting state which anneals slowly at room temperature toward a non-metallic, non-superconducting phase. Monoclinic Se behaves much like amorphous Se. X-ray diffraction indicates that all samples are in the hexagonal phase after release of pressure.     

Experimental determination of thermal expansivity of several alkali halides at high pressures

Unit-cell volumes of four alkali halides, LiF, NaF, KF and CSCl, were measured to 90 kbar and 800°C using X-ray powder diffraction techniques. NaCl was used as an internal pressure standard. Experimental results were analyzed based on Decker's equation of state for NaCl and thermal expansívities of these four materials were determined as a function of pressure. Volume dependence of thermal expansivity is different for the NaCl and CsCl structures. Comparisons of the present results with theoretical calculations by Birch and Anderson are presented.     

Neutron Diffraction Study of the p - T Phase Diagram for Erbium

Electrical resistivity measurements performed on a single crystal of erbium as a function of temperature and hydrostatic pressure have provided a preliminary p - T phase diagram. The results have been interpreted in terms of a model for the magnetic structures of Er deduced from neutron diffraction studies at ambient pressure. This model predicted the existence of a magnetic structure with a wave vector of Q =2/7 c * at 4.2 K, when the applied pressure is larger than 3 kbar. This paper reports a neutron diffraction study of erbium made in the temperature range of 4 to 100 K, at pressures between 0.5 and 6 kbar. We have observed the predicted suppression of the low temperature conical ferromagnetic phase and the emergence of a new phase with Q =8/33 c *. The neutron diffraction measurements has enabled us to identify the various phases that develop from the cycloidal phases previously observed at atmospheric pressure.     

Equilibrium lines and barriers to phase transitions: the cubic diamond to beta-tin transition in Si from first principles

The phase transition between the cubic diamond (cd) and beta-tin (β-Sn) phases of Si under pressure and the region of interaction of the two phases are studied by first-principles total energy calculations. For a non-vibrating crystal we determine the pressure of the thermodynamic phase transition p(t) = 96 kbar, the Gibbs free energy barrier at p(t) of ΔG = 19.6 mRyd/atom that stabilizes the phases against a phase transition and the finite pressure range in which both phases are stable. We show that the phases in that pressure range are completely described by three equilibrium lines of states along which the structure, the total energy E, the hydrostatic pressure p that would stabilize the structure and the values of G all vary. Two equilibrium lines describe the two phases (denoted the ph-eq line, ph is cd or β-Sn phase); a third line is a line of saddle points of G with respect to structure (denoted the sp-eq line) that forms a barrier of larger G against instability of the metastable ranges of the phase lines. An important conclusion is that the sp-eq line merges with the two ph-eq lines: one end of the sp-eq line merges with the cd-eq line at high pressure, the other end merges with the β-Sn-eq line at low pressure. The mergers end the barrier protecting the metastable ranges of the two ph-eq lines, hence the lines go unstable beyond the mergers. The mergers thus simplify the phase diagram by providing a natural termination to the stable parts of all metastable ranges of the ph-eq lines. Although 96 kbar is lower than the experimental transition pressure, we note that phonon pressure raises the observed transition pressure.     

Pressure induced transition from intermediate valence to metallic behaviour in collapsed SmS

The resistivity ? and Hall coefficient R_h of nominally stoichiometric pressure collapsed SmS single crystals were measured as a function of temperature T (1.5 K< T < 300 K) at several pressures P from 4 to 22 kbar. With increasing pressure we observed a change in the ? (T) and R_h (T) variations from an intermediate valence behaviour (P < 20 kbar) to a metallic behaviour with Kondo like scattering (P > 20 kbar).     

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.     

GaP at ultrahigh pressure

An x-ray diffraction experiment has been carried out on GaP compressed in a quasi-hydrostatic pressurizing medium to 296 ± 5 kbar. The transformation pressure was found to be increased from the value of 220 kbar (22 GPa) reported in a less hydrostatic environment, since two phases of GaP (I and II) were found in coexistence at 250 ± 5 kbar. No evidence of disproportionation was found at this pressure, or 296 kbar, where sharp lines of phase II were found (body centered tetragonal). No evidence of amorphization was found on release of pressure.