arXiv subjects

A. J. Archer

Publications and source records attributed to A. J. Archer.

At least 37 records · Page 2Linked to original sources

arXiv2013

Quasicrystalline order and a crystal-liquid state in a soft-core fluid

A two-dimensional system of soft particles interacting via a two-length-scale potential is studied. Density functional theory and Brownian dynamics simulations reveal a fluid phase and two crystalline phases with different lattice spacing. Of these the larger lattice spacing phase can form an exotic periodic state with a fraction of highly mobile particles: a crystal liquid. Near the transition between this phase and the smaller lattice spacing phase, quasicrystalline structures may be created by a competition between linear instability at one scale and nonlinear selection of the other.

cond-mat.soft↗

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.

cond-mat.soft↗

arXiv2012

Solidification fronts in supercooled liquids: how rapid fronts can lead to disordered glassy solids

We determine the speed of a crystallisation (or more generally, a solidification) front as it advances into the uniform liquid phase after the system has been quenched into the crystalline region of the phase diagram. We calculate the front speed by assuming a dynamical density functional theory model for the system and applying a marginal stability criterion. Our results also apply to phase field crystal (PFC) models of solidification. As the solidification front advances into the unstable liquid phase, the density profile behind the advancing front develops density modulations and the wavelength of these modulations is a dynamically chosen quantity. For shallow quenches, the selected wavelength is precisely that of the crystalline phase and so well-ordered crystalline states are formed. However, when the system is deeply quenched, we find that this wavelength can be quite different from that of the crystal, so that the solidification front naturally generates disorder in the system. Significant rearrangement and ageing must subsequently occur for the system to form the regular well-ordered crystal that corresponds to the free energy minimum. Additional disorder is introduced whenever a front develops from random initial conditions. We illustrate these findings with results obtained from the PFC.

cond-mat.soft↗

arXiv2011

Phase separation dynamics in a two-dimensional magnetic mixture

Based on classical density functional theory (DFT), we investigate the demixing phase transition of a two-dimensional, binary Heisenberg fluid mixture. The particles in the mixture are modeled as Gaussian soft spheres, where one component is characterized by an additional classical spin-spin interaction of Heisenberg type. Within the DFT we treat the particle interactions using a mean-field approximation. For certain magnetic coupling strengths we calculate phase diagrams in the density-concentration plane. For sufficiently large coupling strengths and densities, we find a demixing phase transition driven by the ferromagnetic interactions of the magnetic species. We also provide a microscopic description (i.e., density profiles) of the resulting non-magnetic/magnetic fluid-fluid interface. Finally, we investigate the phase separation using dynamical density functional theory (DDFT), considering both nucleation processes and spinodal demixing.

cond-mat.soft↗

arXiv2011

Phase separation in fluids exposed to spatially periodic external fields

We consider the liquid-vapor type phase transition for fluids confined within spatially periodic external fields. For a fluid in d=3 dimensions, the periodic field induces an additional phase, characterized by large density modulations along the field direction. At the triple point, all three phases (modulated, vapor, and liquid) coexist. At temperatures slightly above the triple point and for low (high) values of the chemical potential, two-phase coexistence between the modulated phase and the vapor (liquid) is observed. We study this phenomenon using computer simulations and mean-field theory for the Ising model. The theory shows that, in order for the modulated phase to arise, the field wavelength must exceed a threshold value. We also find an extremely low tension of the interface between the modulated phase and the vapor/liquid phases. The tension is of the order 10^{-4} kB T per squared lattice spacing, where kB is the Boltzmann constant, and T the temperature. In order to detect such low tensions, a new simulation method is proposed. We also consider the case of d=2 dimensions. The modulated phase then does not survive, leading to a radically different phase diagram.

cond-mat.stat-mech↗

arXiv2011

Criticality and phase separation in a two-dimensional binary colloidal fluid induced by the solvent critical behavior

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.

cond-mat.soft↗

arXiv2011

Modelling the evaporation of thin films of colloidal suspensions using Dynamical Density Functional Theory

Recent experiments have shown that various structures may be formed during the evaporative dewetting of thin films of colloidal suspensions. Nano-particle deposits of strongly branched `flower-like', labyrinthine and network structures are observed. They are caused by the different transport processes and the rich phase behaviour of the system. We develop a model for the system, based on a dynamical density functional theory, which reproduces these structures. The model is employed to determine the influences of the solvent evaporation and of the diffusion of the colloidal particles and of the liquid over the surface. Finally, we investigate the conditions needed for `liquid-particle' phase separation to occur and discuss its effect on the self-organised nano-structures.

cond-mat.soft↗

arXiv2010

Modelling approaches to the dewetting of evaporating thin films of nanoparticle suspensions

We review recent experiments on dewetting thin films of evaporating colloidal nanoparticle suspensions (nanofluids) and discuss several theoretical approaches to describe the ongoing processes including coupled transport and phase changes. These approaches range from microscopic discrete stochastic theories to mesoscopic continuous deterministic descriptions. In particular, we describe (i) a microscopic kinetic Monte Carlo model, (ii) a dynamical density functional theory and (iii) a hydrodynamic thin film model. Models (i) and (ii) are employed to discuss the formation of polygonal networks, spinodal and branched structures resulting from the dewetting of an ultrathin 'postcursor film' that remains behind a mesoscopic dewetting front. We highlight, in particular, the presence of a transverse instability in the evaporative dewetting front, which results in highly branched fingering structures. The subtle interplay of decomposition in the film and contact line motion is discussed. Finally, we discuss a simple thin film model (iii) of the hydrodynamics on the mesoscale. We employ coupled evolution equations for the film thickness profile and mean particle concentration. The model is used to discuss the self-pinning and depinning of a contact line related to the 'coffee-stain' effect. In the course of the review we discuss the advantages and limitations of the different theories, as well as possible future developments and extensions.

cond-mat.soft↗

arXiv2010

Dynamical density functional theory for the dewetting of evaporating thin films of nanoparticle suspensions exhibiting pattern formation

Recent experiments have shown that the striking structure formation in dewetting films of evaporating colloidal nanoparticle suspensions occurs in an ultrathin `postcursor' layer that is left behind by a mesoscopic dewetting front. Various phase change and transport processes occur in the postcursor layer, that may lead to nanoparticle deposits in the form of labyrinthine, network or strongly branched `finger' structures. We develop a versatile dynamical density functional theory to model this system which captures all these structures and may be employed to investigate the influence of evaporation/condensation, nanoparticle transport and solute transport in a differentiated way. We highlight, in particular, the influence of the subtle interplay of decomposition in the layer and contact line motion on the observed particle-induced transverse instability of the dewetting front.

cond-mat.soft↗

arXiv2008

Dynamical density functional theory for molecular and colloidal fluids: a microscopic approach to fluid mechanics

In recent years, a number of dynamical density functional theories (DDFTs) have been developed for describing the dynamics of the one-body density of both colloidal and atomic fluids. In the colloidal case, the particles are assumed to have stochastic equations of motion and theories exist for both the case when the particle motion is over-damped and also in the regime where inertial effects are relevant. In this paper we extend the theory and explore the connections between the microscopic DDFT and the equations of motion from continuum fluid mechanics. In particular, starting from the Kramers equation which governs the dynamics of the phase space probability distribution function for the system, we show that one may obtain an approximate DDFT that is a generalisation of the Euler equation. This DDFT is capable of describing the dynamics of the fluid density profile down to the scale of the individual particles. As with previous DDFTs, the dynamical equations require as input the Helmholtz free energy functional from equilibrium density functional theory (DFT). For an equilibrium system, the theory predicts the same fluid one-body density profile as one would obtain from DFT. Making further approximations, we show that the theory may be used to obtain the mode coupling theory that is widely used for describing the transition from a liquid to a glassy state.

cond-mat.soft↗

arXiv2008

Theory for the phase behaviour of a colloidal fluid with competing interactions

We study the phase behaviour of a fluid composed of particles which interact via a pair potential that is repulsive for large inter-particle distances, is attractive at intermediate distances and is strongly repulsive at short distances (the particles have a hard core). As well as exhibiting gas-liquid phase separation, this system also exhibits phase transitions from the uniform fluid phases to modulated inhomogeneous fluid phases. Starting from a microscopic density functional theory, we develop an order parameter theory for the phase transition in order to examine in detail the phase behaviour. The amplitude of the density modulations is the order parameter in our theory. The theory predicts that the phase transition from the uniform to the modulated fluid phase can be either first order or second order (continuous). The phase diagram exhibits two tricritical points, joined to one another by the line of second order transitions.

cond-mat.soft↗

arXiv2008

Two-dimensional fluid with competing interactions exhibiting microphase separation: theory for bulk and interfacial properties

Colloidal particles that are confined to an interface such as the air-water interface are an example of a two-dimensional fluid. Such dispersions have been observed to spontaneously form cluster and stripe morphologies in certain systems with isotropic pair potentials between the particles, due to the fact that the pair interaction between the colloids has competing attraction and repulsion over different length scales. Here we present a simple density functional theory for a model of such a two-dimensional fluid. The theory predicts a bulk phase diagram exhibiting cluster, stripe and bubble modulated phases, in addition to homogeneous fluid phases. Comparing with simulation results for this model from the literature, we find that the theory is qualitatively reliable. The model allows for a detailed investigation of the structure of the fluid and we are able to obtain simple approximate expressions for the static structure factor and for the length scale characterising the modulations in the microphase separated phases. We also investigate the behaviour of the system under confinement between two parallel hard walls. We find that the confined fluid phase behaviour can be rather complex.

cond-mat.soft↗

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.

cond-mat.soft↗

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.

cond-mat.soft↗

arXiv2006

Dynamical density functional theory for dense atomic liquids

Starting from Newton's equations of motion, we derive a dynamical density functional theory (DDFT) applicable to atomic liquids. The theory has the feature that it requires as input the Helmholtz free energy functional from equilibrium density functional theory. This means that, given a reliable equilibrium free energy functional, the correct equilibrium fluid density profile is guaranteed. We show that when the isothermal compressibility is small, the DDFT generates the correct value for the speed of sound in a dense liquid. We also interpret the theory as a dynamical equation for a coarse grained fluid density and show that the theory can be used (making further approximations) to derive the standard mode coupling theory that is used to describe the glass transition. The present theory should provide a useful starting point for describing the dynamics of inhomogeneous atomic fluids.

cond-mat.soft↗

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.

cond-mat.soft↗

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.

cond-mat.soft↗

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.

cond-mat.soft↗