A smooth cut-off formulation of the Hierarchical Reference Theory (HRT) is developed and applied to a Yukawa fluid. The HRT equations are derived and numerically solved leading to: the expected renormalization group structure in the critical region, non classical critical exponents and scaling laws, a convex free energy in the whole phase diagram (including the two-phase region), finite compressibility at coexistence, together with a fully satisfactory comparison with available numerical simulations. This theory, which also guarantees the correct short range behavior of two body correlations, represents a major improvement over the existing liquid state theories.
We present a microscopic Hamiltonian framework to develop Maxwell demon like engine. Our model consists of a equilibrium thermal bath and a non-equilibrium bath; latter generated by driving with an external stationary, Gaussian noise. The engine we develop, can be considered as a device to extract work by modifying internal fluctuations. Our theoretical analysis focusses on finding the essential ingredients necessary for generating fluctuation induced transport under non-equilibrium condition. An important outcome of our model is that the net motion occurs when the non-linear bath is modulated…
The origin of the spurious interface velocity in finite difference lattice Boltzmann models for liquid - vapor systems is related to the first order upwind scheme used to compute the space derivatives in the evolution equations. A correction force term is introduced to eliminate the spurious velocity. The correction term helps to recover sharp interfaces and sets the phase diagram close to the one derived using the Maxwell construction.
In this work the interface system of the van der Waals fluid is investigated by using the density gradient theory incorporated with the mean-field theory. Based on the mean-field dividing interface generated by the Maxwell construction, we propose a highly accurate density profile model for the density gradient theory, which facilitates reliable predictions of various properties for the interface region. It is found that the local intrinsic Helmholtz free energy peaks at the interface and that the maximum difference of the normal and tangential components of the pressure tensor corresponds to …
In this work we define a mean-field crossover generated by the Maxwell construction as the dividing interface for the vapor-liquid interface area. A highly accurate density-profile equation is thus derived, which is physically favorable and leads to reliable predictions of interfacial properties. By using the density gradient theory and a mean-field equation of sate for the Lennard-Jones fluid, we are able to extensively explore the interface system in terms of the Gibbs free energy, the Helmholtz free energy and heat capacity. The results show that the mean-field dividing interface is the nat…
The interface between the vapor and liquid phase of quadrupolar-dipolar fluids is the seat of an electric interfacial potential whose influence on ion solvation and distribution is not yet fully understood. To obtain further microscopic insight into water specificity we first present extensive classical molecular dynamics simulations of a series of model liquids with variable molecular quadrupole moments that interpolates between SPC/E water and a purely dipolar liquid. We then pinpoint the essential role played by the competing multipolar contributions to the vapor-liquid and the solute-liqui…
We study a system of particles which jump on the sites of the interval $[1,L]$ of $\mathbb Z$. The density at the boundaries is kept fixed to simulate the action of mass reservoirs. The evolution depends on two parameters $λ'\ge 0$ and $λ"\ge 0$ which are the strength of an external potential and respectively of an attractive potential among the particles. When $λ'=λ"= 0$ the system behaves diffusively and the density profile of the final stationary state is linear, Fick's law is satisfied. When $λ'> 0$ and $λ"= 0$ the system models the diffusion of carbon in the presence of silicon as in the …
We use the density functional method to examine the properties of the nonuniform (two-phase) fluid of two-level atoms, a part of which is excited. Basing on the analysis of the equation of state of a gas of two-level atoms, a part of which is excited, we suggest a simple density functional of the grand thermodynamical potential. We use the proposed density functional of the grand thermodynamical potential to calculate the nucleation barrier for vapor-to-liquid phase transition in the presence of excited atoms.
It is shown that the dynamics of a two-dimensional crystal with a finite concentration of dislocations, as well as vacancy and interstitial defects, is governed by the hydrodynamic equations of a viscoelastic medium. At the longest length scales the viscoelasticity is described by the simplest Maxwell model, whose shear and compressional relaxation times are obtained in terms of microscopic quantities, including the density of free dislocations. At short length scales, bond orientational order effects become important and lead to wavevector dependent corrections to the relaxation times.
Depletion of the liquid density near a solid surface with a weak long-range fluid-surface interaction was studied by computer simulations of the liquid-vapor coexistence of a LJ fluid confined in slitlike pores. In a wide temperature range the liquid density decreases towards the surface without the formation of a {\it vapor} layer between the liquid and the solid surface. This evidences the absence of a drying transition up to the liquid-vapor critical point. Two contributions to the excess desorption {\it $Γ_{tot}$} were found. The first one {\it $Γ_ξ$} $\sim$ $ρ_{bulk}$ $ξ$ exists at any te…
Dissipative effects in electromagnetism on macroscopic scales are examined by coarse graining the microscopic Maxwell equations with respect to time. We illustrate a procedure to derive the dissipative effects on the macroscopic scale by using a Green-Kubo type expression in terms of the microscopic fluctuations and the correlations between them. The resulting macroscopic Maxwell equations are formulated within the General Equation for the Non-Equilibrium Reversible-Irreversible Coupling (GENERIC) framework, accounting also for inhomogeneous temperature.
Kinetics of separation between the low and high density phases in a single component Lennard-Jones model has been studied via molecular dynamics simulations, at a very low temperature, in the space dimension $d=2$. For densities close to the vapor (low density) branch of the coexistence curve, disconnected clusters of the high density phase exhibit ballistic motion, the kinetic energy distribution of the clusters being closely Maxwellian. Starting from nearly circular shapes, at the time of nucleation, these clusters grow via sticky collisions, gaining filament-like nonequilibrium structure at…
Although there is not a complete "proof" of the second law of thermo- dynamics based on microscopic dynamics, two properties of Hamiltonian systems have been used to prove the impossibility of work extraction from a single thermal reservoir: Liouville's theorem and the adiabatic invariance of the volume enclosed by an energy shell. In this paper we analyze these two properties in the Szilard engine and other systems related with the Maxwell demon. In particular, we recall that the enclosed volume is no longer an adiabatic invariant in non ergodic systems and explore the consequences of this on…
Maxwell's demon explores the role of information in physical processes. Employing information about microscopic degrees of freedom, this "intelligent observer" is capable of compensating entropy production (or extracting work), apparently challenging the second law of thermodynamics. In a modern standpoint, it is regarded as a feedback control mechanism and the limits of thermodynamics are recast incorporating information-to-energy conversion. We derive a trade-off relation between information-theoretic quantities empowering the design of an efficient Maxwell's demon in a quantum system. The d…
We present the results of an analytical theory and simulations of the field inside a cavity created in a dipolar liquid placed in a uniform external electric field. The analytical theory shows that the limit of continuum electrostatics is reached through a singularity in the microscopic response function responsible for a non-decaying longitudinal polarization wave. Fields in microscopic cavities are much different from macroscopic predictions, and low-polarity dielectrics are predicted to have a continuum limit distinct from the solution of Maxwell's equations. Computer Monte Carlo simulation…
Based on a microscopic density functional theory we calculate the internal structure of the three-phase contact line between liquid, vapor, and a confining wall as well as the morphology of liquid wetting films on a substrate exhibiting a chemical step. We present a refined numerical analysis of the nonlocal density functional which describes the interface morphologies and the corresponding line tensions. These results are compared with those predicted by a more simple phenomenological interface displacement model. Except for the case that the interface exhibits large curvatures, we find that …
It is known that purely repulsive self-propelled colloids can undergo bulk liquid-vapor phase separation. In experiments and large scale simulations, however, more complex steady states are also seen, comprising a dynamic population of dense clusters in a sea of vapor, or dilute bubbles in a liquid. Here we show that these microphase-separated states should emerge generically in active matter, without any need to invoke system-specific details. We give a coarse-grained description of them, and predict transitions between regimes of bulk phase separation and microphase separation. We achieve th…
Driven diffusive systems may undergo phase transitions to sustain atypical values of the current. This leads in some cases to symmetry-broken space-time trajectories which enhance the probability of such fluctuations. Here we shed light on both the macroscopic large deviation properties and the microscopic origin of such spontaneous symmetry breaking in the open weakly asymmetric exclusion process. By studying the joint fluctuations of the current and a collective order parameter, we uncover the full dynamical phase diagram for arbitrary boundary driving, which is reminiscent of a $\mathbb{Z}_…
