Determination of the vapor–liquid transition of square-well particles using a novel generalized-canonical-ensemble-based method

The square-well(SW) potential is one of the simplest pair potential models and its phase behavior has been clearly revealed, therefore it has become a benchmark for checking new theories or numerical methods. We introduce the generalized canonical ensemble(GCE) into the isobaric replica exchange Monte Carlo(REMC) algorithm to form a novel isobaric GCE-REMC method, and apply it to the study of vapor–liquid transition of SW particles. It is validated that this method can reproduce the vapor–liquid diagram of SW particles by comparing the estimated vapor–liquid binodals and the critical point with those from the literature. The notable advantage of this method is that the unstable vapor–liquid coexisting states,which cannot be detected using conventional sampling techniques, are accessed with a high sampling efficiency. Besides,the isobaric GCE-REMC method can visit all the possible states, including stable, metastable or unstable states during the phase transition over a wide pressure range, providing an effective pathway to understand complex phase transitions during the nucleation or crystallization process in physical or biological systems.     

A multicomponent multiphase lattice Boltzmann model with large liquid–gas density ratios for simulations of wetting phenomena

A multicomponent multiphase(MCMP) pseudopotential lattice Boltzmann(LB) model with large liquid–gas density ratios is proposed for simulating the wetting phenomena. In the proposed model, two layers of neighboring nodes are adopted to calculate the fluid–fluid cohesion force with higher isotropy order. In addition, the different-time-step method is employed to calculate the processes of particle propagation and collision for the two fluid components with a large pseudoparticle mass contrast. It is found that the spurious current is remarkably reduced by employing the higher isotropy order calculation of the fluid–fluid cohesion force. The maximum spurious current appearing at the phase interfaces is evidently influenced by the magnitudes of fluid–fluid and fluid–solid interaction strengths, but weakly affected by the time step ratio.The density ratio analyses show that the liquid–gas density ratio is dependent on both the fluid–fluid interaction strength and the time step ratio. For the liquid–gas flow simulations without solid phase, the maximum liquid–gas density ratio achieved by the present model is higher than 1000:1. However, the obtainable maximum liquid–gas density ratio in the solid–liquid–gas system is lower. Wetting phenomena of droplets contacting smooth/rough solid surfaces and the dynamic process of liquid movement in a capillary tube are simulated to validate the proposed model in different solid–liquid–gas coexisting systems. It is shown that the simulated intrinsic contact angles of droplets on smooth surfaces are in good agreement with those predicted by the constructed LB formula that is related to Young's equation. The apparent contact angles of droplets on rough surfaces compare reasonably well with the predictions of Cassie's law. For the simulation of liquid movement in a capillary tube, the linear relation between the liquid–gas interface position and simulation time is observed, which is identical to the analytical prediction. The simulation results regarding the wetting phenomena of droplets on smooth/rough surfaces and the dynamic process of liquid movement in the capillary tube demonstrate the quantitative capability of the proposed model.     

Measurement scheme to detect α relaxation time of glass-forming liquid

A measurement scheme for detecting the α relaxation time(τ) of glass-forming liquid is proposed, which is based on the measured ionic conductivity of the liquid doped with probing ions by low-and middle-frequency dielectric spectroscopy and according to the Nernst–Einstein, Stokes–Einstein, and Maxwell equations. The obtained τ values of glycerol and propylene carbonate by the scheme are consistent with those obtained by traditional dielectric spectroscopy, which confirms its reliability and accuracy. Moreover, the τ of 1,2-propanediol in a larger temperature range is compared with existing data.     

Abnormal breakdown of Stokes–Einstein relation in liquid aluminium

We present the results of systematic molecular dynamics simulations of pure aluminium melt with a well-accepted embedded atom potential. The structure and dynamics were calculated over a wide temperature range, and the calculated results(including the pair correlation function, self-diffusion coefficient, and viscosity) agree well with the available experimental observations. The calculated data were used to examine the Stokes–Einstein relation(SER). The results indicate that the SER begins to break down at a temperature T_x(~1090 K) which is well above the equilibrium melting point(912.5 K).This high-temperature breakdown is confirmed by the evolution of dynamics heterogeneity, which is characterised by the non-Gaussian parameter α_2(t). The maximum value of α 2(t), α_(2,max), increases at an accelerating rate as the temperature falls below Tx. The development of α_(2,max) was found to be related to the liquid structure change evidenced by local fivefold symmetry. Accordingly, we suggest that this high-temperature breakdown of SER has a structural origin. The results of this study are expected to make researchers reconsider the applicability of SER and promote greater understanding of the relationship between dynamics and structure.     

Analysis of meniscus beneath metastable droplets and wetting transition on micro/nano textured surfaces

The expressions of interface free energy(IFE) of composite droplets with meniscal liquid–air interface in metastable state on micro/nano textured surfaces were formulated. Then the parameters to describe the meniscus were determined based on the principle of minimum IFE. Furthermore, the IFE barriers and the necessary and sufficient conditions of drop wetting transition from Cassie to Wenzel were analyzed and the corresponding criteria were formulated. The results show that the liquid–air interface below a composite droplet is flat when the post pitches are relatively small, but in a shape of curved meniscus when the piteches are comparatively large and the curvature depends on structural parameters. The angle between meniscus and pillar wall is just equal to the supplementary angle of intrinsic contact angle of post material. The calculations also illustrate that Cassie droplets will transform to Wenzel state when post pitch is large enough or when drop volume is sufficiently small. The opposite transition from Wenzel to Cassie state, however, is unable to take place spontaneously because the energy barrier is always positive. Finally, the calculation results of this model are well consistent with the experimental observations in literatures for the wetting transition of droplets from Cassie to Wenzel state.     

Non-monotonic temperature evolution of nonlocal structure–dynamics correlation in CuZr glass-forming liquids

The structure–dynamics correlations in a nonlocal manner were investigated in CuZr metallic glass-forming liquids via classical molecular dynamics simulations. A spatial coarse-graining approach was employed to incorporate the nonlocal structural information of given structural order parameters in the structure–dynamics relationship. It is found that the correlation between structure order parameters and dynamics increases with increasing coarse-graining length and has a characteristic length scale. Moreover, the characteristic correlation length exhibits a non-monotonic temperature evolution as temperature approaches glass transition temperature, which is not sensitive to the considered structure order parameters.Our results unveil a striking change in the structure–dynamics correlation, which involves no fitting theoretical interpretation. These findings provide new insight into the structure–dynamics correlation in glass transition.     

Quantum phase transitions of fermionic atoms in an anisotropic triangular optical lattice

The effect of anisotropy caused by a confining potential on the properties of fermionic cold atoms in a triangular optical lattice is systematically investigated by using the dynamical cluster approximation combined with the continuous time quantum Monte–Carlo algorithm.The quantum phase diagrams which reflect the temperature–interaction relation and the competition between the anisotropic parameter and the interaction are presented with full consideration of the anisotropy of the system.Our results show that the system undergoes a transition from Fermi liquid to Mott insulator when the repulsive interaction reaches a critical value.The Kondo effect also can be observed in this system and the pseudogap is suppressed at low temperatures due to the Kondo effect.A feasible experiment protocol to observe these phenomena in an anisotropic triangular optical lattice with cold atoms is proposed,in which the hopping terms are closely related to the lattice confining potential and the atomic interaction can be adjusted via the Feshbach resonance.     

Studies of flow field characteristics during the impact of a gaseous jet on liquid–water column

Both experimental and numerical studies were presented on the flow field characteristics in the process of gaseous jet impinging on liquid–water column. The effects of the impinging process on the working performance of rocket engine were also analyzed. The experimental results showed that the liquid–water had better flame and smoke dissipation effect in the process of gaseous jet impinging on liquid–water column. However, the interaction between the gaseous jet and the liquid–water column resulted in two pressure oscillations with large amplitude appearing in the combustion chamber of the rocket engine with instantaneous pressure increased by 17.73% and 17.93%, respectively. To analyze the phenomena, a new computational method was proposed by coupling the governing equations of the MIXTURE model with the phase change equations of water and the combustion equation of propellant. Numerical simulations were carried out on the generation of gas, the accelerate gas flow, and the mutual interaction between gaseous jet and liquid–water column.Numerical simulations showed that a cavity would be formed in the liquid–water column when gaseous jet impinged on the liquid–water column. The development speed of the cavity increased obviously after each pressure oscillation. In the initial stage of impingement, the gaseous jet was blocked due to the inertia effect of high-density water, and a large amount of gas gathered in the area between the nozzle throat and the gas–liquid interface. The shock wave was formed in the nozzle expansion section. Under the dual action of the reverse pressure wave and the continuously ejected high-temperature gas upstream, the shock wave moved repeatedly in the nozzle expansion section, which led to the flow of gas in the combustion chamber being blocked, released, re-blocked, and re-released. This was also the main reason for the pressure oscillations in the combustion chamber.     

Characterization of structural transitions and lattice dynamics of hybrid organic–inorganic perovskite CH_3NH_3PbI_3

By combining temperature-dependent x-ray diffraction(XRD) with temperature-dependent Raman scattering, we have characterized the structural transitions and lattice dynamics of the hybrid organic–inorganic perovskite CH_3NH_3PbI_3.The XRD measurements cover distinct phases between 15 K and 370 K and demonstrate a general positive thermal expansion.Clear anomalies are found around the transition temperatures.The temperature evolution of the lattice constants reveals that the transition at 160 K/330 K is of the first-/second-order type.Raman measurements uncover three strong lowfrequency modes, which can be ascribed to the vibration of the Pb/I atoms.The temperature evolution of the modes clearly catches these transitions at 160 K and 330 K, and confirms the transition types, which are exactly consistent with the XRD results.The present study may set an experimental basis to understand the high conversion efficiency in methylammonium lead iodide.     

Piezoelectric and electro optic properties of tetragonal(1-x)Pb(Mg_(1/3)Nb_(2/3))O_3-xPbTiO_3 single crystals by phenomenological theory

An eighth-order Landau–Devonshire theory is constructed to investigate the piezoelectric and electro–optic properties of tetragonal(1- x)Pb(Mg1/3Nb2/3)O3–x Pb Ti O3 single crystals(x = 0.38 and x = 0.4). The dielectric stiffness coefficients of the Landau potential are obtained by fitting to the dielectric properties and the phase transition temperature between cubic phase and tetragonal phase. It is indicated that tetragonal(1- x)Pb(Mg1/3Nb2/3)O3–x Pb Ti O3 single crystals have the firstorder cubic-tetragonal phase transitions. The dielectric constants are in great agreement with the experimental results.The piezoelectric coefficients d33 and d31at room temperature are about 145 p C/N and-62 p C/N respectively which are smaller than that of(1- x)Pb(Mg1/3Nb2/3)O3–x Pb Ti O3 single crystals around the morphotropic phase boundary.Moreover, tetragonal(1- x)Pb(Mg1/3Nb2/3)O3–x Pb Ti O3 single crystals have the linear electro–optic coefficients rc =33.7 pm/V and rc = 28.8 pm/V for x = 0.38 and x = 0.4, respectively which are in accordance with the measurements.     

液体-液体相变与反常特性

绝大多数物质的液态密度随温度降低而增大,即常见的热胀冷缩现象.但存在一类物质,如水及第四主族的硅、锗等,其液态密度在一定温度范围内随温度的升高而增大,即密度反常现象.此外,该类物质还存在动力学反常(密度越大粒子运动越快)、热力学反常(热力学量的涨落随温度降低而升高)等其他反常特性.这类材料的化学性质千差万别,但却具有相似的物理反常特性.进一步的理论研究发现部分材料具有两种液态,即高密度液态和低密度液态,两者之间存在一级相变.因此,反常特性与液体-液体相变是否有直接关联是一个值得深入研究的课题.本文主要介绍了具有液体-液体相变的一类材料及其反常特性,包括高温高压下氢的液体-液体相变及其超临界现象,镓的反常特性及其与液体-液体相变的关联等.     

Liquid-liquid phase transition in water

Water shows anomalies different from most of other materials.Different sceniaros have been proposed to explain water anomalies,among which the liquid-liquid phase transition(LLPT)is the most discussed one.It attributes water anomalies to the existence of a hypothesized liquid-liquid critical point(LLCP)buried deep in the supercooled region.We briefly review the recent experimental and theoretical progresses on the study of the LLPT in water.These studies include the discussion on the existence of the first order LLPT in supercooled water and the detection of liquid-liquid critical point.Simulational results of different water models for LLPT and the experimental evidence in confined water are also discussed.     

Liquid-liquid phase transition in elemental carbon: a first-principles investigation

It has been recently suggested that elemental carbon may be a promising candidate to exhibit a liquid-liquid phase transition (LLPT). We report the results of first-principles molecular dynamics simulations showing no evidence of LLPT in carbon, in the same temperature and pressure range where such a transition was found using empirical calculations. Our simulations indicate a continuous evolution from a primarily sp-bonded liquid to an sp(2)-like and an sp(3)-like fluid, as a function of pressure, above the graphite melting line. The discrepancy between quantum and classical simulations is attributed to the inability of empirical potentials to describe complex electronic effects in condensed carbon phases.     

Density and bond-orientational relaxations in supercooled water

ABSTRACT

Recent computational studies have reported evidence of a metastable liquid–liquid phase transition (LLPT) in molecular models of water under deeply supercooled conditions. A competing hypothesis suggests, however, that non-equilibrium artefacts associated with coarsening of the stable crystal phase have been mistaken for an LLPT in these models. Such artefacts are posited to arise due to a separation of time scales in which density fluctuations in the supercooled liquid relax orders of magnitude faster than those associated with bond-orientational order. Here, we use molecular simulation to investigate the relaxation of density and bond-orientational fluctuations in three molecular models of water (ST2, TIP5P and TIP4P/2005) in the vicinity of their reported LLPT. For each model, we find that density is the slowly relaxing variable under such conditions. We also observe similar behaviour in the coarse-grained mW model of water. Our findings, therefore, challenge the key physical assumption underlying the competing hypothesis.     

Transport properties of supercooled confined water

This article presents an overview of recent experiments performed on transport properties of water in the deeply supercooled region, a temperature region of fundamental importance in the science of water. We report data of nuclear magnetic resonance, quasi-elastic neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy, studying water confined in nanometer-scale environments. When contained within small pores, water does not crystallise, and can be supercooled well below its homogeneous nucleation temperature T_h. On this basis it is possible to carry out a careful analysis of the well known thermodynamical anomalies of water. Studying the temperature and pressure dependencies of water dynamics, we show that the liquid-liquid phase transition (LLPT) hypothesis represents a reliable model for describing liquid water. In this model, water in the liquid state is a mixture of two different local structures, characterised by different densities, namely the low density liquid (LDL) and the high-density liquid (HDL). The LLPT line should terminate at a special transition point: a low-T liquid-liquid critical point. We discuss the following experimental findings on liquid water: (i) a crossover from non-Arrhenius behaviour at high T to Arrhenius behaviour at low T in transport parameters; (ii) a breakdown of the Stokes-Einstein relation; (iii) the existence of a Widom line, which is the locus of points corresponding to maximum correlation length in the p-T phase diagram and which ends in the liquid-liquid critical point; (iv) the direct observation of the LDL phase; (v) a minimum in the density at approximately 70 K below the temperature of the density maximum. In our opinion these results represent the experimental proofs of the validity of the LLPT hypothesis.     

The Boson peak in confined water: An experimental investigation of the liquid-liquid phase transition hypothesis

The Boson peak (BP) of deeply cooled confined water is studied by using inelastic neutron scattering (INS) in a large interval of the (P, T) phase plane. By taking into account the different behavior of such a collective vibrational mode in both strong and fragile glasses as well as in glass-forming materials, we were able to determine the Widom line that characterizes supercooled bulk water within the frame of the liquid-liquid phase transition (LLPT) hypothesis. The peak frequency and width of the BP correlated with the water polymorphism of the LLPT scenario, allowing us to distinguish the “low-density liquid” (LDL) and “high-density liquid” (HDL) phases in deeply cooled bulk water.Moreover, the BP properties afford a further confirmation of theWidom line temperature T_W as the (P, T) locus in which the local structure of water transforms from a predominately LDL form to a predominately HDL form.     

Hydrophobic nanoconfinement suppresses fluctuations in supercooled water

We perform very efficient Monte Carlo simulations to study the phase diagram of a water monolayer confined in a fixed disordered matrix of hydrophobic nanoparticles between two hydrophobic plates. We consider different hydrophobic nanoparticle concentrations c. We adopt a coarse-grained model of water that, for c = 0, displays a first-order liquid-liquid phase transition (LLPT) line with negative slope in the pressure-temperature (P-T) plane, ending in a liquid-liquid critical point at about 174 K and 0.13 GPa. We show that upon increase of c the liquid-gas spinodal and the temperature of the maximum density line are shifted with respect to the c = 0 case. We also find dramatic changes in the region around the LLPT. In particular, we observe a substantial (more than 90%) decrease of isothermal compressibility, thermal expansion coefficient and constant-pressure specific heat upon increasing c, consistent with recent experiments. Moreover, we find that a hydrophobic nanoparticle concentration as small as c = 2.4% is enough to destroy the LLPT for P ≥ 0.16 GPa. The fluctuations of volume apparently diverge at P ≈ 0.16 GPa, suggesting that the LLPT line ends in an LL critical point at 0.16 GPa. Therefore, nanoconfinement reduces the range of P-T where the LLPT is observable. By increasing the hydrophobic nanoparticle concentration c, the LLPT becomes weaker and its P-T range smaller. The model allows us to explain these phenomena in terms of a proliferation of interfaces among domains with different local order, promoted by the hydrophobic effect of the water-hydrophobic-nanoparticle interfaces.     

P granules phase transition induced by cytoplasmic streaming in Caenorhabditis elegans embryo

P granules are germ granules contained in Caenorhabditis elegans germ cells.The first germ cell is specified by the one-cell embryo in which P granules localize to the posterior.Previous studies suggested that the mechanism of the localization phenomena is induced by liquid-liquid phase transition(LLPT),in which the polarity proteins control the saturation point of P granules.In the present study,we propose that the P granules phase transition can be triggered by the cytoplasmic streaming.A two-phase flow model is employed to simulate the localization of P granules,i.e.,the cytoplasm is considered as a liquid phase,and the droplet-like P granules are another liquid phase.With the presence of the cytoplasmic streaming,P granules,initially distributing uniformly in the entire one-cell embryo,eventually condense/dissolve in the cytoplasm phase,regulated by difference between the saturation pressure and the hydrodynamic pressure.The numerical results reveal that the cytoplasmic streaming has significant effects on the localization of P granules,as well as the embryo division.     

A computational investigation of the thermodynamics of the Stillinger-Weber family of models at supercooled conditions

The existence of metastable liquid-liquid phase transitions (LLPTs) in tetrahedral liquids such as water, silicon, and silica has been the subject of vigorous scientific debate. Because high crystallization rates hinder experimental investigation at deeply supercooled conditions, computer simulation has been widely employed to investigate the existence of LLPTs in molecular models of tetrahedral liquids. The Stillinger-Weber (SW) model of silicon (and more generally, the SW family of models) has been actively studied along these lines. Whereas some studies observe evidence of an LLPT in this model, others report that only a single metastable liquid exists under deeply supercooled conditions. Here, we perform extensive state-of-the-art free energy calculations to investigate the possibility of an LLPT in the SW model of silicon. A similar analysis is also presented for the generalized SW family of models constructed by varying the strength of the three-body energetic term. Our analysis does not show any evidence of an LLPT in SW silicon nor in the generalized family of SW models over the parameter ranges studied. Explanations for the aforementioned discrepancies between previous studies are provided, along with explicit demonstrations of how these discrepancies may have occurred. Outstanding ambiguities and directions for future work are also discussed.