We consider a two-dimensional (d=2) kagomé lattice gas model with attractive three-particle interactions around each triangular face of the kagomé lattice. Exact solutions are obtained for multiparticle correlations along the liquid and vapor branches of the coexistence curve and at criticality. The correlation solutions are also determined along the continuation of the curvilinear diameter of the coexistence region into the disordered fluid region. The method generates a linear algebraic system of correlation identities with coefficients dependent only upon the interaction parameter. Using a priori knowledge of pertinent solutions for the density and elementary triplet correlation, one finds a closed and linearly independent set of correlation identities defined upon a spatially compact nine-site cluster of the kagomé lattice. Resulting exact solution curves of the correlations are plotted and discussed as functions of the temperature, and are compared with corresponding results in a traditional kagomé lattice gas having nearest-neighbor pair interactions. An example of application for the multiparticle correlations is demonstrated in cavitation theory.
We consider a S=1 kagomé Ising model with triquadratic interactions around each triangular face of the kagomé lattice, single-ion anisotropy and an applied magnetic field. A mapping establishes an equivalence between the magnetic canonical partition function of the model and the grand canonical partition function of a kagomé lattice-gas model with localized three-particle interactions. Since exact phase diagrams are known for condensation in the one-parameter lattice-gas model, the mapping directly provides the corresponding exact phase diagrams of the three-parameter S=1 Ising model. As aniso…
We report on the coexistence of liquid-like and gas-like structures in supercritical fluid (SCF). The deltoid coexistence region encloses the Widom line, and may therefore be termed the "Widom delta". Machine learning analysis of simulation data shows continuous transition across the delta, from liquid-like to gas-like states, with fractions following a simplified two-state model. This suggests a microscopic view of the SCF as a mixture of liquid-like and gas-like structures, where the anomalous behavior near the critical point originates from fluctuations between the two types.
The mixed spin-1/2 and spin-3/2 Ising model on the extended Kagomé lattice is solved by establishing a mapping correspondence with the eight-vertex model. Letting the parameter of uniaxial single-ion anisotropy tend to infinity, the model becomes exactly soluble as a free-fermion eight-vertex model. Under this restriction, the critical points are characterized by critical exponents from the standard Ising universality class. In a certain subspace of interaction parameters that corresponds to a coexistence surface between two ordered phases, the model becomes exactly soluble as a symmetric zero…
We study the gas-liquid phase diagram and the crossover behavior of a simple model of ionic fluid: an equimolar binary mixture of equisized hard spheres interacting through screened Coulomb potentials which are repulsive between particles of the same species and attractive between particles of different species. Using our previous results, we obtain explicit expressions for the relevant coefficients of the effective $φ^{4}$ Ginzburg-Landau Hamiltonian in a one-loop approximation. Within the framework of this approximation, we calculate the critical parameters and gas-liquid coexistence curves …
We present a systematic study of the effect of the ion pairing on the gas-liquid phase transition of hard-core 1:1 electrolyte models. We study a class of dipolar dimer models that depend on a parameter R_c, the maximum separation between the ions that compose the dimer. This parameter can vary from sigma_{+/-} that corresponds to the tightly tethered dipolar dimer model, to R_c --> infinity, that corresponds to the Stillinger-Lovett description of the free ion system. The coexistence curve and critical point parameters are obtained as a function of R_c by grand canonical Monte Carlo technique…
In this note we investigate using basic free energy considerations the location of the gas-liquid critical point with respect to solidification for narrow attractive interactions down to the Baxter limit. Possible experimental and simulation realizations leading to a stable critical point are briefly discussed.
Investigation of simple far-from-equilibrium systems exhibiting phase separation leads to the conclusion that phase coexistence is not well defined in this context. This is because the properties of the coexisting nonequilibrium systems depend on how they are placed in contact, as verified in the driven lattice gas with attractive interactions, and in the two-temperature lattice gas, under (a) weak global exchange between uniform systems, and (b) phase-separated (nonuniform) systems. Thus, far from equilibrium, the notions of universality of phase coexistence (i.e., independence of how systems…
Finite size scaling (FSS) analysis of the liquid gas criticality is complicated by the absence of any broken symmetry. This, in particular, does not allow a straightforward finding of the coexistence line and the critical point. The numerical flowgram (NF) method is adapted for a controlled determination of the coexistence line and the critical point, with the critical indices $μ,\, ν$ measured within 1-2% of the total error. The approach based on the NF for measuring the non-analytical corrections to the diameter - the mean density of the liquid and gas phases along the coexistence line - is …
The high-field regime of the spin-s XXZ antiferromagnet on the kagome lattice gives rise to macroscopically degenerate ground states thanks to a completely flat lowest single-magnon band. The corresponding excitations can be localized on loops in real space and have been coined "localized magnons". Thus, the description of the many-body ground states amounts to characterizing the allowed classical loop configurations and eliminating the quantum mechanical linear relations between them. Here, we investigate this loop-gas description on finite kagome lattices with open boundary conditions and co…
We study the polydisperse Baxter model of sticky hard spheres (SHS) in the modified Mean Spherical Approximation (mMSA). This closure is known to be the zero-order approximation (C0) of the Percus-Yevick (PY) closure in a density expansion. The simplicity of the closure allows a full analytical study of the model. In particular we study stability boundaries, the percolation threshold, and the gas-liquid coexistence curves. Various possible sub-cases of the model are treated in details. Although the detailed behavior depends upon the particularly chosen case, we find that, in general, polydispe…
We report an extensive Monte Carlo study of critical end point behaviour in a symmetrical binary fluid mixture. On the basis of general scaling arguments, singular behaviour is predicted in the diameter of the liquid-gas coexistence curve as the critical end point is approached. The simulation results show clear evidence for this singularity, as well as confirming a previously predicted singularity in the coexistence chemical potential. Both singularities should be detectable experimentally.
The binodal of a boson square-well fluid is determined as a function of the particle mass through the newly devised quantum Gibbs ensemble Monte Carlo algorithm [R. Fantoni and S. Moroni, {\sl to be published}]. In the infinite mass limit we recover the classical result. As the particle mass decreases the gas-liquid critical point moves at lower temperatures. We explicitely study the case of a quantum delocalization de Boer parameter close to the one of $\mbox{}^4$He. For comparison we also determine the gas-liquid coexistence curve of $\mbox{}^4$He for which we are able to observe the binodal…
Properties of the weakly non-ideal Bose gas are considered without suggestion on C-number representation of the creation and annihilation operators with zero momentum. The "density-density" correlation function and the one-particle Green function of the degenerated Bose gas are calculated on the basis of the self-consistent Hartree-Fock approximation. It is shown that the spectrum of the one-particle excitations possesses a gap whose value is connected with the density of particles in the "condensate". At the same time, the pole in the "density-density" Green function determines the phonon-rot…
Molecular dynamics simulations are performed on a system of model linear polymers to look at the violations of Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations near the mode coupling theory transition temperature $T_c$ at three (one higher and two lower) densities. At low temperatures, both lower density systems show stable gas-supercooled-liquid coexistence whereas the higher density system is homogeneous. We show that monomer density relaxation exhibits SE violation for all three densities, whereas molecular density relaxation shows a weak violation of the SE relation near $T_c…
We consider the liquid-gas phase boundary in a binary fluid mixture near its critical end point. Using general scaling arguments we show that the diameter of the liquid-gas coexistence curve exhibits singular behaviour as the critical end point is approached. This prediction is tested by means of extensive Monte-Carlo simulations of a symmetrical Lennard-Jones binary mixture within the grand canonical ensemble. The simulation results show clear evidence for the proposed singularity, as well as confirming a previously predicted singularity in the coexistence chemical potential [Fisher and Upton…
A novel mathematical rigorous method to obtain the vapor-liquid equilibrium curves near the critical point has been proposed covering the cases of well-known and commonly used equations of state for real gases - Van der Waals and Dieterici, which are prototypes to determine the critical exponent value of the coexistence curves system. We explain that the critical exponent value of the vapor-liquid equilibrium curves can be regarded as the analogy to the results based on classical assumptions - mean field theory. The novelty of our method has been exposed in comparison to the standard thermodyn…
We revisit motility-induced phase separation in two models of active particles interacting by pairwise repulsion. We show that the resulting dense phase contains gas bubbles distributed algebraically up to a typically large cutoff scale. At large enough system size and/or global density, all the gas may be contained inside the bubbles, at which point the system is microphase-separated with a finite cut-off bubble scale. We observe that the ordering is anomalous, with different dynamics for the coarsening of the dense phase and of the gas bubbles. This phenomenology is reproduced by a "reduced …
Multicanonical ensemble sampling simulations have been performed to calculate the phase diagram of a Lennard-Jones fluid embedded in a fractal random matrix generated through diffusion limited cluster aggregation. The study of the system at increasing size and constant porosity shows that the results are independent from the matrix realization but not from the size effects. A gas-liquid transition shifted with respect to bulk is found. On growing the size of the system on the high density side of the gas-liquid coexistence curve it appears a second coexistence region between two liquid phases.…
Systems of charged particles on anisotropic three-dimensional lattices are investigated theoretically using Debye-Huckel theory. It is found that the thermodynamics of these systems strongly depends on the degree of anisotropy. For weakly anisotropic simple cubic lattices, the results indicate the existence of order-disorder phase transitions and a tricritical point, while the possibility of low-density gas-liquid coexistence is suppressed. For strongly anisotropic lattices this picture changes dramatically: the low-density gas-liquid phase separation reappears and the phase diagram exhibits c…
We evaluate the free energy of the fluid and crystal phases for the ST2 potential [F.H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)] with reaction field corrections for the long-range interactions. We estimate the phase coexistence boundaries in the temperature-pressure plane, as well as the gas-liquid critical point and gas-liquid coexistence conditions. Our study frames the location of the previously identified liquid-liquid critical point relative to the crystalline phase boundaries, and opens the way for exploring crystal nucleation in a model where the metastable liquid-liqui…
Specialized Monte Carlo simulations and the moment free energy (MFE) method are employed to study liquid-gas phase equilibria in size-disperse fluids. The investigation is made subject to the constraint of fixed polydispersity, i.e. the form of the `parent' density distribution $ρ^0(σ)$ of the particle diameters $σ$, is prescribed. This is the experimentally realistic scenario for e.g. colloidal dispersions. The simulations are used to obtain the cloud and shadow curve properties of a Lennard-Jones fluid having diameters distributed according to a Schulz form with a large (40%) degree of polyd…
We propose several versions of primitive models of room temperature ionic liquids (RTILs) and develop a mean spherical approximation (MSA)-type theory for their description. RTIL is modeled as a two-component mixture of hard-sphere anions and flexible linear chain cations, represented by tangentially bonded hard spheres with the charge located on one of the terminal beads. The theoretical description of the model is carried out using the solution of the appropriately modified associative MSA (AMSA). Our solution reduces to solving one nonlinear algebraic equation for the Blum's screening param…
Free energy differences and coexistence of clathrate structures II and H via lattice-switch Monte Carlo
Université Marie et Louis Pasteur, CNRS, Institut UTINAM (UMR 6213)（玛丽和路易·巴斯德大学，法国国家科学研究中心，UTINAM研究所）；HH Wills Physics Laboratory, Royal Fort, University of Bristol（布里斯托大学）
We consider a model fluid with long-ranged, dispersion interparticle potentials confined between competing parallel walls. One wall is solvophilic and would be completely wet at bulk liquid-gas coexistence while the other is solvophobic and would be completely dry at bulk coexistence. When the wall separation L is large and the system is below the bulk critical temperature and close to bulk liquid-gas coexistence, a `delocalized interface' or `soft mode' phase forms with a liquid-gas interface near to the centre of the slit; this interacts with the walls via the power-law tails of the interpar…
We study theoretically the equilibrium phase behaviour of a mixture of polydisperse hard-sphere colloids and monodisperse polymers, modelled using the Asakura-Oosawa model within the free volume approximation of Lekkerkerker et al. We compute full phase diagrams in the plane of colloid and polymer volume fractions, using the moment free energy method. The intricate features of phase separation in pure polydisperse colloids combine with the appearance of polymer-induced gas-liquid coexistence to give a rich variety of phase diagram topologies as the polymer-colloid size ratio and the colloid po…
Motility-induced phase separation (MIPS), the phenomenon in which purely repulsive active particles undergo a liquid-gas phase separation, is among the simplest and most widely studied examples of a nonequilibrium phase transition. Here, we show that states of MIPS coexistence are in fact only metastable for three-dimensional active Brownian particles over a very broad range of conditions, decaying at long times through an ordering transition we call active crystallization. At an activity just above the MIPS critical point, the liquid-gas binodal is superseded by the crystal-fluid coexistence …
The distribution of the largest fragment is studied in different regions of the Lattice Gas model phase diagram. We show that first and second order transitions can be clearly distinguished in the grancanonical ensemble, while signals typical of a continuous transition are seen inside the coexistence region if a mass conservation constraint is applied. Some possible implications of these findings for heavy ion multifragmentation experiments are discussed.
We study lattice gas models with the imposition of a constraint on the maximum number of bonds (nearest neighbor interactions) that particles can participate in. The critical parameters, as well as the coexistence region are studied using the mean field approximation and the Bethe-Peierls approximation. We find that the reduction of the number of interactions suppresses the temperature-density region where the liquid and gas phases coexist. We confirm these results from simulations using the histogram reweighting method employing grand Canonical Monte Carlo simulations.
We consider liquid-vapor systems in finite volume $V\subset\R^d$ at parameter values corresponding to phase coexistence and study droplet formation due to a fixed excess $δN$ of particles above the ambient gas density. We identify a dimensionless parameter $Δ\sim(δN)^{(d+1)/d}/V$ and a \textrm{universal} value $\Deltac=\Deltac(d)$, and show that a droplet of the dense phase occurs whenever $Δ>\Deltac$, while, for $Δ<\Deltac$, the excess is entirely absorbed into the gaseous background. When the droplet first forms, it comprises a non-trivial, \textrm{universal} fraction of excess particles. Si…
