Abstract Recent theoretical work on the microscopic structure and surface tension of liquid-vapour interface simple (argon-like) fluids is critically reviewed. In particular, form pairwise intermolecular correlations in liquid capillary wave treatment are examined some detail. It argued that conventional theory, which leads to divergences width density profile, unsatisfactory for describing all equilibrium aspects interface. The functional formalism has been developed study can also be...

We develop a density functional for hard-sphere mixtures which keeps the structure of Rosenfeld's fundamental measure theory (FMT) whilst inputting Mansoori–Carnahan–Starling–Leland bulk equation state. Density profiles pure fluid and some binary adsorbed at planar hard wall obtained from present exhibit improvement over those original FMT. The pair direct correlation function c(2) (r) fluid, differentiation, is also improved. When tensor weight incorporated system our yields good...

When gases or liquids are adsorbed in narrow pores capillaries their properties significantly different from those a bulk phase. This article reviews recent developments the statistical theory and computer simulation of simple fluids confined model pores, emphasizing microscopic structure phase equilibria. The reflects packing atoms molecules confining geometries while behavior presence surface contributions to fluid's free energy. Confinement shifts first-order transitions, such as...

Phase transitions at fluid interfaces and in fluids confined pores have been investigated by means of a density functional approach that treats attractive forces between molecules mean-field approximation models repulsive hard-spheres. Two types were employed for the hard-sphere free energy functional: (a) well-known local (LDA) omits short-ranged correlations (b) non-local smoothed (SDA) includes such therefore accounts oscillations profile near walls. Three different kinds phase transition...

By means of a density functional approach the phase equilibria simple fluid confined by two adsorbing walls have been investigated as function wall separation H and chemical potential μ for temperature T corresponding to both partial complete wetting situations. For large values small undersaturations Δμ ≡ μsat−μ, we recover macroscopic formulas undersaturation at which first- order transition (capillary condensation) from dilute ‘‘gas’’ dense ‘‘liquid’’ occurs in single, infinitely long...

We study the phase behavior and structure of highly asymmetric binary hard-sphere mixtures. By first integrating out degrees freedom small spheres in partition function we derive a formal expression for effective Hamiltonian large spheres. Then using an explicit pairwise (depletion) potential approximation to this computer simulations, determine fluid-solid coexistence size ratios $q=0.033,0.05,0.1,0.2$, 1.0. The resulting two-phase region becomes very broad packing fractions as q small....

The nature of adsorption simple fluids confined in model pores is investigated by means a density functional approach. For temperatures T corresponding to partial wetting situation first-order phase transition (capillary condensation) from dilute ‘gas’ dense ‘liquid’ occurs at relative pressures p/psat close those predicted the macroscopic Kelvin equation, even for radii Rc or wall separations H as small 10 molecular diameters. In complete situation, where thick films develop, equation is,...

We present an alternative derivation of the dynamical density functional theory for one body profile a classical fluid developed by Marconi and Tarazona [J. Chem. Phys., 110, 8032 (1999)]. Our elucidates further some physical assumptions inherent in shows that it is not restricted to fluids composed particles interacting solely via pair potentials; rather applies general, multi-body interactions. The starting point our Smoluchowski equation therefore Brownian as such applicable colloidal...

We use density functional methods to develop a new nonclassical theory for the homogeneous nucleation of gas liquid phase transition. The extent agreement between our results and classical prediction Becker, Döring, Zeldovich is strongly dependent on range attractive potential which we employ. show that predictions are consistent with experimental data using cloud chambers, suggest several directions in experimentalists might look order find effects. In particular, cavitation (gas bubble...

We use supervised machine learning together with the concepts of classical density functional theory to investigate effects interparticle attraction on pair structure, thermodynamics, bulk liquid-gas coexistence, and associated interfacial phenomena in many-body systems. Local one-body direct correlation is based Monte Carlo simulations inhomogeneous systems randomized thermodynamic conditions, planar shapes external potential, box sizes. Focusing prototypical Lennard-Jones system, we test...

We present a versatile density functional approach (DFT) for calculating the depletion potential in general fluid mixtures. For standard situation of single big particle immersed sea small particles near fixed object, system is regarded as an inhomogeneous binary mixture and external field limit vanishing species, rho(b)-->0, taken explicitly. In this our requires only equilibrium profile one-component knowledge independent weight functions which characterize functional. Thus, planar wall or...

The thermodynamics of fluids confined between two adsorbing solid substrates (walls) is revisited. Attention focused on the phase equilibria an open system characterized by variables μ (chemical potential), T (temperature), and H (wall separation). Clapeyron equations for shape lines coexistence are derived used to interpret results earlier calculations first-order transitions, namely capillary condensation undersaturated ‘‘gas’’ ‘‘liquid’’ prewetting (thick–thin film transition) at finite...

We study the phase behaviour and structure of model colloid-polymer mixtures. By integrating out degrees freedom non-adsorbing ideal polymer coils, we derive a formal expression for effective one-component Hamiltonian colloids. Using two-body (Asakura-Oosawa pair potential) approximation to this in computer simulations, determine size ratios q = p/c 0.1, 0.4, 0.6, 0.8, where c p denote diameters colloids respectively. For large q, find both fluid-solid stable fluid-fluid transition. However,...

Reviews some recent theoretical and computer simulation studies of simple atomic fluids adsorbed at structureless substrates. Emphasis is placed on phase transitions, especially the various types wetting transition. Criticality associated with capillary-wave-like fluctuations in a continuously growing film. This subtle nature, which best understood terms pairwise correlation function fluid. Other surface such as prewetting layering, occur out bulk coexistence. Theory suggests that for...

A simple free energy functional, which incorporates both ‘local’ thermodynamics and short ranged correlations, is formulated applied to the calculation of density profile fluids near hard walls. For sphere calculated profiles are in reasonable agreement with Monte Carlo results. a Lennard-Jones liquid exhibit phenomenon wetting by gas; oscillations become much less pronounced layer gas develops wall as bulk approaches its value at coexistence. Such behaviour was found earlier simulations but...

We investigate the entropic depletion force that arises between two big hard spheres of radius ${R}_{b},$ mimicking colloidal particles, immersed in a fluid small ${R}_{s}.$ Within framework Derjaguin approximation, which becomes exact as ${s=R}_{s}{/R}_{b}\ensuremath{\rightarrow}0$, we examine an expression for and corresponding potential range $0<h<{2R}_{s},$ where $h$ is separation spheres. These expressions, depend only on bulk pressure planar wall-fluid interfacial tension, are...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTemperature dependence of gas adsorption on a mesoporous solid: capillary criticality and hysteresisP. C. Ball R. EvansCite this: Langmuir 1989, 5, 3, 714–723Publication Date (Print):May 1, 1989Publication History Published online1 May 2002Published inissue 1 1989https://pubs.acs.org/doi/10.1021/la00087a026https://doi.org/10.1021/la00087a026research-articleACS PublicationsRequest reuse permissionsArticle Views1246Altmetric-Citations228LEARN ABOUT...

A simple nearly free electron model for the electrical resistivity of liquid noble and transition metals their alloys is presented. The scattering described in terms phase shifts muffin tin potentials constructed liquids.

We consider the asymptotic decay of structural correlations in pure fluids, fluid mixtures, and fluids subject to various types inhomogeneity. For short ranged potentials, both form amplitude longest range are determined by leading order poles complex Fourier transform bulk structure factor. Generically, for such falls into two classes: (i) controlled a single simple pole on imaginary axis (monotonic exponential decay) (ii) conjugate pair (exponentially damped oscillatory decay). General...

Recent work has highlighted the existence of a unified theory for asymptotic decay density profile ρ(r) an inhomogeneous fluid and bulk radial distribution function g(r). For given short-ranged interatomic potential decays into in same fashion as g(r), i.e. with exponential length (α0/-1) and, sufficiently high (ρb) and/or temperature (T), oscillatory wavelength (2π/α1). The quantities α0 α1 are determined by linear stability analysis fluid; they depend on only direct correlation function....

By integrating out the degrees of freedom small spheres in a binary mixture large and hard spheres, we derive an explicit effective Hamiltonian for spheres. Using two-body (depletion potential) contribution to this simulations, find stable fluid-solid both metastable fluid-fluid solid-solid coexistence with size ratio $q\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0.1$. For $q\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}0.05$ becomes stable.

A fluid confined between two parallel walls that exert different (competitive) surface fields may exhibit phase equilibria strikingly from those found for equal fields. Macroscopic arguments and an explicit mean-field analysis predict if the are such wets one wall dries other (above a certain critical wetting transition temperature ${T}_{w}$) coexistence of phases can only occur, finite separation L, when T${T}_{c}$,L, where ${T}_{c}$,L lies below ${T}_{w}$. scaling Ansatz suggests...

Using mean field free energy functionals of the type employed by Sullivan, we have investigated nature transition from partial to complete wetting that occurs at a solid-gas interface. We show this can be first or second order phase transition. If it is order, as predicted Cahn, coverage diverges discontinuously and temperature derivative interfacial tension changes whereas if these properties change continuously, found Sullivan. For given model system depends strongly on range solid-fluid...