Application of the density functional method to study phase transitions in an associating Lennard-Jones fluid adsorbed in energetically heterogeneous slit-Like pores

A density functional approach is used to study the adsorption of the four-bonding-site model associating Lennard-Jones fluid in slit-Like pores with energetically heterogeneous walls. The fluid-wall potential is qualitatively similar to that invoked by Röcken, P., Somoza, A., Tarazona, P., and Findenegg, G. H., 1999, J. chem. Phys., 108, 8089, i.e. it consists of a homogeneous part that varies in the direction perpendicular to the wall and a periodic part, varying also in one direction parallel to the wall. Both parts are modelled by Lennard-Jones 9,3-type functions. The structure of the adsorbed film is characterized by the local densities of all particles and the densities of the monomers. The phase diagrams are evaluated for several systems characterized by different corrugation of the adsorbing potential. The adsorbing field is strong enough to allow for the layering transition. As well as the formation of the so-called bridge phase that fills the pore space over the most energetic parts of the wall and of capillary condensation, the layering transition is observed within the first layer adjacent to the pore walls. If the adsorbing potential due to each pore wall is shifted in phase by π/2, the bridge phase is not formed.     

受限于对称性破缺狭缝间氢键流体的相平衡研究

利用密度泛函理论并结合改进的基本度量理论研究了受限于对称性破缺狭缝间氢键流体的相平衡. 首先根据氢键流体的吸附-脱附等温线及相应巨势获得不同条件下氢键流体的相图. 进一步讨论了氢键作用、狭缝间距、狭缝与流体分子间相互作用及对称性破缺程度等因素对氢键流体相平衡的影响. 结果表明, 由于狭缝与流体分子及流体分子间的相互作用存在竞争, 使得受限于对称性破缺条件下的氢键流体呈现更为复杂的相态特征.     

Demixing transitions in a binary Gaussian-core fluid confined in narrow slit-like pores

Using a mean-field density functional approach we investigate phase separation transition in a binary mixture of Gaussian-core molecules confined in narrow slit-like pores. We consider pores with repulsive and attractive walls. In the case of fluid confinement in pores with repulsive and non-selective attracting walls, no phase separation in the confined fluid, prior to the bulk separation transition, was observed. However, in the case of pores with the walls selectively attracting fluid particles, we reveal that the separation transition may take place as a two-step process. During the first step the composition change occurs within a few layers adjacent to the pore walls, whereas in the second step, it takes place in the pore interior.     

Helium-4 Bose fluids formed in one-dimensional 18 A diameter pores

Bose fluids restricted in one dimension (1D) are realized by adsorbing 4He atoms on the 1D pore walls with a diameter of about 18 A. The Bose fluid appears above an adsorbed amount after the pore walls are coated with the inert 4He atoms. Heat capacity of the fluid was observed to have a temperature-linear term at low temperatures. This corresponds to the phonon heat capacity of the Bose fluid in the 1D pores. We estimate the phonon velocity and the interaction of the 1D Bose fluid.     

Phase coexistence and dynamic properties of water in nanopores

The dynamical properties of a confined fluid depend strongly on the (spatially varying) density. Its knowledge is therefore an important prerequisite for molecular-dynamics (MD) simulations and the analysis of experimental data. In a mixed Gibbs ensemble Monte Carlo (GEMC)/MD simulation approach we first apply the GEMC method to find possible phase states of water in hydrophilic and hydrophobic nanopores. The obtained phase diagrams evidence that a two-phase state is the most probable state of a fluid in incompletely filled pores in a wide range of temperature and level of pore filling. Pronounced variations of the average and local densities are observed. Subsequently, we apply constant-volume MD simulations to obtain water diffusion coefficients and to study their spatial variation along the pore radius. In general, water diffusivity slightly decreases in a hydrophilic pore and noticeably increases in a hydrophobic pore (up to about 40% with respect to the bulk value). In the range of gradual density variations the local diffusivity essentially follows the inverse density and the water binding energy. The diffusivity in the quasi-two-dimensional water layers near the hydrophilic wall decreases by 10 to 20% with respect to the bulk value. The average diffusivity of water in incompletely filled pore is discussed on the basis of the water diffusivities in the coexisting phases.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.20.Ja Computer simulation of liquid structure - 64.70.Fx Liquid-vapor transitions     

Demixing of a binary mixture in slit-like pores at high temperatures

We investigate the fluid—fluid demixing transitions in the case of adsorption of so-called symmetric binary mixtures in slit-like pores at temperatures higher than the bulk gas—liquid critical temperature. The aim of the study is to determine how the demixing of such mixtures in the pores depends on the bulk phase composition and on the parameters characterizing the pore. The calculations have been carried out by means of a density functional theory. In the case of an equimolar bulk mixture, the demixing transition inside the pore occurs only when the adsorption potentials of both species are identical. The occurrence of this transition is manifested by a cusp in the adsorption isotherm. For nonequimolar bulk phase compositions, the transition can also take place if the adsorption energies of both components are different. However, the difference in the adsorption energies should be small enough, otherwise a continuous demixing takes place. For non-equimolar compositions two branches of the grand canonical potential intersect, whereas for equimolar bulk composition they meet tangentially. We have determined phase behaviour for several model systems.     

Pair superfluidity of three-body constrained bosons in two dimensions

We examine the equilibrium properties of lattice bosons with attractive on-site interactions in the presence of a three-body hard-core constraint that stabilizes the system against collapse and gives rise to a dimer superfluid phase. Employing quantum Monte Carlo simulations, the ground state phase diagram of this system on the square lattice is analyzed. In particular, we study the quantum phase transition between the atomic and dimer superfluid regime and analyze the nature of the superfluid-insulator transitions. Evidence is provided for the existence of a tricritical point along the saturation transition line, where the transition changes from being first order to a continuous transition of the dilute Bose gas of holes. The Berzinskii-Kosterlitz-Thouless transition from the dimer superfluid to the normal fluid is found to be consistent with an anomalous stiffness jump, as expected from the unbinding of half-vortices.     

Parastatistics and phase transition from a cluster as a fluctuation to a cluster as a distinguishable object

A phase transition of the first kind is a jump of a function, a phase transition of the second kind is a jump of its first derivative, a phase transition of the third kind, a jump of the second derivative. A phase transition from one statistic to another is very gradual, but finally it is as considerable as the phase transition of the first kind. However, we cannot introduce a clearly defined parameter to which this transition corresponds. This is due to the fact that the fluctuations near the critical point are huge, and this violates, in the vicinity of that point, the main law of equilibrium thermodynamics, which asserts that fluctuations are relatively small. The paper describes the transition in the supercritical fluid region of equilibrium thermodynamics from parastatistics to mixed statistics, in which the Boltzmann statistics is realized for long-living clusters. In economics this corresponds to a negative nominal credit rate. Examples of this non-standard situation are presented.     

Reentrant filling transitions in Lennard-Jones fluids confined in nanoscopic slit-like pores

The reentrant first-order pore filling transition in a Lennard-Jones (LJ) fluid confined between the parallel (100) planes of the face centered cubic (fcc) crystal is studied by means of Monte Carlo simulations in the canonical as well as grand canonical ensembles. Slit-like pores of the width allowing for the formation of only three adsorbate layers are used. It is demonstrated that the reentrant first-order pore filling transition, associated with the condensation of the middle layer, appears only when the height of the potential barrier between adjacent sites, V_D, fulfills a condition V_D∈[V_D,min,V_D,max]. The lower limit of V_D (V_D,min) is primarily determined by the stability of commensurate monolayers formed at both pore walls during the first step of adsorbate condensation, while the upper limit of V_D (V_D,max) depends on the stability of the commensurate three-layer structure. It is also shown that both the misfit between the size of adsorbed atom and the surface lattice as well as the pore width have a great influence on the phase behavior of confined fluids. Moreover, the effects of the phase shift between the confining lattices on the reentrant first-order filling transition are discussed.     

石膏溶解相变过程中流体效应的拉曼光谱研究

应用拉曼光谱仪,原位观测了不同流体中石膏随温度变化的溶解相变过程。纯水流体升温过程中,石膏在170～190℃范围内发生脱水,相变为无水石膏,随后升至250℃再快速降至常温,无水石膏无变化,脱水相变过程不可逆;1mol.L-1 Na2SO4溶液升温过程中,石膏在170～190℃范围内发生脱水,相变为无水石膏,升至250℃再快速降至常温,无水石膏重新相变为含水石膏,脱水相变过程可逆。该研究反映流体效应会影响矿物溶解相变机制,研究过程中不可忽视。     

CRITICAL SCALING THEORY OF GENERALIZED PHASE TRANSITION AND ITS UNIVERSALITY

Generalized phase transition (GPT) refers to the transition process of material systems from one steady-state to another. It includes equilibrium phase transition (EPT) and nonequilibrium phase transition (NPT), and phase transitions intermediate between them. In this paper some results on the study of critical scaling relations of the NPT and EPT are obtained. We developed the critical scaling theory of EPT and advanced a universal critical scaling theory of GPT. The critical scaling relations(scaling laws) has more niversality. The critical exponents calculated from our theory are identical with the results of experiments and other theories about EPT and NPT systems. Because the basic model of the theory does not depend on the concrete material system, it has a certain unversality. Its results thus can be applied to generlized phase transition systems, such as the electrorheological fluid and magnetorheological fluid systems.     

Constant pressure Gibbs ensemble Monte Carlo simulations of adsorption into narrow pores

An extension to the Gibbs ensemble method for the study of adsorption of fluids into pores is proposed. Since equality of pressure is not a necessary condition for full thermodynamic equilibrium between the bulk fluid and that confined in a narrow cavity, previous studies have been performed with the volume of both simulation cells fixed. More naturally, the pressure of the bulk fluid should be constrained and the volume (and hence density) allowed to attain its equilibrium value. Thus we propose a scheme in which volume fluctuations within the bulk box are permitted; the volume of the pore remains constant. The pressure is an input parameter and the amount of adsorption, as a function of applied pressure, is obtained directly. We demonstrate that the novel moves obey microscopic reversibility. Such a method is most useful when the equation of state for the model fluid is unknown. Thus, we illustrate the method by simulating an associating model of water adsorbed into a slit-shaped carbon pore with activated sites. Good qualitative correspondence with experiment is obtained; further refinement of our model is expected to yield quantitative agreement.     

Stability analysis of a model equilibrium for a gravito-electrostatic sheath in a colloidal plasma under external gravity effect

The present contribution tries to find a scientific answer to the question of stability of an equilibrium plasma sheath in a colloidal plasma system under external gravity effect. A model equilibrium of hydrodynamical character has been discussed on the basis of quasi-hydrostatic approximation of levitational condition. It is found that such an equilibrium is highly unstable to a modified-ion acoustic wave with a conditional likelihood of linear driving of the so-called acoustic mode too. Thus, it is reported (within fluid treatment) that a plasma-sheath edge in a colloidal plasma under external gravity effect could be highly sensitive to the acoustic turbulence. Its consequential role on possible physical mechanism of Coulomb phase transition has been conjectured. However, more rigorous calculations as future course of work are required to corroborate our phenomenological suggestions.     

Polymer-mediated interactions of fluid membranes in a lyotropic lamellar phase: a small angle X-ray and neutron scattering study

Small angle X-ray and neutron scattering data on an effective three-component lamellar phase composed of water, a non adsorbing water-soluble polymer (polyvynilpyrolidone), fluid membranes, made from a mixture of a cationic surfactant (cetylpiridiumchloride) and a cosurfactant (hexanol), are presented for various membrane as well as polymer concentrations. The data are fitted with a recently proposed model which takes into account the geometry and the fluctuations of these periodic structures. This allows a quantitative study of the polymer contribution to the smectic compression modulus of the lamellar phase. Four different regimes of polymer confinement are expected. The associated variations in are compared to a recent theoretical model, which predicts the polymer-mediated contribution to the smectic compression modulus. Received 20 January 1998     

Demixing of amphiphile–polymer mixtures investigated using density functional theory

We construct a functional for amphiphile–polymer mixtures and investigate the demixing transition by using a proposed version of density functional theory. It is found that increase of the amphiphilic size ratio and polymer length can effectively promote phase separation of the systems. Phase diagrams are plotted to clarify these influences. The results provide an effective way of controlling the stability of the fluid–fluid phase equilibrium of the mixtures.     

Metastable molecular fluid hydrogen at high pressures

Warm dense hydrogen is studied in the region of fluid–fluid phase transition within the framework of the density functional theory. We report a procedure of obtaining metastable states and calculate the equation of state. Metastable states are diagnosed by pair correlation functions and values of conductivity. We obtain a strong overlapping through the density of metastable and equilibrium branches of pressure isotherms. This indicates the plasma nature of the phase transition.     

Spontaneous Breaking of Translational Invariance and Spatial Condensation in Stationary States on a Ring. I. The Neutral System

We consider a model in which positive and negative particles with equal densities diffuse in an asymmetric, CP-invariant way on a ring. The positive particles hop clockwise, the negative counterclockwise, and oppositely charged adjacent particles may swap positions. The model depends on two parameters. Analytic calculations using quadratic algebras, inhomogeneous solutions of the mean-field equations, and Monte Carlo simulations suggest that the model has three phases: (1) a pure phase in which one has three pinned blocks of only positive or negative particles and vacancies and in which translational invariance is broken; (2) a mixed phase in which the current has a linear dependence on one parameter, but is independent of the other one and of the density of the charged particles; in this phase one has a bump and a fluid, the bump (condensate) containing positive and negative particles only, the fluid containing charged particles and vacancies uniformly distributed; and (3) the mixed phase is separated from the disordered phase by a second-order phase transition which has many properties of the Bose–Einstein phase transition observed in equilibrium. Various critical exponents are found.     

气泡成核过程的格子Boltzmann方法模拟

利用精确差分格子Boltzmann模型探讨水在特定温度下的亚稳态及不稳定平衡态, 获得等温相变过程中形成气泡和液滴的条件, 模型预测结果与理论解符合良好. 在该等温模型的基础上耦合能量方程, 通过调节流体-壁面相互作用力获得不同的气泡与固壁间接触角, 从而建立了一种新的描述气液相变的格子Boltzmann理论模型. 利用该新模型模拟不同流体-壁面相互作用力下凹坑气泡成核过程, 再现了气泡成核过程中的三阶段特性; 探讨了接触角、曲率半径及气泡体积随气泡成核过程的变化关系, 获得了与文献结果定性符合的曲率-气泡体积关系曲线. 关键词： 格子Boltzmann方法 气泡成核过程 气液相变 接触角     

Spurious character of singularities associated with phase transitions in cylindrical pores

Phase transitions of simple fluids and binary fluid mixtures confined into long cylindrical pores are re-examined, such as capillary condensation/evaporation and wetting transitions. While a large part of the literature ignores the fact that due to the quasi-one-dimensional character of these systems a singular behavior associated with a sharp phase transition cannot occur, we pay attention to the extent in which these phase transitions are smoothed out (in relation to the magnitude of the pore cross-sectional area). We argue that the finiteness of the pore length is an important parameter which controls the physical phenomena that are observed in simulations (and presumably also experiments explaining the distinction between the apparent “pore critical temperature” and the “hysteresis critical temperature”). We illustrate our arguments with recent findings from simulations of a lattice gas/Ising system and of the Asakura-Oosawa model of colloid-polymer mixtures.