arXiv subjects

R. Evans

Publications and source records attributed to R. Evans.

At least 37 records · Page 2Linked to original sources

arXiv2015

Liquid-Gas Asymmetry and the Wavevector-Dependent Surface Tension

Attempts to extend the capillary-wave theory of fluid interfacial fluctuations to microscopic wavelengths, by introducing an effective wave-vector ($q$) dependent surface tension $σ_\text{eff}(q)$, have encountered difficulties. There is no consensus as to even the shape of $σ_\text{eff}(q)$. By analysing a simple density functional model of the liquid-gas interface, we identify different schemes for separating microscopic observables into background and interfacial contributions. In order for the backgrounds of the density-density correlation function and local structure factor to have a consistent and physically meaningful interpretation in terms of weighted bulk gas and liquid contributions, the background of the total structure factor must be characterised by a microscopic $q$-dependent length $ζ(q)$ not identified previously. The necessity of including the $q$ dependence of $ζ(q)$ is illustrated explicitly in our model and has wider implications, i.e. in typical experimental and simulation studies, an indeterminacy in $ζ(q)$ will always be present, reminiscent of the cut-off used in capillary-wave theory. This leads inevitably to a large uncertainty in the $q$ dependence of $σ_\text{eff}(q)$.

cond-mat.stat-mech↗

arXiv2014

Pair correlation functions and the wavevector-dependent surface tension in a simple density functional treatment of the liquid-vapour interface

We study the density-density correlation function $G({\bf r},{\bf r}')$ in the interfacial region of a fluid (or Ising-like magnet) with short-ranged interactions using square gradient density functional theory. Adopting a simple double parabola approximation for the bulk free-energy density, we first show that the parallel Fourier transform $G(z,z';q)$ and local structure factor $S(z;q)$ separate into bulk and excess contributions. We attempt to account for both contributions by deriving an interfacial Hamiltonian, characterised by a wavevector dependent surface tension $σ(q)$, and then reconstructing density correlations from correlations in the interface position. We show that the standard crossing criterion identification of the interface, as a surface of fixed density (or magnetization), does not explain the separation of $G(z,z';q)$ and the form of the excess contribution. We propose an alternative definition of the interface position based on the properties of correlations between points that "float" with the surface and show that this describes the full $q$ and $z$ dependence of the excess contributions to both $G$ and $S$. However, neither the "crossing-criterion" nor the new "floating interface" definition of $σ(q)$ are quantities directly measurable from the total structure factor $S^{tot}(q)$ which contains additional $q$ dependence arising from the non-local relation between fluctuations in the interfacial position and local density. Since it is the total structure factor that is measured experimentally or in simulations, our results have repercussions for earlier attempts to extract and interpret $σ(q)$.

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arXiv2012

Relationship between Local Molecular Field Theory and Density Functional Theory for non-uniform liquids

The Local Molecular Field Theory (LMF) developed by Weeks and co-workers has proved successful for treating the structure and thermodynamics of a variety of non-uniform liquids. By reformulating LMF in terms of one-body direct correlation functions we recast the theory in the framework of classical Density Functional Theory (DFT). We show that the general LMF equation for the effective reference potential phi_R follows directly from the standard mean-field DFT treatment of attractive interatomic forces. Using an accurate (Fundamental Measures) DFT for the non-uniform hard-sphere reference fluid we determine phi_R for a hard-core Yukawa liquid adsorbed at a planar hard wall. In the approach to bulk liquid-gas coexistence we find the effective potentials exhibit rich structure that can include damped oscillations at large distances from the wall as well as the repulsive hump near the wall required to generate the low density 'gas' layer characteristic of complete drying. We argue that it would be difficult to obtain the same level of detail from other (non DFT based) implementations of LMF. LMF emphasizes the importance of making an intelligent division of the interatomic pair potential of the full system into a reference part and a remainder that can be treated in mean-field approximation. We investigate different divisions for an exactly solvable one- dimensional model where the pair potential has a hard-core plus a linear attractive tail. Results for the structure factor and the equation of state of the uniform fluid show that including a significant portion of the attraction in the reference system can be much more accurate than treating the full attractive tail in mean-field approximation. We discuss further aspects of the relationship between LMF and DFT.

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arXiv2012

The phase behaviour and structure of a fluid confined between competing (solvophobic and solvophilic) walls

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 interparticle potentials. We use a coarse-grained effective Hamiltonian approach to derive explicit scaling expressions for the Gibbs adsorption, the surface tension, the solvation force and the total susceptibility. Using a non-local density functional theory (DFT) we calculate density profiles for the asymmetrically confined fluid at different chemical potentials and, for sufficiently large L, confirm the scaling predictions for the four thermodynamic quantities. Since the upper critical dimension for complete wetting with power-law potentials is <3 we argue that our (mean-field) scaling predictions should remain valid in treatments that incorporate the effects of interfacial fluctuations. As the wall separation L is decreased at bulk liquid-gas coexistence we predict a capillary evaporation transition from the `delocalized interface' phase to a dilute gas state with just a thin adsorbed film of liquid-like density next to the solvophilic wall. This transition is connected closely to the first order pre-wetting transition which occurs at the solvophilic wall in the semi-infinite system. We compare the phase diagram for the competing walls system with the phase diagrams for the fluid confined between identical solvophilic and identical solvophobic walls.

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arXiv2007

Effective anisotropies and energy barriers of magnetic nanoparticles with Neel surface anisotropy

Magnetic nanoparticles with Neel surface anisotropy, different internal structures, surface arrangements and elongation are modelled as many-spin systems. The results suggest that the energy of many-spin nanoparticles cut from cubic lattices can be represented by an effective one-spin potential containing uniaxial and cubic anisotropies. It is shown that the values and signs of the corresponding constants depend strongly on the particle's surface arrangement, internal structure and elongation. Particles cut from a simple cubic lattice have the opposite sign of the effective cubic term, as compared to particles cut from the face-centered cubic lattice. Furthermore, other remarkable phenomena are observed in nanoparticles with relatively strong surface effects: (i) In elongated particles surface effects can change the sign of the uniaxial anisotropy. (ii) In symmetric particles (spherical and truncated octahedral) with cubic core anisotropy surface effects can change its sign. We also show that the competition between the core and surface anisotropies leads to a new energy that contributes to both the 2nd- and 4th-order effective anisotropies.

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arXiv2007

Continuous Capillary Condensation

We show that condensation in a capped capillary slit is a continuous interfacial critical phenomenon, related intimately to several other surface phase transitions. In three dimensions (3d), the adsorption and desorption branches correspond to the unbinding of the meniscus from the cap and opening, respectively and are equivalent to 2d-like complete-wetting transitions. For dispersion forces, the singularities on the two branches are distinct, owing to the different interplay of geometry and intermolecular forces. In 2d we establish precise connection, or covariance, with 2d critical-wetting and wedge-filling transitions, i.e. we establish that certain interfacial properties in very different geometries are identical. Our predictions of universal scaling and covariance in finite capillaries are supported by extensive Ising model simulation studies in 2d and 3d.

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arXiv2006

A model colloidal fluid with competing interactions: bulk and interfacial properties

Using a simple mean-field density functional theory theory (DFT), we investigate the structure and phase behaviour of a model colloidal fluid composed of particles interacting via a pair potential which has a hard core of diameter $σ$, is attractive Yukawa at intermediate separations and repulsive Yukawa at large separations. We analyse the form of the asymptotic decay of the bulk fluid correlation functions, comparing results from our DFT with those from the self consistent Ornstein-Zernike approximation (SCOZA). In both theories we find rich crossover behaviour, whereby the ultimate decay of correlation functions changes from monotonic to long-wavelength damped oscillatory decay on crossing certain lines in the phase diagram, or sometimes from oscillatory to oscillatory with a longer wavelength. For some choices of potential parameters we find, within the DFT, a $λ$-line at which the fluid becomes unstable with respect to periodic density fluctuations. SCOZA fails to yield solutions for state points near such a $λ$-line. The propensity to clustering of particles, which is reflected by the presence of a long wavelength $\gg σ$, slowly decaying oscillatory pair correlation function, and a structure factor that exhibits a very sharp maximum at small but non zero wavenumbers, is enhanced in states near the $λ$-line. We present density profiles for the planar liquid-gas interface and for fluids adsorbed at a planar hard wall. The presence of a nearby $λ$-transition gives rise to pronounced long-wavelength oscillations in the one-body densities at both types of interface.

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arXiv2006

Screening in Yukawa fluid mixtures

The effective pair potential between mesoscopic charged particles in a neutralising background medium takes a Yukawa form $\exp(-λr)/r$ with screening length $λ^{-1}$. We consider a dilute suspension of such Yukawa particles dispersed in a solvent with correlation length $ξ<λ^{-1}$ and show that the Yukawa interaction is `screened' if the pair potentials between solvent particles exhibit Yukawa decay with the same screening length $λ^{-1}$. However, if the solvent pair potentials are shorter ranged than the solute Yukawa potentials, then the effective potential between pairs of solute particles is `unscreened', i.e. the effective potential between the solute particles is equal to the bare potential at large particle separations.

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arXiv2005

Pair correlation functions and phase separation in a two component point Yukawa fluid

We investigate the structure of a binary mixture of particles interacting via purely repulsive (point) Yukawa pair potentials with a common inverse screening length $λ$. Using the hyper-netted chain closure to the Ornstein-Zernike equations, we find that for a system with `ideal' (Berthelot mixing rule) pair potential parameters for the interaction between unlike species, the asymptotic decay of the total correlation functions crosses over from monotonic to damped oscillatory on increasing the fluid total density at fixed composition. This gives rise to a Kirkwood line in the phase diagram. We also consider a `non-ideal' system, in which the Berthelot mixing rule is multiplied by a factor $(1+δ)$. For any $δ>0$ the system exhibits fluid-fluid phase separation and remarkably the ultimate decay of the correlation functions is now monotonic for all (mixture) state points. Only in the limit of vanishing concentration of either species does one find oscillatory decay extending to $r = \infty$. In the non-ideal case the simple random phase approximation provides a good description of the phase separation and the accompanying Lifshitz line.

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arXiv2005

Asymptotic decay of pair correlations in a Yukawa fluid

We analyse the $r \to \infty$ asymptotic decay of the total correlation function, $h(r)$, for a fluid composed of particles interacting via a (point) Yukawa pair potential. Such a potential provides a simple model for dusty plasmas. The asymptotic decay is determined by the poles of the liquid structure factor in the complex plane. We use the hypernetted-chain closure to the Ornstein-Zernike equation to determine the line in the phase diagram, well-removed from the freezing transition line, where crossover occurs in the ultimate decay of $h(r)$, from monotonic to damped oscillatory. We show: i) crossover takes place via the same mechanism (coalescence of imaginary poles) as in the classical one-component plasma and in other models of Coulomb fluids and ii) leading-order pole contributions provide an accurate description of $h(r)$ at intermediate distances $r$ as well as at long range.

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arXiv2005

Soft core fluid in a quenched matrix of soft core particles: A mobile mixture in a model gel

We present a density-functional study of a binary phase-separating mixture of soft core particles immersed in a random matrix of quenched soft core particles of larger size. This is a model for a binary polymer mixture immersed in a crosslinked rigid polymer network. Using the replica `trick' for quenched-annealed mixtures we derive an explicit density functional theory that treats the quenched species on the level of its one-body density distribution. The relation to a set of effective external potentials acting on the annealed components is discussed. We relate matrix-induced condensation in bulk to the behaviour of the mixture around a single large particle. The interfacial properties of the binary mixture at a surface of the quenched matrix display a rich interplay between capillary condensation inside the bulk matrix and wetting phenomena at the matrix surface.

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arXiv2005

Inhomogeneous hard-sphere mixtures: Manifestations of structural crossover

We study various manifestations of structural crossover in the properties of a binary mixture of hard-spheres. For homogeneous mixtures that are sufficiently asymmetric, there is a crossover line in the phase diagram such that for thermodynamic states that lie on one side, the decay of the three bulk pair correlation functions is oscillatory with a common wavelength approximately equal to the diameter of the smaller spheres, and for states on the other side, the common wavelength is approximately the diameter of the bigger spheres. Using density functional theory we show that structural crossover manifests itself in the intermediate range decay of i) the one-body density profiles of a hard-sphere mixture adsorbed at planar walls, ii) the effective (depletion) potential between two big hard-spheres immersed in the same binary mixture and iii) the solvation force, or excess pressure, of the same mixture confined between two planar hard-walls. We determine exactly the structural crossover line for a one-dimensional binary mixture of hard-rods and present evidence, based on density functional theory calculations and Monte-Carlo simulations, for structural crossover in homogeneous binary mixtures of hard-disks in two dimensions. By considering a multicomponent mixture of hard-spheres, with an appropriate bimodal distribution of diameters, we argue that structural crossover should still occur in the presence of polydispersity and that our results could be relevant to colloidal mixtures where correlation functions can be measured using real-space techniques.

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arXiv2004

Solvent mediated interactions close to fluid-fluid phase separation: microscopic treatment of bridging in a soft core fluid

Using density functional theory we calculate the density profiles of a binary solvent adsorbed around a pair of big solute particles. All species interact via repulsive Gaussian potentials. The solvent exhibits fluid-fluid phase separation and for thermodynamic states near to coexistence the big particles can be surrounded by a thick adsorbed `wetting' film of the coexisting solvent phase. On reducing the separation between the two big particles we find there can be a `bridging' transition as the wetting films join to form a fluid bridge. The potential between the two big particles becomes long ranged and strongly attractive in the bridged configuration. Within our mean-field treatment the bridging transition results in a discontinuity in the solvent mediated force. We demonstrate that accounting for the phenomenon of bridging requires the presence of a non-zero bridge function in the correlations between the solute particles when our model fluid is described within a full mixture theory based upon the Ornstein-Zernike equations.

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arXiv2004

Non-analytic curvature contributions to solvation free energies: influence of drying

We investigate the solvation of a hard spherical cavity, of radius $R$, immersed in a fluid for which the interparticle forces are short ranged. For thermodynamic states lying close to the liquid binodal, where the chemical potential deviation $δμ\equiv μ- μ_{co}(T)$ is very small and positive, complete wetting by gas (drying) occurs and two regimes of interfacial behavior can be identified. These are characterized by the length scale $R_c=2 γ_{gl}^\infty/(Δρδμ)$, where $γ_{gl}^\infty$ is the planar gas-liquid surface tension and $Δρ$ is the difference in coexisting densities at temperature $T$. For $R>R_c$, the interfacial free energy and the density profile of the fluid near the hard wall can be expanded in powers of the curvature $R^{-1}$, in keeping with the analysis of Stillinger and Cotter, J. Chem. Phys. {\bf 55}, 3449 (1971). In the other regime, $R<R_c$, the interfacial free energy and its derivatives acquire terms depending on $\ln R$. Since $R_c^{-1}$ can be made arbitrarily small this implies non-analytic behavior, as $R^{-1}\to 0$, of the work of formation of a hard spherical cavity and of the Gibbs adsorption and the fluid density at contact with the wall. Our analysis, which is based on an effective interfacial Hamiltonian combined with exact statistical mechanical sum rules, is confirmed fully by the results of microscopic density functional calculations for a square-well fluid.

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arXiv2004

Dynamical density functional theory and its application to spinodal decomposition

We present an alternative derivation of the dynamical density functional theory for the one body density profile of a classical fluid developed by Marconi and Tarazona [J. Chem. Phys., 110, 8032 (1999)]. Our derivation elucidates further some of the physical assumptions inherent in the theory and shows that it is not restricted to fluids composed of particles interacting solely via pair potentials; rather it applies to general, multi-body interactions. The starting point for our derivation is the Smoluchowski equation and the theory is therefore one for Brownian particles and as such is applicable to colloidal fluids. In the second part of this paper we use the dynamical density functional theory to derive a theory for spinodal decomposition that is applicable at both early and intermediate times. For early stages of spinodal decomposition our non-linear theory is equivalent to the (generalised) linear Cahn-Hilliard theory, but for later times it incorporates coupling between different Fourier components of the density fluctuations (modes) and therefore goes beyond Cahn-Hilliard theory. We describe the results of calculations for a model (Yukawa) fluid which show that the coupling leads to the growth of a second maximum in the density fluctuations, at a wavenumber larger than that of the main peak.

cond-mat.stat-mech↗

arXiv2003

Effects of weak surface fields on the density profiles and adsorption of a confined fluid near bulk criticality

The density profile and Gibbs adsorption of a near-critical fluid confined between two identical planar walls is studied by means of Monte Carlo simulation and by density functional theory for a Lennard-Jones fluid. By reducing the strength of wall-fluid interactions relative to fluid-fluid interactions we observe a crossover from behaviour characteristic of the normal surface universality class, strong critical adsorption, to behaviour characteristic of a 'neutral' wall. The crossover is reminiscent of that which occurs near the ordinary surface transition in Ising films subject to vanishing surface fields. For the 'neutral' wall the density profile, away from the walls, is almost constant throughout the slit capillary and gives rise to an adsorption that is constant along the critical isochore. The same 'neutral' wall yields a line of capillary coexistence that is almost identical to the bulk coexistence line. In the crossover regime we observe features in the density profile similar to those found in the magnetisation profile of the critical Ising film subject to weak surface fields, namely two smooth maxima, located away from the walls, which merge into a single maximum at midpoint as the strength of the wall-fluid interaction is reduced or as the distance between walls is decreased. We discuss similarities and differences between the surface critical behaviour of fluids and of Ising magnets.

cond-mat.stat-mech↗

arXiv2003

Wetting at Curved Substrates: Non-Analytic Behavior of Interfacial Properties

We argue that for complete wetting at a curved substrate (wall) the wall-fluid surface tension is non-analytic in $R_i^{-1}$, the curvature of the wall and that the density profile of the fluid near the wall acquires a contribution proportional to the gas-liquid surface tension $\times R_i^{-1}$ plus higher-order contributions which are non-analytic in $R_i^{-1}$. These predictions are confirmed by results of density functional calculations for the square-well model of a liquid adsorbed on a hard sphere and on a hard cylinder where complete wetting by gas (drying) occurs. The implications of our results for the solvation of big solvophobic particles are discussed.

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arXiv2002

Microscopic theory of solvent mediated long range forces: influence of wetting

We show that a general density functional approach for calculating the force between two big particles immersed in a solvent of smaller ones can describe systems that exhibit fluid-fluid phase separation: the theory captures effects of strong adsorption (wetting) and of critical fluctuations in the solvent. We illustrate the approach for the Gaussian core model, a simple model of a polymer mixture in solution and find extremely attractive, long ranged solvent mediated potentials between the big particles for state points lying close to the binodal, on the side where the solvent is poor in the species which is favoured by the big particles.

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