Non-exponential relaxation of nuclear magnetization in solid ortho-para hydrogen mixtures

We report calculations of the decay of the nuclear magnetization of different isochromats in the NMR absorption spectrum of solid mixtures of ortho-para hydrogen. The calculated decays show significant departures from exponential recovery and are in good overall agreement with experimental results reported elsewhere. A slowly component, characteristic of the quadrupolar glass phase is predicted at long times.     

Ab initio simulation of phase transitions and dissociation of H2S at high pressure

By ab initio constant pressure molecular dynamics, we have identified the structure of phase V and phase VI of H2S at 35 and 65 GPa, respectively. The theoretical IR spectra of both phases are consistent with experimental findings and support our proposed structural models. We find that phase V is characterized by the presence of charged SH+3 and SH- species which are created and destroyed dynamically, whereas phase VI is no longer a molecular phase but consists of sheets of S with the majority of H intercalated between the layers. The stability of the two phases with respect to dissociation into elemental crystalline hydrogen and sulfur is discussed.     

Molybdenum at high pressure and temperature: melting from another solid phase

The Gibbs free energies of bcc and fcc Mo are calculated from first principles in the quasiharmonic approximation in the pressure range from 350 to 850 GPa at room temperatures up to 7500 K. It is found that Mo, stable in the bcc phase at low temperatures, has lower free energy in the fcc structure than in the bcc phase at elevated temperatures. Our density-functional-theory-based molecular dynamics simulations demonstrate that fcc melts at higher than bcc temperatures above 1.5 Mbar. Our calculated melting temperatures and bcc-fcc boundary are consistent with the Mo Hugoniot sound speed measurements. We find that melting occurs at temperatures significantly above the bcc-fcc boundary. This suggests an explanation of the recent diamond anvil cell experiments, which find a phase boundary in the vicinity of our extrapolated bcc-fcc boundary.     

Extraordinary wetting phase diagram for mixtures of Bose-Einstein condensates

The possibility of wetting phase transitions in Bose-Einstein condensed gases is predicted on the basis of Gross-Pitaevskii theory. The surface of a binary mixture of Bose-Einstein condensates can undergo a first-order wetting phase transition upon varying the interparticle interactions, using, e.g., Feshbach resonances. Interesting ultra-low-temperature effects shape the wetting phase diagram. The prewetting transition is, contrary to general expectations, not of first order but critical, and the prewetting line does not meet the bulk phase coexistence line tangentially. Experimental verification of these extraordinary results is called for, especially now that it has become possible, using optical methods, to realize a planar "hard wall" boundary for the condensates.     

Fast ortho-para conversion of H2 adsorbed at copper surface step atoms

Ortho-para conversion of H2 adsorbed at the step atoms of a Cu(510) surface proceeds with a short conversion time constant around 1 s as observed in electron-energy-loss measurements of rotational populations. We suggest that this rapid conversion is related to the special character of the adsorption state, which involves a short H2-Cu bond length of 1.8 A. On the flat Cu(100) surface, conversion is found to occur at active sites, most likely step atoms.     

Theoretical melting curves for cubic solids at high pressure

The Lindemann law, the fourth-order anharmonic equation of state and a model for the volume dependence of the Grüneisen coefficient in cubic crystals are used to derive temperature-strain-pressure relations at melting. The relations depend for their application on knowing the values of fourth-order elastic parameters which are not measured experimentally. It is shown that these values can be estimated from melting data at low pressure. A comparative study of the results with previous determinations obtained from shock-wave data is given for copper, silver and gold. Finally, the theoretical fourth-order melting curves of the three selected metals are calculated using both the Lagrangian and Eulerian strain measures.     

Lattice dynamics and phase diagram of aluminum at high temperatures

The dispersion of phonons in the fcc, hcp, and bcc phases of aluminum is calculated at ultrahigh pressures by the method of small displacements in a supercell. The stability of the phonon subsystem is studied. The thermodynamic characteristics are calculated in the quasi-harmonic approximation, and a phase diagram of aluminum is plotted. As compared to the Debye model, the use of a phonon spectrum calculated in the quasi-harmonic approximation significantly broadens the hcp phase field and strongly shifts the phase boundary between the fcc and bcc phases. The normal isentrope is calculated at megabar pressures. It is shown to intersect the fcc-hcp and hcp-bcc phase boundaries. The sound velocity along the normal isentrope is calculated. It is shown to have a nonmonotonic character.     

New phase transition of solid bromine under high pressure

Solid bromine has been studied by x-ray absorption spectroscopy experiments up to a maximum pressure of 75 GPa. The data analysis of the extended fine structure reveals that the intramolecular distance first increases, reaching its maximum value at 25+/-5 GPa. From this value the intramolecular distance abruptly begins to decrease evidencing a nonpreviously observed phase transformation taking place at 25+/-5 GPa. A maximum variation of 0.08 A is observed at 65+/-5 GPa where again a phase transition occurs. This last transformation could correspond with the recently observed change to an incommensurate modulated phase. We discuss the possible generalization of the observed new phase transition at 25+/-5 GPa to the case of the other halogens.     

Theoretical temperature-electric field phase diagram for deuterated thiourea SC(ND2)2

A theoretical temperature-electric field phase diagram is constructed for thiourea SC(ND₂)₂ using a phenomenological approach based on the representation of the thermodynamic potentials for all phases. The theoretical diagram is compared with the experimental diagram. Fiz. Tverd. Tela (St. Petersburg) 39, 1282–1286 (July 1997)     

Crystalline post-quartz phase in silica at high pressure

alpha-quartz, which has been reported to undergo pressure-induced amorphization, was found to transform to a monoclinic, crystalline phase when compressed to 45 GPa at room temperature in a close to hydrostatic, helium pressure medium. The x-ray powder diffraction data obtained could be indexed based on a monoclinic cell, and the intensities are in agreement with a P2(1)/c model structure built up of 3x2 zigzag chains of SiO6 octahedra. This new polymorph of silica, which is metastable under ambient conditions, has been isolated for the first time and is one of several possible competing dense forms containing octahedrally coordinated silicon.     

Phase diagram of aqueous solution at high pressure and low temperature

Abstract

This paper presents a constant mass high pressure isothermal calorimeter and describes the range of applications that this type of equipment can deal with. As an example, the thermophysical properties of an aqueous solution of MgSO₄ at low temperature and at high pressure have been investigated. The main results showed that the phase change heat of the solution decreased with increasing pressure and the phase change temperature of the eutectic concentration was depressed under high pressure. Those changes could be related to the MgSO₄ solubility and to water latent heat changes.     

Comparison of local ordering of orthohydrogen molecules above and below the percolation threshold in solid ortho-para mixtures

We report measurements of the local orientational ordering in solid ortho-para hydrogen mixtures for ortho concentrations near the site percolation threshold. The results indicate a weak collective ordering for concentrations above percolation which is absent for low concentrations.     

The change in phase behaviour and orientational order of solid N2 at high pressure under the influence of Ar: a simulation study

We have studied the influence of Ar atoms on the high-pressure phase behaviour of N₂ by a Monte Carlo study of Ar _x (N₂)_1-x mixed solids. The results were obtained on the N₂ rich side (0 ≤ x ≤ 0.25), in the region where the ? and δ phases exist in pure N₂. The ??—δ? transition shifts rapidly to lower temperatures with x: it has vanished for x ? 0.05. For x ? 0.12, a cubic orientationally ordered phase appears. The transition from this phase to the δ? phases shifts to higher temperatures with increasing x. The temperature of the onset as well as the completion of the cascade process, responsible for the δ?_loc—δ?_rot transition, is independent of composition. This transition disappears in the x-region where the ordered phase is present for all temperatures below the transition to the δ?_rot phase. Therefore, the influence of the isotropic diluents on the orientational behaviour of the N₂ molecules is threefold. In the δ?_loc phase, the vibron frequencies show a splitting that shifts as a function of x, which might be related to the occurrence of a tetragonal modification of this phase.     

Enantiotropic nematic reentrant behaviour at atmospheric pressure in a pure compound

By the way of microscopic observations (contact method) we conclude for the first time to the existence of a reentrant nematic at atmospheric pressure in a pure compound.