Andrew J. Archer

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, multibody 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 nonlinear theory is equivalent to the (generalized) 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 wave number larger than that of the main peak.

Dynamical density functional theory for interacting brownian particles: Stochastic or deterministic?

We aim to clarify confusions in the literature as to whether or not dynamical density functional theories for the one-body density of a classical Brownian fluid should contain a stochastic noise term. We point out that a stochastic as well as a deterministic equation of motion for the density distribution can be justified, depending on how the fluid one-body density is defined-i.e. whether it is an ensemble averaged density distribution or a spatially and/or temporally coarse grained density distribution.

Phase behavior of a fluid with competing attractive and repulsive interactions

Fluids in which the interparticle potential has a hard core, is attractive at moderate separations, and repulsive at large separations are known to exhibit unusual phase behavior, including stable inhomogeneous phases. Here we report a joint simulation and theoretical study of such a fluid, focusing on the relationship between the liquid-vapor transition line and any new phases. The phase diagram is studied as a function of the amplitude of the attraction for a certain fixed amplitude of the long ranged repulsion. We find that the effect of the repulsion is to substitute the liquid-vapor critical point and a portion of the associated liquid-vapor transition line, by two first-order transitions. One of these transitions separates the vapor from a fluid of spherical liquidlike clusters; the other separates the liquid from a fluid of spherical voids. At low temperature, the two transition lines intersect one another and a vapor-liquid transition line at a triple point. While most integral equation theories are unable to describe the new phase transitions, the Percus-Yevick approximation does succeed in capturing the vapor-cluster transition, as well as aspects of the structure of the cluster fluid, in reasonable agreement with the simulation results.

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 overdamped 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 generalization 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.

Dynamical model for the formation of patterned deposits at receding contact lines.

We describe the formation of deposition patterns that are observed in many different experiments where a three-phase contact line of a volatile nanoparticle suspension or polymer solution recedes. A dynamical model based on a long-wave approximation predicts the deposition of irregular and regular line patterns due to self-organized pinning-depinning cycles corresponding to a stick-slip motion of the contact line. We analyze how the line pattern properties depend on the evaporation rate and solute concentration.

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 characterizing the modulations in the microphase separated phases. We also investigate the behavior of the system under confinement between two parallel hard walls. We find that the confined fluid phase behavior can be rather complex.

Model colloidal fluid with competing interactions: Bulk and interfacial properties

Using a simple mean field density functional theory (DFT), the authors investigate the structure and phase behavior of a model colloidal fluid composed of particles interacting via a pair potential which has a hard core of diameter sigma, is attractive Yukawa at intermediate separations, and is repulsive Yukawa at large separations. The authors analyze the form of the asymptotic decay of the bulk fluid correlation functions, comparing results from DFT with those from the self-consistent Ornstein-Zernike approximation (SCOZA). In both theories the authors find rich crossover behavior, 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 the authors find, within the DFT, a lambda line at which the fluid becomes unstable with respect to periodic density fluctuations. SCOZA fails to yield solutions for state points near such a lambda line. The propensity towards clustering of particles, which is reflected by the presence of a long wavelength (>>sigma) slowly decaying oscillatory pair correlation function, and a structure factor that exhibits a very sharp maximum at small but nonzero wave numbers, is enhanced in states near the lambda line. The authors present density profiles for the planar liquid-gas interface and for fluids adsorbed at a planar hard wall. The presence of a nearby lambda transition gives rise to pronounced long wavelength oscillations in the one-body density profiles at both types of interface.

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 each other by the line of second order transitions.

Dynamical density functional theory for dense atomic liquids

Starting from Newtons 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.

Thermodynamically consistent description of the hydrodynamics of free surfaces covered by insoluble surfactants of high concentration

In this paper, we propose several models that describe the dynamics of liquid films which are covered by a high concentration layer of insoluble surfactant. First, we briefly review the “classical” hydrodynamic form of the coupled evolution equations for the film height and surfactant concentration that are well established for small concentrations. Then we re-formulate the basic model as a gradient dynamics based on an underlying free energy functional that accounts for wettability and capillarity. Based on this re-formulation in the framework of nonequilibrium thermodynamics, we propose extensions of the basic hydrodynamic model that account for (i) nonlinear equations of state, (ii) surfactant-dependent wettability, (iii) surfactant phase transitions, and (iv) substrate-mediated condensation. In passing, we discuss important differences to most of the models found in the literature.