Elastic properties of liquid and glassy propane-based alcohols under high pressure: the increasing role of hydrogen bonds in a homologous family.

We have measured the elastic moduli of liquid and glassy n-propanol and propylene glycol (PG) under pressure by ultrasonic techniques and have recalculated similar characteristics for glycerol from the previous experiment. All three substances form a ternary homologous family with the common formula C3H8-n(OH)n (n = 1, 2, 3), where the number of hydrogen bonds per molecule increases with the number of oxygen atoms approximately as ≈2n. In turn, the enhancement of hydrogen bonding results in an increase in elastic moduli (bulk modulus for liquids or bulk and shear moduli for glasses) from n-propanol to glycerol at all pressures, while the volume per molecule Vm shows the opposite trend at atmospheric pressure in spite of an increase in the molecular size. Nevertheless, the ratios between the Vm values at pressure P > 0.05 GPa are inverted in liquids and tend to the ratios of molecule volumes which indicates a decrease of the relative contribution of hydrogen bonds to the repulsive intermolecular forces with increasing pressure regardless of increase or decrease in the number of hydrogen bonds and their strength. A similar volume behavior is observed for glasses at T = 77 K. We have also established that the relative difference between corresponding moduli of liquid or glassy n-propanol and PG is remarkably less than that between corresponding values for PG and glycerol. We explain this property by the formation of a three-dimensional network of hydrogen bonds in glycerol, where the number of hydrogen bonds per molecule is close to six.

Structural and Dielectric Relaxations in Vitreous and Liquid State of Monohydroxy Alcohol at High Pressure.

2-Ethyl-1-hexanol monoalcohol is a well-known molecular glassformer, which for a long time attracts attention of researchers. As in all other monohydroxy alcohols, its dielectric relaxation reveals two distinct relaxation processes attributed to the structural relaxation and another more intense process, which gives rise to a low-frequency Debye-like relaxation. In this monoalcohol, the frequency separation between these two processes reaches an extremely high value of 3 orders of magnitude, which makes this substance a rather convenient object for studies of mechanisms (supposedly common to all monoalcohols) leading to vitrification of this type of liquids. In this work, we apply two experimental techniques, dielectric spectroscopy and ultrasonic measurements (in both longitudinal and transverse polarizations) at high pressure, to study interference between different relaxation mechanisms occurring in this liquid, which could shed light on both structural and dielectric relaxation processes observed in a supercooled liquid and a glass state. Application of high pressure in this case leads to the simplification of the frequency spectrum of dielectric relaxation, where only one asymmetric feature is observed. Nonetheless, the maximum attenuation of the longitudinal wave in ultrasonic experiments at high pressure is observed at temperatures ≈50 K above the corresponding temperature for the transverse wave. This might indicate different mechanisms of structural relaxation in shear and bulk elasticities in this liquid.

Magnetoresistance of the high-pressure ferromagnetic phases (GaSb)2M (M=Cr,Mn).

For the first time magnetoresistance of the ferromagnetic high-pressure phases (GaSb)2M (M=Cr,Mn) has been measured in a wide range of temperature and magnetic field. It was found that the magnetic field dependencies of resistivity of both systems contain several contributions, including relatively smaller s-d exchange (Yosida-type) components in low fields and a quadratic positive term (PMR) in the low temperature region. The magnitude of the predominated negative term (NMR), which can be attributed to the quantum corrections effects, demonstrates a peak in the vicinity of Curie temperature.

"Liquid-gas" transition in the supercritical region: fundamental changes in the particle dynamics.

Recently, we have proposed a new dynamic line on the phase diagram in the supercritical region, the Frenkel line. Crossing the line corresponds to the radical changes of system properties. Here, we focus on the dynamics of model Lennard-Jones and soft-sphere fluids. We show that the location of the line can be rigorously and quantitatively established on the basis of the velocity autocorrelation function (VAF) and mean-square displacements. VAF is oscillatory below the line at low temperature, and is monotonically decreasing above the line at high temperature. Using this criterion, we show that the crossover of particle dynamics and key liquid properties occur on the same line. We also show that positive sound dispersion disappears in the vicinity of the line in both systems. We further demonstrate that the dynamic line bears no relationship to the existence of the critical point. Finally, we find that the region of existence of liquidlike dynamics narrows with the increase of the exponent of the repulsive part of interatomic potential.

Dielectric spectroscopy and ultrasonic study of propylene carbonate under ultra-high pressures.

We present the high pressure dielectric spectroscopy (up to 4.2 GPa) and ultrasonic study (up to 1.7 GPa) of liquid and glassy propylene carbonate (PC). Both of the methods provide complementary pictures of the glass transition in PC under pressure. No other relaxation processes except α-relaxation have been found in the studied pressure interval. The propylene carbonate liquid is a glassformer where simple relaxation and the absence of ß-relaxation are registered in the record-breaking ranges of pressures and densities. The equation of state of liquid PC was extended up to 1 GPa from ultrasonic measurements of bulk modulus and is in good accordance with the previous equations developed from volumetric data. We measured the bulk and shear moduli and Poisson's ratio of glassy PC up to 1.7 GPa. Many relaxation and elastic properties of PC can be qualitatively described by the soft-sphere or Lennard-Jones model. However, for the quantitative description of entire set of the experimental data, these models are insufficient. Moreover, the Poisson coefficient value for glassy PC indicates a significant contribution of non-central forces to the intermolecular potential. The well-known correlation between Poisson's ratio and fragility index (obtained from dielectric relaxation) is confirmed for PC at ambient pressure, but it is violated with pressure increase. This indicates that different features of the potential energy landscape are responsible for the evolution of dielectric response and elasticity with pressure increase.

Two liquid states of matter: a dynamic line on a phase diagram.

It is generally agreed that the supercritical region of a liquid consists of one single state (supercritical fluid). On the other hand, we show here that liquids in this region exist in two qualitatively different states: "rigid" and "nonrigid" liquids. Rigid to nonrigid transition corresponds to the condition τ≈τ(0), where τ is the liquid relaxation time and τ(0) is the minimal period of transverse quasiharmonic waves. This condition defines a new dynamic crossover line on the phase diagram and corresponds to the loss of shear stiffness of a liquid at all available frequencies and, consequently, to the qualitative change in many important liquid properties. We analyze this line theoretically as well as in real and model fluids and show that the transition corresponds to the disappearance of high-frequency sound, to the disappearance of roton minima, qualitative changes in the temperature dependencies of sound velocity, diffusion, viscous flow, and thermal conductivity, an increase in particle thermal speed to half the speed of sound, and a reduction in the constant volume specific heat to 2k(B) per particle. In contrast to the Widom line that exists near the critical point only, the new dynamic line is universal: It separates two liquid states at arbitrarily high pressure and temperature and exists in systems where liquid-gas transition and the critical point are absent altogether. We propose to call the new dynamic line on the phase diagram "Frenkel line".

Electrotransport and magnetic properties of Cr-GaSb phases synthesized under high pressure.

The electrotransport and magnetic properties of new phases in the Cr-GaSb system were studied. The samples were prepared by high-pressure (P=6-8 GPa), high-temperature treatment and identified by x-ray diffraction and scanning electron microscopy. One of the CrGa(2)Sb(2) phases with an orthorhombic structure Iba2 has a combination of ferromagnetic and semiconductor properties and is potentially promising for spintronic applications. Another high-temperature phase is paramagnetic and identified as tetragonal I4/mcm.

Widom line for the liquid-gas transition in Lennard-Jones system.

The locus of extrema (ridges) for heat capacity, thermal expansion coefficient, compressibility, and density fluctuations for model particle systems with Lennard-Jones (LJ) potential in the supercritical region have been obtained. It was found that the ridges for different thermodynamic values virtually merge into a single Widom line at T < 1.1T(c) and P < 1.5P(c) and become practically completely smeared at T < 2.5T(c) and P < 10P(c), where T(c) and P(c) are the critical temperature and pressure. The ridge for heat capacity approaches close to critical isochore, whereas the lines of extrema for other values correspond to density decrease. The lines corresponding to the supercritical maxima for argon and neon are in good agreement with the computer simulation data for LJ fluid. The behavior of the ridges for LJ fluid, in turn, is close to that for the supercritical van der Waals fluid, which is indicative of a fairly universal behavior of the Widom line for a liquid-gas transition.

Structural transformations and anomalous viscosity in the B2O3 melt under high pressure.

Liquid B2O3 represents an archetypical oxide melt with a superhigh viscosity at the melting temperature. We present the results of the in situ x-ray diffraction study and the in situ viscosity measurements of liquid B2O3 under high pressure up to 8 GPa. Additionally, the 11B solid state NMR spectroscopy study of B2O3 glasses quenched from the melt at five different pressures has been carried out. Taken together, the results obtained provide understanding of the nature of structural transformations in liquid B2O3. The fraction of the boroxol rings in the melt structure rapidly decreases with pressure. From pressures of about 4.5 GPa, four-coordinated boron states begin to emerge sharply, reaching the fraction 40%-45% at 8 GPa. The viscosity of the B2O3 melt along the melting curve drops by 4 orders of magnitude as the pressure increases up to 5.5 GPa and remains unchanged on further pressure increase.

Glassy dynamics under superhigh pressure.

Nearly all glass-forming liquids feature, along with the structural alpha-relaxation process, a faster secondary process (beta relaxation), whose nature belongs to the great mysteries of glass physics. However, for some of these liquids, no well-pronounced secondary relaxation is observed. A prominent example is the archetypical glass-forming liquid glycerol. In the present work, by performing dielectric spectroscopy under superhigh pressures up to 6 GPa, we show that in glycerol a significant secondary relaxation peak appears in the dielectric loss at P>3 GPa. We identify this beta relaxation to be of Johari-Goldstein type and discuss its relation to the excess wing. We provide evidence for a smooth but significant increase in glass-transition temperature and fragility on increasing pressure.

Compressibility and polymorphism of α-As(4)S(4) realgar under high pressure.

The energy-dispersive x-ray diffraction technique has been employed to study the structure and equation of state of realgar As(4)S(4) under pressures up to 8 GPa at room temperature. We have obtained pressure dependences of the unit cell parameters and volume for the monoclinic structure of realgar. An approximation of the equation of state through the Murnaghan equation gives the bulk modulus and its derivative, B(0) = 8.1 ± 0.5 GPa and B(0)(') = 9.0 ± 0.5, respectively. A comparison of the obtained values with the corresponding values for other molecular crystals is drawn and discussed. At a pressure of around 7 GPa, realgar showed a polymorph transition to a new molecular phase with a supposedly orthorhombic structure. Such identification is evidenced by the presence of geometrical correlations between the parameters of the parent monoclinic phase and those of the new phase, and the phase transition is likely to be associated with the removal of a monoclinic distortion in the unit cell.

Nature of the structural transformations in B2O3 glass under high pressure.

We study high-pressure polyamorphism of B2O3 glass using x-ray diffraction up to 10 GPa in the 300-700 K temperature range, in situ volumetric measurements up to 9 GPa, and first-principles simulations. Under pressure, glass undergoes two-stage transformations including a gradual increase of the first B-O (O-B) coordination numbers above 5 GPa. The fraction of boron atoms in the fourfold-coordinated state at P<10 GPa is smaller than was assumed from inelastic x-ray scattering spectroscopy data, but is considerably larger than was previously suggested by the classical molecular dynamics simulations. The observed transformations under both compression and decompression are broad in hydrostatic conditions. On the basis of ab initio results, we also predict one more transformation to a superdense phase, in which B atoms are sixfold coordinated.

AsS melt under pressure: one substance, three liquids.

An in situ high-temperature--high-pressure study of liquid chalcogenide AsS by x-ray diffraction, resistivity measurements, and quenching from melt is presented. The obtained data provide direct evidence for the existence in the melt under compression of two transformations: one is from a moderate-viscosity molecular liquid to a high-viscosity nonmetallic polymerized liquid at P approximately 1.6-2.2 GPa; the other is from the latter to a low-viscosity metallic liquid at P approximately 4.6-4.8 GPa. Upon rapid cooling, molecular and metallic liquids crystallize to normal and high-pressure phases, respectively, while a polymerized liquid is easily quenched to a new AsS glass. General aspects of multiple phase transitions in liquid AsS, including relations to the phase diagram of the respective crystalline, are discussed.

Pressure-driven "molecular metal" to "atomic metal" transition in crystalline Ga.

We present the ultrasonic study of gallium (Ga I) under high pressure up to 1.7 GPa, including the measurements of the density and elastic properties during phase transitions to Ga II and to a liquid state. The observed large drop of both bulk and shear moduli (by 30% and 55%, correspondingly) during the phase transition to Ga II, as well as the increase of the Poisson's ratio from typically "covalent" ( approximately 0.22) to "metallic" ( approximately 0.32) values, experimentally testifies to the coexistence of a molecular and metallic behavior in Ga I and to the disappearance of the "covalency" during the transition to Ga II. A high value of the pressure derivative of the bulk modulus for Ga I and the increase in the Poisson's ratio can be associated with the weakening of the covalency in compressed Ga I and considered as a precursor of the transition to normal metal.

Molecular-network-ionic structure transitions in liquid AlCl(3) and ZnCl(2) halogenides under pressure.

We present the in situ high-pressure-high-temperature x-ray diffraction study of the liquid AlCl(3) and ZnCl(2) halogenides having a quasi-molecular network structure in liquid state at normal pressure. These liquids are intermediate between pure covalent and ionic melts. Structural study of these liquid halogenides is indicative of a rapid and strong breakdown of an intermediate-range order in a tetrahedral network of melts for the initial pressure range, 0-2.5 GPa for AlCl(3) and 0-1.8 GPa for ZnCl(2), and points to rather sharp transitions in liquids with the formation of a short-range order structure similar to ionic melt structures around 4 GPa for AlCl(3) and 3 GPa for ZnCl(2). Thus, pseudo-covalent liquid halogenides like AlCl(3) and ZnCl(2) provide testimony to two phenomena under high pressures, namely, a gradual decay of structural correlations in the tetrahedral network of the melt and a sharp transition from molecular-network to ionic structure in liquid on further compression. Such a two-stage structural transformation under pressure is the general feature for a wide class of simple melts, including most of the pseudo-covalent halogenides.

Metastable high-pressure phases of low-Z compounds: creation of a new chemistry or a prompt for old principles?

Recent experiments demonstrate that high pressure is a powerful tool for the synthesis of new unusual inorganic polymers consisting of low-Z elements. However, experience within organic chemistry, for example, polyethylene, provides evidence that polymeric phases with high thermal stability can be potentially synthesised by conventional chemical techniques without applying high pressure.

Pressure-induced crossover between diffusive and displacive mechanisms of phase transitions in single-crystalline alpha-GeO2.

We present the first example of the phase transition occurring via the different kinetic mechanisms, displacive or diffusive, competing with each other in quartz-like alpha-GeO2 single crystals. Upon room-pressure heating, alpha-GeO2 transforms to the rutile-type phase (the alpha-->r transition) via the diffusive mechanism. With increase of the treatment pressure the diffusive mode of the temperature-induced alpha-->r transition is substituted at approximately 4 GPa by a displacive-like mode, and then at approximately 6 GPa the transition type changes from the alpha-->r sequence to a displacive martensitic-like transition to a distorted rutile-like phase (alpha-->r'. A crossover between diffusive and displacive transition modes suggests a new way to control the meso- and nanometer-scale morphology of high-pressure phases.