Critical properties of a liquid film between two planar walls are investigated in the canonical ensemble, within which the total number of particles, rather than their chemical potential, is kept constant. The effect of this constraint is analyzed within mean field theory (MFT) based on a Ginzburg-Landau free energy functional as well as via Monte Carlo simulations of the 3D Ising model with fixed total magnetization. Within MFT and for finite adsorption strengths at the walls, the thermodynamic properties of the film in the canonical ensemble can be mapped exactly onto a grand canonical ensemble in which the corresponding chemical potential plays the role of the Lagrange multiplier associated with the constraint. However, due to a non-integrable divergence of the mean field order parameter profile near a wall, the limit of infinitely strong adsorption turns out to be not well-defined within MFT, because it would necessarily violate the constraint. The critical Casimir force (CCF) acting on the two planar walls of the film is generally found to behave differently in the canonical and grand canonical ensembles. For instance, the canonical CCF in the presence of equal preferential adsorption at the two walls is found to have the opposite sign and a slower decay behavior as a function of the film thickness compared to its grand canonical counterpart. We derive the stress tensor in the canonical ensemble and find that it has the same expression as in the grand canonical case, but with the chemical potential playing the role of the Lagrange multiplier associated with the constraint. The different behavior of the CCF in the two ensembles is rationalized within MFT by showing that, for a prescribed value of the thermodynamic control parameter of the film, i.e., density or chemical potential, the film pressures are identical in the two ensembles, while the corresponding bulk pressures are not.
We study the critical Casimir force for a film geometry in the Ising universality class. We employ a homogeneous adsorption preference on one of the confining surfaces, while the opposing surface exhibits quenched random disorder, leading to a random local adsorption preference. Disorder is characterized by a parameter p, which measures, on average, the portion of the surface that prefers one component, so that p=0, 1 correspond to homogeneous adsorption preference. By means of Monte Carlo simulations of an improved Hamiltonian and finite-size scaling analysis, we determine the critical Casimi…
Motivated by recent experiments with confined binary liquid mixtures near demixing, we study the universal critical properties of a system, which belongs to the Ising universality class, in the film geometry. We employ periodic boundary conditions in the two lateral directions and fixed boundary conditions on the two confining surfaces, such that one of them has a spatially homogeneous adsorption preference while the other one exhibits a laterally alternating adsorption preference, resembling locally a single chemical step. By means of Monte Carlo simulations of an improved Hamiltonian, so tha…
When masless excitations are limited or modified by the presence of material bodies one observes a force atcing between them generally called Casimir force. Such excitations are present in any fluid system close to its true bulk critical point. We derive exact analytical results for both the temperature and external ordering field behavior of the thermodynamic Casimir force within the mean-field Ginzburg-Landau Ising type model of a simple fluid or binary liquid mixture. We investigate the case when under a film geometry the boundaries of the system exhibit strong adsorption onto one of the ph…
Geometrical structures of confining surfaces profoundly influence the adsorption of fluids upon approaching a critical point T_c in their bulk phase diagram, i.e., for t=(T-T_c)/T_c -> +/-0. Guided by general scaling considerations, we calculate, within mean-field theory, the temperature dependence of the order parameter profile in a wedge with opening angle gamma<pi and close to a ridge (gamma>pi) for T>T_c and T<T_c and in the presence of surface fields. For a suitably defined reduced excess adsorption Gamma_\pm(gamma,t -> +/-0)~Gamma_\pm(gamma)|t|^{beta-2nu} we compute the universal amplitu…
When massless excitations are limited or modified by the presence of material bodies one observes a force acting between them generally called Casimir force. Such excitations are present in any fluid system close to its true bulk critical point. We derive exact analytical results for both the temperature and external ordering field behavior of the thermodynamic Casimir force within the mean-field Ginzburg-Landau Ising type model of a simple fluid or binary liquid mixture. We investigate the case when under a film geometry the boundaries of the system exhibit strong adsorption onto one of the p…
Extended de Gennes-Fisher (EdGF) local-functional method has been applied to the thermodynamic Casimir effect {\it away} from the critical point for systems in the Ising universality class confined between parallel plane plates with symmetric boundary conditions (denoted $(ab)=(++)$). Results on the universal scaling functions of the Casimir force $W_{++}(y)$ ($y$ is a temperature-dependant scaling variable) and Gibbs adsorption $\tilde G(y)$ are presented in spatial dimension $d=3$. Also, the mean-field form of the universal scaling function of the Gibbs adsorption $\tilde G(y)$ is derived wi…
The effect of imposing a constraint on a fluctuating scalar order parameter field in a system of finite volume is studied within statistical field theory. The canonical ensemble, corresponding to a fixed total integrated order parameter, is obtained as a special case of the theory. A perturbative expansion is developed which allows one to systematically determine the constraint-induced finite-volume corrections to the free energy and to correlation functions. In particular, we focus on the Landau-Ginzburg model in a film geometry (i.e., a rectangular parallelepiped with a small aspect ratio) w…
Recent experiments have measured the critical Casimir force acting on a colloid immersed in a binary liquid mixture near its continuous demixing phase transition and exposed to a chemically structured substrate. Motivated by these experiments, we study the critical behavior of a system, which belongs to the Ising universality class, for the film geometry with one planar wall chemically striped, such that there is a laterally alternating adsorption preference for the two species of the binary liquid mixture, which is implemented by surface fields. For the opposite wall we employ alternatively a…
Recent experimental realizations of the critical Casimir effect have been implemented by monitoring colloidal particles immersed in a binary liquid mixture near demixing and exposed to a chemically structured substrate. In particular, critical Casimir forces have been measured for surfaces consisting of stripes with periodically alternating adsorption preferences, forming chemical steps between them. Motivated by these experiments, we analyze the contribution of such chemical steps to the critical Casimir force for the film geometry and within the Ising universality class. By means of Monte Ca…
Motivated by recent experiments with confined binary liquid mixtures near their continous demixing phase transition we study the critical behavior of a system, which belongs to the Ising universality class, for the film geometry with one planar wall chemically structured such that there is a laterally alternating adsorption preference for the species of the binary liquid mixture. By means of Monte Carlo simulations and finite-size scaling analysis we determine the critical Casimir force and the corresponding universal scaling function.
A classical density functional theory (cDFT) based on the PC-SAFT equation of state is proposed for the calculation of adsorption equilibria of pure substances and their mixtures in covalent organic frameworks (COFs). Adsorption isotherms of methane, ethane, n-butane and nitrogen in the COFs TpPa-1 and 2,3-DhaTph are calculated and compared to results from grand canonical Monte Carlo (GCMC) simulations. Mixture adsorption is investigated for the methane/ethane and methane/n-butane binary systems. Excellent agreement between PC-SAFT DFT and GCMC is obtained for all adsorption isotherms up to pr…
A lattice gas model of adsorption inside cylindrical pores is evaluated with Monte Carlo simulations. The model incorporates two kinds of site: (a line of) ``axial'' sites and surrounding ``cylindrical shell'' sites, in ratio 1:7. The adsorption isotherms are calculated in either the grand canonical or canonical ensembles. At low temperature, there occur quasi-transitions that would be genuine thermodynamic transitions in mean-field theory. Comparison between the exact and mean-field theory results for the heat capacity and adsorption isotherms are provided.
We derive an efficient method for the insertion of structured particles in grand canonical Monte Carlo simulations of adsorption in very confining geometries. We extend this method to path integral simulations and use it to calculate the isotherm of adsorption of hydrogen isotopes in narrow carbon nanotubes (2D confinement) and slit pores (1D confinement) at the temperatures of 20 K and 77 K, discussing its efficiency by comparison to the standard path integral grand canonical Monte Carlo algorithm. We use this algorithm to perform multicomponent simulations in order to calculate the hydrogen …
In this study, we consider motion of the massive and charged Bose gas trapped in electric and magnetic fields between two parallel plates in the $x-y$ plane that are separated by a distance $d$ in the $z$ direction. We derive analytical expression of the grand canonical potential of the quantum particles by using of Ketterle and van Druten approximation. By evaluating canonical potential, we obtain Casimir potential and force at the Bose-Einstein condensation temperature $T_{c}$. We also show that Casimir force oscillates depends on distance $d$ for fixed parameters.
In soft and condensed matter physics, effective interactions often emerge as a result of the spatial confinement of a fluctuating field. For instance, microscopic particles in a binary liquid mixture are subject to critical Casimir forces whenever their surfaces confine the thermal fluctuations of the order parameter of this kind of solvent, the range of which diverges upon approaching the critical demixing point. Critical Casimir forces are predicted to be nonadditive on a particular large scale. However, a direct experimental evidence of this fact is still lacking. Here, we fill in this gap …
We show that critical Casimir effects can be accessed through direct simulation of a model binary fluid passing through the demixing transition. We work in the semi grand canonical ensemble, in slab geometry, in which the Casimir force appears as the excess of the generalized pressure, $P_{\bot}-nμ$. The excesses of the perpendicular pressure, $P_{\bot}$, and of $nμ$, are individually of much larger amplitude. A critical pressure anisotropy is observed between forces parallel and perpendicular to the confinement direction, which collapses onto a universal scaling function closely related to th…
In a recent study [Phys. Rev. E \textbf{94}, 022103 (2016)] it has been shown that, for a fluid film subject to critical adsorption, the resulting critical Casimir force (CCF) may significantly depend on the thermodynamic ensemble. Here, we extend that study by considering fluid films within the so-called ordinary surface universality class. We focus on mean-field theory, within which the OP profile satisfies Dirichlet boundary conditions and produces a nontrivial CCF in the presence of external bulk fields or, respectively, a nonzero total order parameter within the film. Our analytical resul…
We study the crossover from the ordinary to the normal surface universality class in the three-dimensional Ising universality class. This crossover is relevant for the behavior of films of binary mixtures near the demixing point and a weak adsorption at one or both surfaces. We perform Monte Carlo simulations of the improved Blume-Capel model on the simple cubic lattice. We consider systems with film geometry, where various boundary conditions are applied. We discuss corrections to scaling that are caused by the surfaces and their relation with the so called extrapolation length. To this end w…
A huge amount of entropy is produced at places where fresh water and seawater mix, for example at river mouths. This mixing process is a potentially enormous source of sustainable energy, provided it is harnessed properly, for instance by a cyclic charging and discharging process of porous electrodes immersed in salt and fresh water, respectively [D. Brogioli, Phys. Rev. Lett. 103, 058501 (2009)]. Here we employ a modified Poisson-Boltzmann free-energy density functional to calculate the ionic adsorption and desorption onto and from the charged electrodes, from which the electric work of a cyc…
Using analytic and numerical approaches, we study the spatio-temporal evolution of a conserved order parameter of a fluid in film geometry, following an instantaneous quench to the critical temperature $T_c$ as well as to supercritical temperatures. The order parameter dynamics is chosen to be governed by model B within mean field theory and is subject to no-flux boundary conditions as well as to symmetric surface fields at the confining walls. The latter give rise to critical adsorption of the order parameter at both walls and provide the driving force for the non-trivial time evolution of th…
We study colloidal particles with chemically inhomogeneous surfaces suspended in a critical binary liquid mixture. The inhomogeneous particle surface is composed of patches with alternating adsorption preferences for the two components of the binary solvent. By describing the binary liquid mixture \emph{at} its consolute point in terms of the critical Ising model we exploit its conformal invariance in two spatial dimension. This allows us to determine exactly the universal profiles of the order parameter, the energy density, and the stress tensor as well as some of their correlation functions …
We study the Casimir effect for the perfect Bose-gase in the slab geometry for various boundary conditions. We show that the grand canonical potential per unit area at the bulk critical chemical potential $μ=0$ has the standard asymptotic form with universal Casimir terms.
If a fluctuating medium is confined, the ensuing perturbation of its fluctuation spectrum generates Casimir-like effective forces acting on its confining surfaces. Near a continuous phase transition of such a medium the corresponding order parameter fluctuations occur on all length scales and therefore close to the critical point this effect acquires a universal character, i.e., to a large extent it is independent of the microscopic details of the actual system. Accordingly it can be calculated theoretically by studying suitable representative model systems. We report on the direct measurement…
Casimir versus Helmholtz forces in the Gaussian model: exact results for Dirichlet--Dirichlet, Neumann--Dirichlet, Neumann--Neumann, and periodic boundary conditions
Institute of Mechanics, Bulgarian Academy of Sciences（保加利亚科学院力学研究所）；Center of Competence for Mechatronics and Clean Technologies “Mechatronics, Innovation, Robotics, Automation and Clean Technologies” - MIRACle（机电一体化与清洁技术能力中心“机电一体化、创新、机器人、自动化与清洁技术”-MIRACle）；Max-Planck-Institut für Intelligente Systeme（马克斯·普朗克智能系统研究所）；Department of Physics and Astronomy, University of California, Los Angeles（加州大学洛杉矶分校物理与天文学系）
Grand canonical Monte Carlo simulations have been performed to determine the adsorption behavior of Ar and Kr atoms on the exterior surface of a rope (bundle) consisting of many carbon nanotubes. The computed adsorption isotherms reveal phase transitions associated with the successive creation of quasi-one dimensional lines of atoms near and parallel to the intersection of two adjacent nanotubes.
We present a study of the Casimir effect in an imperfect (mean-field) Bose gas contained between two infinite parallel plane walls. The derivation of the Casimir force follows from the calculation of the excess grand canonical free energy density under periodic, Dirichlet, and Neumann boundary conditions with the use of the steepest descent method. In the one-phase region the force decays exponentially fast when distance $D$ between the walls tends to infinity. When Bose-Einstein condensation point is approached the decay length in the exponential law diverges with critical exponent $ν_{IMP}=1…
We consider an ideal Bose gas enclosed in a $d$-dimensional slab of thickness $D$. Using the grand canonical ensemble we calculate the variance of the thermal Casimir force acting on the slab's walls. The variance evaluated per unit wall area is shown to decay like $ Δ_{var}/D$ for large $D$. The amplitude $ Δ_{var}$ is a non-universal function of two scaling variables $λ/ ξ$ and $D/ ξ$, where $λ$ is the thermal de Broglie wavelength and $ξ$ is the bulk correlation length. It can be expressed via the bulk pressure, the Casimir force per unit wall area, and its derivative with respect to chemic…
We present here exact results for a one-dimensional gas, or fluid, of hard-sphere particles with attractive boundaries. The particles, which can exchange with a bulk reservoir, mediate an interaction between the boundaries. A two-dimensional lattice of such one-dimensional gas `columns' represents a discrete approximation of a three-dimensional gas of particles between two surfaces. The effective particle-mediated interaction potential of the boundaries, or surfaces, is calculated from the grand-canonical partition function of the one-dimensional gas of particles, which is an extension of the …
Some properties of an ideal gas of massive bosons in a mean field potential and, confined between two infinite parallel slabs in a d-dimensional configuration space are investigated systematically. Here, one particle density of states approach is employed to study the critical temperature, shift of density, Casimir effects and critical exponents, starting from the evaluation of the grand canonical free energy in d-dimension. We have found that, the shift of density, Casimir force and the critical temperature depend on the space dimensionality. But the Casimir force decays as an inverse power l…
We present an experimental and theoretical study of the phase behavior of a binary mixture of colloids with opposite adsorption preferences in a critical solvent. As a result of the attractive and repulsive critical Casimir forces, the critical fluctuations of the solvent lead to a further critical point in the colloidal system, i.e. to a critical colloidal-liquid--colloidal-liquid demixing phase transition which is controlled by the solvent temperature. Our experimental findings are in good agreement with calculations based on a simple approximation for the free energy of the system.
Grand canonical simulations are used to calculate adsorption isotherms of various classical gases on alkali metal and Mg surfaces. Ab initio adsorption potentials and Lennard-Jones gas-gas interactions are used. Depending on the system, the resulting behavior can be nonwetting for all temperatures studied, complete wetting, or (in the intermediate case) exhibit a wetting transition. An unusual variety of wetting transitions at the triple point is found in the case of a specific adsorption potential of intermediate strength. The general threshold for wetting near the triple point is found to be…
After a review of the standard calculation of the Casimir force between two metallic plates at zero and non-zero temperatures, we present the study of microscopic models to determine the large-distance asymptotic force in the high-temperature regime. Casimir's conducting plates are modelized by plasmas of interacting charges at temperature T. The charges are either classical, or quantum-mechanical and coupled to a (classical) radiation field. In these models, the force obtained is twice weaker than that arising from standard treatments neglecting the microscopic charge fluctutations inside the…
