Role of spin-glass behavior in the formation of exotic magnetic states in GdB6.

Randomness and frustration are believed to be two crucial criteria for the formation of spin glass state. However, the spin freezing occurs in some well-ordered crystals below the related temperature Tf due to the instability of each spin state, which induces the variation of either magnetic moment value or exchange energy. Here we explore the new mechanism of the in-site originated disorder in antiferromagnets Gd0.73La0.27B6 and GdB6, which is caused by the random mutual shifts of Gd3+ spins from the centrally symmetrical positions in the regular cubic lattice. The universal scaling of ESR linewidth temperature dependencies to the power law ΔH(T) ~ ((T - TD)/TD)α with α = - 1.1 ± 0.05 in the paramagnetic phase of both compounds demonstrates the identity of the origin of magnetic randomness. In Gd0.73La0.27B6 the resulting random spin configurations freeze at Tf ≈ 10.5 K where the maximum of magnetization is observed. Below Tf the splitting of ZFC and FC magnetization curves takes place as well as the magnetic state depends on the antecedent sample history. In the case of GdB6 the coherent displacement of Gd ions compete with these random shifts forming an antiferromagnetic (AFM) phase at TN = 15.5 K, which prevails over the spin freezing at Tf ≈ 13 K, expected from the ESR data. The observation of the hysteresis of the ESR spectrum in the AFM phase suggests that its properties may be determined by the competition of two types of AFM orders, which results in formation of stable magnetic domains with nonequivalent positions of AFM Gd pairs at T < 10 K.

Evolution of thermoelectric properties in EuxYb1-xB6 family.

Seebeck effect in the crystalline samples of EuxYb1-xB6 (x = 0, 0.082, 0.127, 0.9, 1) was investigated at temperatures 2-300 K. For all the compounds thermopower is shown to be well described by the sum of diffusion (S d = AT) and phonon drag components. The latter contribution is induced by quasilocal (Einstein) modes of ytterbium and europium ions with characteristic temperatures ΘE(YbB6) ≈ 91 K and ΘE(EuB6) ≈ 122 K. The estimation of effective mass m * of the charge carriers proves that increasing of Eu content induces crossover from 'heavy' holes with m h *(x ⩽ 0.127) ≈ 0.3-0.36 m 0 to 'light' electrons with m e *(x ⩾ 0.9) ≈ 0.12-0.13 m 0 (m 0-free electron mass). For the Eu-rich compounds we propose the existence of additional point on the phase diagram, which corresponds to short-range magnetic order with enhanced spin fluctuations preceding the stabilization of magnetic polarons.

Communication: minimum in the thermal conductivity of supercooled water: a computer simulation study.

We report the results of a computer simulation study of the thermodynamic properties and the thermal conductivity of supercooled water as a function of pressure and temperature using the TIP4P-2005 water model. The thermodynamic properties can be represented by a two-structure equation of state consistent with the presence of a liquid-liquid critical point in the supercooled region. Our simulations confirm the presence of a minimum in the thermal conductivity, not only at atmospheric pressure, as previously found for the TIP5P water model, but also at elevated pressures. This anomalous behavior of the thermal conductivity of supercooled water appears to be related to the maximum of the isothermal compressibility or the minimum of the speed of sound. However, the magnitudes of the simulated thermal conductivities are sensitive to the water model adopted and appear to be significantly larger than the experimental thermal conductivities of real water at low temperatures.

Entropy-driven liquid-liquid separation in supercooled water.

Twenty years ago Poole et al. suggested that the anomalous properties of supercooled water may be caused by a critical point that terminates a line of liquid-liquid separation of lower-density and higher-density water. Here we present a thermodynamic model based on this hypothesis, which describes all available experimental data for supercooled water with better quality and fewer adjustable parameters than any other model. Liquid water at low temperatures is viewed as an 'athermal solution' of two molecular structures with different entropies and densities. Alternatively to popular models for water, in which liquid-liquid separation is driven by energy, the phase separation in the athermal two-state water is driven by entropy upon increasing the pressure, while the critical temperature is defined by the 'reaction' equilibrium constant. The model predicts the location of density maxima at the locus of a near-constant fraction of the lower-density structure.

Comparison of complete scaling and a field-theoretic treatment of asymmetric fluid criticality.

We investigate the connection between the theory of complete scaling and a field-theoretic (FT) treatment of asymmetric fluid criticality. To facilitate the comparison, we develop an equation of state from a simplified form of the complete scaling transformations and systematically compare this equation of state with the equation of state generated by a FT treatment of an asymmetric Landau-Ginzburg-Wilson Hamiltonian. We find, with care in interpretation, that these two approaches may be read as equivalent up to terms involving an independent higher-order asymmetric correction-to-scaling exponent.

Thermodynamics of supercooled water.

We review the available experimental information on the thermodynamic properties of supercooled water and demonstrate the possibility of modeling these thermodynamic properties on a theoretical basis. We show that by assuming the existence of a liquid-liquid critical point in supercooled water, the theory of critical phenomena can give an accurate account of the experimental thermodynamic-property data up to a pressure of 150 MPa. In addition, we show that a phenomenological extension of the theoretical model can account for all currently available experimental data in the supercooled region, up to 400 MPa. The stability limit of the liquid state and possible coupling between crystallization and liquid-liquid separation are also discussed. It is concluded that critical-point thermodynamics describes the available thermodynamic data for supercooled water within experimental accuracy, thus establishing a benchmark for further developments in this area.

Critical behavior of the dielectric constant in asymmetric fluids.

By applying a thermodynamic theory that incorporates the concept of complete scaling, we derive the asymptotic temperature dependence of the critical behavior of the dielectric constant above the critical temperature along the critical isochore and below the critical temperature along the coexistence curve. The amplitudes of the singular terms in the temperature expansions are related to the changes of the critical temperature and the critical chemical potential upon the introduction of an electric field. The results of the thermodynamic theory are then compared with the critical behavior implied by the classical Clausius-Mossotti approximation. The Clausius-Mossotti approximation fails to account for any singular temperature dependence of the dielectric constant above the critical temperature. Below the critical temperature it produces an apparent asymmetric critical behavior with singular terms similar to those implied by the thermodynamic theory, but with significantly different coefficients. We conclude that the Clausius-Mossotti approximation only can account for the observed asymptotic critical behavior of the dielectric constant when the dependence of the critical temperature on the electric field is negligibly small.

Peculiar thermodynamics of the second critical point in supercooled water.

On the basis of the principle of critical-point universality, we examine the peculiar thermodynamics of the liquid-liquid critical point in supercooled water. We show that the liquid-liquid criticality in water represents a special kind of critical behavior in fluids, intermediate between two limiting cases: the lattice gas, commonly used to model liquid-vapor transitions, and the lattice liquid, a weakly compressible liquid with an entropy-driven phase separation. While the ordering field in the lattice gas is associated with the chemical potential and the order parameter with the density, in the lattice liquid the ordering field is the temperature and the order parameter is the entropy. The behavior of supercooled water is much closer to lattice-liquid behavior than to lattice-gas behavior. Using new experimental data recently obtained by Mishima [J. Chem. Phys. 2010, 133, 144503], we have revised the parametric scaled equation of state, previously suggested by Fuentevilla and Anisimov [Phys. Rev. Lett. 2006, 97, 195702], and obtain a consistent description of the thermodynamic anomalies of supercooled water by adjusting linear backgrounds, one critical amplitude, and the critical pressure. We also show how the lattice-liquid description affects the finite-size scaling description of supercooled water in confined media.

Complete scaling for inhomogeneous fluids.

"Complete scaling," which maps asymmetric fluid criticality onto the symmetric Ising model, is extended to spatially inhomogeneous fluids. This extension enables us to obtain a fluctuation-modified asymmetric interfacial density profile, which incorporates leading effects from the asymmetry of fluid phase coexistence and the asymmetry of the correlation length. The derived asymmetric interfacial profile is used to calculate Tolman's length, the diverging coefficient of the curvature correction to the surface tension. The amplitude of the divergent Tolman length is found to depend on the asymmetry of the correlation length.

Asymmetric criticality in weakly compressible liquid mixtures.

The thermodynamics of asymmetric liquid-liquid criticality is updated by incorporating pressure effects into the complete-scaling formulation earlier developed for incompressible liquid mixtures [C. A. Cerdeirina et al., Chem. Phys. Lett. 424, 414 (2006); J. T. Wang et al., Phys. Rev. E 77, 031127 (2008)]. Specifically, we show that pressure mixing enters into weakly compressible liquid mixtures as a consequence of the pressure dependence of the critical parameters. The theory is used to analyze experimental coexistence-curve data in the mole fraction-temperature, density-temperature, and partial density-temperature planes for a large number of binary liquid mixtures. It is shown how the asymmetry coefficients in the scaling fields are related to the difference in molecular volumes of the two liquid components. The work resolves the question of the so-called "best order parameter" discussed in the literature during the past decades.

Multiscale dynamics of pretransitional fluctuations in the isotropic phase of a lyotropic liquid crystal.

Using an improved static and dynamic light-scattering technique, we have observed multiscale relaxation of the pretransitional fluctuations in the isotropic phase of a cromolyn aqueous solution, a lyotropic liquid crystal where rods are formed by aggregates of disklike molecules. We have detected the onset of cromolyn aggregation about 12 degrees C above the transition temperature. The onset is manifested by the emergence of strong scattering due to the fluctuations of local anisotropy and by the split of the diffusion dynamics into two distinctly different modes, one associated with the relatively fast diffusion of monomer-size particles and the other one with the much slower diffusion of the cromolyn aggregates. A third observed dynamic mode is associated with the pretransitional slowing down of fluctuations of the local anisotropy. This mode behaves differently in polarized and depolarized light scattering, due to a coupling between fluctuations of the local-anisotropy and velocity fluctuations.

Dynamics of critical fluctuations in polymer solutions.

Using dynamic light scattering we have investigated the time dependence of fluctuations near the critical point of phase separation in solutions of polystyrene in cyclohexane with polymer molecular weights ranging from 196,000 to 11.4 x 10(6) g mol(-1). At the lowest polymer molecular weight the dynamic correlation function follows a single-exponential decay with a decay rate that can be represented by the mode-coupling theory of critical dynamics but with a mesoscopic viscosity that characterizes the hydrodynamic environment of the polymers in the solution. At all higher polymer molecular weights two distinct dynamic modes are observed, a slow and a fast mode, that originate from a coupling of the critical concentration fluctuations with viscoelastic relaxation of the polymer chain in solutions. This coupling causes an additional slowing down of the fluctuations on top of the well-known critical slowing down expected in the absence of a coupling between the two modes. From an analysis of the time dependence of the experimental dynamic correlation functions in terms of a theory of coupling of dynamic modes we are able to determine the viscoelastic properties of the polymers in the solution. These viscoelastic properties diverge in the theta-point limit of infinite polymer molecular weight.

Divergence of Tolman's length for a droplet near the critical point.

The application of "complete scaling" [Kim et al., Phys. Rev. E 67, 061506 (2003); Anisimov and Wang, Phys. Rev. Lett. 97, 025703 (2006)] to the interfacial behavior of fluids shows that Tolman's length, a curvature correction to the surface tension, diverges at the critical point of fluids much more strongly than is commonly believed. The amplitude of the divergence depends on the degree of asymmetry in fluid phase coexistence. In highly asymmetric fluids and fluid mixtures the Tolman length may become large enough to significantly affect the interfacial behavior.

Scaled equation of state for supercooled water near the liquid-liquid critical point.

We have developed a scaled parametric equation of state to describe and predict thermodynamic properties of supercooled water. The equation of state, built on the growing evidence that the critical point of supercooled liquid-liquid water separation exists, is universal in terms of theoretical scaling fields and is shown to belong to the Ising-model class of universality. The theoretical scaling fields are postulated to be analytical combinations of the physical fields, pressure, and temperature. The equation of state enables us to accurately locate the "Widom line" (the locus of stability minima) and determine that the critical pressure is considerably lower than predicted by computer simulations.

Competition of mesoscales and crossover to theta-point tricriticality in near-critical polymer solutions.

The approach to asymptotic critical behavior in polymer solutions is governed by a competition between the correlation length of critical fluctuations diverging at the critical point of phase separation and an additional mesoscopic length scale, the radius of gyration. In this paper we present a theory for crossover between two universal regimes: a regime with Ising (fluctuation-induced) asymptotic critical behavior, where the correlation length prevails, and a mean-field tricritical regime with theta-point behavior controlled by the mesoscopic polymer chain. The theory yields a universal scaled description of existing experimental phase-equilibria data and is in excellent agreement with our light-scattering experiments on polystyrene solutions in cyclohexane with polymer molecular weights ranging from 2 x 10(5) up to 11.4 x 10(6). The experiments demonstrate unambiguously that crossover to theta-point tricriticality is controlled by a competition of the two mesoscales. The critical amplitudes deduced from our experiments depend on the polymer molecular weight as predicted by de Gennes [Phys. Lett. 26A, 313 (1968)]. Experimental evidence for the presence of logarithmic corrections to mean-field tricritical theta-point behavior in the molecular-weight dependence of the critical parameters is also presented.

Pretransitional fluctuations in the isotropic phase of a lyotropic chromonic liquid crystal.

We have studied isotropic-to-nematic pretransitional fluctuations in an aqueous solution of disodium cromoglycate (cromolyn) by static and dynamic light scattering. Cromolyn is a representative of lyotropic chromonic liquid crystals with building units being elongated rods formed by aggregates of disk-like molecules. By combining light-scattering and viscosity measurements we have determined the correlation length and relaxation time of the orientational order-parameter fluctuations and estimated the size of the cromolyn aggregates. The pretransitional behavior of light scattering does not completely follow the classic Landau-de Gennes model. This feature is most probably associated with the variable length of cromolyn aggregates. We have observed a dramatic increase of the shear viscosity near the transition to the nematic phase, the fact which correlates with the idea of growing supramolecular aggregates. The steep temperature dependence of the viscosity is accompanied by a practically temperature-independent translational diffusion coefficient.

Criticality in aqueous solutions of 3-methylpyridine and sodium bromide.

We address a controversial issue regarding the nature of critical behavior in ternary electrolyte solutions of water, 3-methylpyridine, and sodium bromide. Earlier light-scattering studies showed an anomalous critical behavior in this system that was attributed to the formation of a microheterogeneous phase associated with ion-molecule clustering [M.A. Anisimov, J. Jacob, A. Kumar, V.A. Agayan, and J. V. Sengers, Phys. Rev. Lett. 85, 2336 (2000)]], while some other investigators subsequently found this system to exhibit ordinary Ising-like critical behavior. This contradiction forced us to revisit the problem and perform an accurate and comprehensive study of light scattering in this system paying attention to the achievement of thermodynamic equilibrium, hysteresis effects, aging, and prehistory of the samples, and a possible role of impurities. We show that properly aged, equilibrium samples of aqueous solutions of 3-methylpyridine with NaBr exhibit universal Ising-like critical behavior, typical for other aqueous solutions. No evidence for an equilibrium microheterogeneous phase was found. We have been able to reproduce anomalous behavior (similar to that reported initially) in a fast run on a freshly prepared sample. We attribute the observed anomalies to mesoscopic nonequilibrium aggregates, possibly associated with supramolecular restructuring in aqueous solutions. To support this conclusion we performed a study of aqueous solutions of 3-methylpyridine without NaBr and have found long-living nonequilibrium states in aqueous solutions of 3-methylpyridine.

The Yana RHS site: humans in the Arctic before the last glacial maximum.

A newly discovered Paleolithic site on the Yana River, Siberia, at 71 degrees N, lies well above the Arctic circle and dates to 27,000 radiocarbon years before present, during glacial times. This age is twice that of other known human occupations in any Arctic region. Artifacts at the site include a rare rhinoceros foreshaft, other mammoth foreshafts, and a wide variety of tools and flakes. This site shows that people adapted to this harsh, high-latitude, Late Pleistocene environment much earlier than previously thought.

Dynamic crossover to tricriticality and anomalous slowdown of critical fluctuations by entanglements in polymer solutions.

We have performed accurate dynamic light-scattering measurements near critical demixing points of solutions of polystyrene in cyclohexane with polymer molecular weight ranging from 200 000 to 11.4 x 10(6). Two dynamic modes have been observed, "slow" and "fast," which result from a coupling between diffusive relaxation of critical fluctuations of the concentration and viscoelastic relaxation associated with the entanglement network of the polymer chains. The coupling with the viscoelastic mode causes an additional slowdown of the critical mode on top of the uncoupled diffusion mode. By implementing crossover from the critical to the theta-point tricritical behavior for both static and dynamic properties, we are able to present a quantitative description of the phenomenon and obtain a scaling of the viscoelastic parameters as a function of the molecular weight.