arXiv subjects

Andrew J. Archer

Publications and source records attributed to Andrew J. Archer.

At least 19 recordsLinked to original sources

arXiv2026

A route to the thermodynamics of colloid-polymer mixtures from structural information

Liquid-state theory provides a fundamental connection between microscopic structure and macroscopic thermodynamic behaviour. Here, we develop a framework for predicting thermodynamics and phase behaviour directly from structural correlations, using either radial distribution functions or static structure factors as input. The approach constructs a free-energy functional from structural information obtained at a single thermodynamic state point, without requiring explicit knowledge of the underlying interaction potentials. This circumvents a central difficulty in modelling complex fluids, for which effective interactions are often unknown or rely on approximations. We demonstrate the framework for a range of model fluids, including colloidal and colloid--polymer systems, with predictions in good agreement with molecular simulation data. The results show that structural information at a single state point can provide sufficient information to predict the broader thermodynamic response of a system. This establishes a route toward inferring phase behaviour directly from experimentally measured structure, even when the microscopic interactions are not known a priori.

cond-mat.soft↗

arXiv2026

Liquid bridges between horizontal cylinders: effects of gravity and electric fields

Liquid bridges suspended between two parallel horizontal cylinders are studied using experiments, reduced-order mathematical modelling and numerical simulations. Both non-electrified and electrified configurations are considered, with the cylinders acting as electrodes between which a potential difference can be applied. The initial focus is on equilibrium bridge shapes, while the dynamics is examined only in the non-electrified case. In the experiments, transformer-oil bridges are investigated and modelled as perfect dielectrics. The electric field counteracts the gravitational effects and causes the bridges to rise and become flatter, with shapes that are well described by Young--Laplace-type equations containing non-local electric-field contributions evaluated using a boundary-element method. Bifurcation diagrams of these solutions are constructed by pseudo-arclength continuation to characterise the dependence of bridge shapes on liquid volume and electric-field strength. In the absence of an electric field, the transient relaxation to equilibrium is analysed using a reduced-order model developed using Onsager's variational principle, with comparison to direct numerical simulations. The steady states predicted by the reduced-order model agree closely with those of the full formulation over a wide parameter range, and the dynamics is well captured in the overdamped regime.

physics.flu-dyn↗

arXiv2026

Navigating complex phase diagrams in soft matter systems

Colloidal fluids can exhibit complex phase behavior and determining phase diagrams via experiments or computer simulations can be laborious. We demonstrate that the dispersion relation $ω(k)$, obtained from dynamical density functional theory for the uniform density system, is a highly versatile tool for {\it predicting} where in the phase diagram complex crystals form. The sign of $ω(k)$ determines whether density modes with wavenumber $k$ grow or decay over time. We demonstrate the predictive power by investigating the complex phase behavior of particles interacting via core-shoulder pair potentials. With complementary Monte Carlo simulations, we show that regions of the phase diagram where $ω(k)$ has one or several unstable (growing) wavenumbers are also where crystalline phases occur. Going further, by tuning these unstable wavenumbers via the interaction-potential and state-point parameters, we design systems with quasicrystals in the phase diagram. We identify a system with a certain shoulder-range exhibiting at least 10 different phases. Our general approach accelerates considerably the mapping of complex phase diagrams, crucial for the design of new materials.

cond-mat.soft↗

arXiv2024

Coexisting multiphase and interfacial behaviour of ouzo

Multi-component liquid mixtures can be both complex and fascinating, with some systems being amenable to simple experimentation at home, giving valuable insight into fundamental aspects of bulk and interfacial phase behaviour. One particularly interesting mixture is the popular drink ouzo, which has charmed both the general public and scientists by virtue of its ability to display spontaneous emulsification when water is added. When these two clear (and potable) liquids are poured into each other, a single milky-coloured liquid is formed. In previous work [Archer et al., Soft Matter 20, 5889 (2024)], the equilibrium phase-diagram for the stable liquid phases of ouzo was captured via experiment and modelling. Here we consider the case when the two liquid phases also coexist with the vapour phase (i.e. along a line of triple points) and within our model uncover the complex bulk phase behaviour for this simple beverage. As a consequence, this leads to some interesting observations, that also apply more widely, about visualising phase diagrams in ternary systems of this type. We also examine the interfacial behaviour, connecting microscopic density functional theory results with macroscopic (Neumann) predictions for the shape of droplets at interfaces.

cond-mat.soft↗

arXiv2024

Fingerprints of ordered self-assembled structures in the liquid phase of a hard-core, square-shoulder system

We investigate the phase ordering (pattern formation) of systems of two-dimensional core-shell particles using Monte-Carlo (MC) computer simulations and classical density functional theory (DFT). The particles interact via a pair potential having a hard core and a repulsive square shoulder. Our simulations show that on cooling, the liquid state structure becomes increasingly characterised by long wavelength density modulations, and on further cooling forms a variety of other phases, including clustered, striped and other patterned phases. In DFT, the hard core part of the potential is treated using either fundamental measure theory or a simple local density approximation, whereas the soft shoulder is treated using the random phase approximation. The different DFTs are bench-marked using large-scale grand-canonical-MC and Gibbs-ensemble-MC simulations, demonstrating their predictive capabilities and shortcomings. We find that having the liquid state static structure factor $S(k)$ for wavenumber $k$ is sufficient to identify the Fourier modes governing both the liquid and solid phases. This allows to identify from easier-to-obtain liquid state data the wavenumbers relevant to the periodic phases and to predict roughly where in the phase diagram these patterned phases arise.

cond-mat.soft↗

arXiv2024

Experimental and Theoretical Bulk Phase Diagram and Interfacial Tension of Ouzo

Ouzo is a well-known drink in Mediterranean countries, with ingredients water, alcohol and trans-anethole oil. The oil is insoluble in water, but completely soluble in alcohol, so when water is added to the spirit, the available alcohol is depleted and the mixture exhibits spontaneous emulsification. This process is commonly known as the louche or Ouzo effect. Although the phase boundaries of this archetypal ternary mixture are well known, the properties of coexisting phases have not previously been studied. Here, we present a detailed experimental investigation into the phase behaviour, including tie-lines connecting coexisting phases, determination of the critical point (also called the plait point in ternary systems) and measurements of the surface tension and density for varying alcohol concentrations. Additionally, we present a theory for the thermodynamics and phase diagram of the system. With suitable selection of the interaction parameters, the theory captures nearly all features of the experimental work. This simple model can be used to determine both bulk and non-uniform (e.g. interfacial) properties, paving the way for a wide range of future applications of the model to ternary mixtures in general. We show how our accurate equilibrium phase diagram can be used to provide improved understanding of non-equilibrium phenomena.

cond-mat.soft↗

arXiv2024

Dynamic Density Functional Theory with Inertia and Background Flow

We present dynamic density functional theory (DDFT) incorporating general inhomogeneous, incompressible, time dependent background flows and inertia, describing externally driven passive colloidal systems out of equilibrium. We start by considering the underlying nonequilibrium Langevin dynamics, including the effect of the local velocity of the surrounding liquid bath, to obtain the nonlinear, nonlocal partial differential equations governing the evolution of the (coarse--grained) density and velocity fields describing the dynamics of colloids. Additionally, we show both with heuristic arguments, and by numerical solution, that our equations and solutions agree with existing DDFTs in the overdamped (high friction) limit. We provide numerical solutions that model the flow of hard spheres, in both unbounded and confined domains, and compare to previously--derived DDFTs with and without the background flow.

cond-mat.soft↗

arXiv2024

Binding potential and wetting behaviour of binary liquid mixtures on surfaces

We present a theory for the interfacial wetting phase behaviour of binary liquid mixtures on rigid solid substrates, applicable to both miscible and immiscible mixtures. In particular, we calculate the binding potential as a function of the adsorptions, i.e. the excess amounts of each of the two liquids at the substrate. The binding potential fully describes the corresponding interfacial thermodynamics. Our approach is based on classical density functional theory. Binary liquid mixtures can exhibit complex bulk phase behaviour, including both liquid-liquid and vapour-liquid phase separation, depending on the nature of the interactions between all the particles of the two different liquids, the temperature and the chemical potentials. Here we show that the interplay between the bulk phase behaviour of the mixture and the properties of the interactions with the substrate gives rise to a wide variety of interfacial phase behaviours, including mixing and demixing situations. We find situations where the final state is a coexistence of up to three different phases. We determine how the liquid density profiles close to the substrate change as the interaction parameters are varied and how these determine the form of the binding potential, which in certain cases can be a multi-valued function of the adsorptions. We also present profiles for sessile droplets of both miscible and immiscible binary liquids.

cond-mat.soft↗

arXiv2022

Thermodynamics, formation dynamics and structural correlations in the bulk amorphous phase of the phase-field crystal model

We investigate bulk thermodynamic and microscopic structural properties of amorphous solids in the framework of the phase-field crystal (PFC) model. These are metastable states with a non-uniform density distribution having no long-range order. From extensive numerical simulations we determine the distribution of free energy density values in varying size amorphous systems and also the point-to-set correlation length, which is the radius of the largest volume of amorphous one can take while still having the particle arrangements within the volume determined by the particle ordering at the surface of the chosen volume. We find that in the thermodynamic limit, the free energy density of the amorphous tends to a value that has a slight dependence on the initial state from which it was formed -- i.e.\ it has a formation history dependence. The amorphous phase is observed to form on both sides of the liquid linear-stability limit, showing that the liquid to amorphous transition is first order, with an associated finite free energy barrier when the liquid is metastable. In our simulations this is demonstrated when noise in the initial density distribution is used to induce nucleation events from the metastable liquid. Depending on the strength of the initial noise, we observe a variety of nucleation pathways, in agreement with previous results for the PFC model, and which show that amorphous precursor mediated multi-step crystal nucleation can occur in colloidal systems.

cond-mat.soft↗

arXiv2022

Rectangle--triangle soft-matter quasicrystals with hexagonal symmetry

Aperiodic (quasicrystalline) tilings, such as Penrose's tiling, can be built up from e.g. kites and darts, squares and equilateral triangles, rhombi or shield shaped tiles and can have a variety of different symmetries. However, almost all quasicrystals occurring in soft-matter are of the dodecagonal type. Here, we investigate a class of aperiodic tilings with hexagonal symmetry that are based on rectangles and two types of equilateral triangles. We show how to design soft-matter systems of particles interacting via pair potentials containing two length-scales that form aperiodic stable states with two different examples of rectangle--triangle tilings. One of these is the bronze-mean tiling, while the other is a generalization. Our work points to how more general (beyond dodecagonal) quasicrystals can be designed in soft-matter.

cond-mat.soft↗

arXiv2022

Smectic Layering: Landau theory for a complex-tensor order parameter

Composed of microscopic layers that stack along one direction while maintaining fluid-like positional disorder within layers, smectics are excellent systems for exploring topology, defects and geometric memory in complex confining geometries. However, the coexistence of crystalline-like characteristics in one direction and fluid-like disorder within layers makes lamellar liquid crystals notoriously difficult to model - especially in the presence of defects and large distortions. Nematic properties of smectics can be comprehensively described by the Q-tensor but to capture the features of the smectic layering alone, we develop a phenomenological Landau theory for a complex-tensor order parameter E, which is capable of describing the local degree of lamellar ordering, layer displacement, and orientation of the layers. This theory can account for both parallel and perpendicular elastic contributions. In addition to resolving the potential ambiguities inherent to complex scalar order parameter models, this model reduces to previous employed models of simple smectics, and opens new possibilities for numerical studies on smectics possessing many defects, within complex geometries and under extreme confinement.

cond-mat.soft↗

arXiv2021

Density Distribution in Soft Matter Crystals and Quasicrystals

The density distribution in solids is often represented as a sum of Gaussian peaks (or similar functions) centred on lattice sites or via a Fourier sum. Here, we argue that representing instead the $\mathit{logarithm}$ of the density distribution via a Fourier sum is better. We show that truncating such a representation after only a few terms can be highly accurate for soft matter crystals. For quasicrystals, this sum does not truncate so easily, nonetheless, representing the density profile in this way is still of great use, enabling us to calculate the phase diagram for a 3-dimensional quasicrystal forming system using an accurate non-local density functional theory.

cond-mat.soft↗

arXiv2021

Dynamical density functional theory for the drying and stratification of binary colloidal dispersions

We develop a dynamical density functional theory based model for the drying of colloidal films on planar surfaces. We consider mixtures of two different sizes of hard-sphere colloids. Depending on the solvent evaporation rate and the initial concentrations of the two species, we observe varying degrees of stratification in the final dried films. Our model predicts the various structures described in the literature previously from experiments and computer simulations, in particular the small-on-top stratified films. Our model also includes the influence of adsorption of particles to the interfaces.

cond-mat.soft↗

arXiv2021

How ice grows from premelting films and water droplets

Close to the triple point, the surface of ice is covered by a thin liquid layer (so-called quasi-liquid layer) which crucially impacts growth and melting rates. Experimental probes cannot observe the growth processes below this layer, and classical models of growth by vapor deposition do not account for the formation of premelting films. Here, we develop a mesoscopic model of liquid-film mediated ice growth, and identify the various resulting growth regimes. At low saturation, freezing proceeds by terrace spreading, but the motion of the buried solid is conveyed through the liquid to the outer liquid-vapor interface. At higher saturations water droplets condense, a large crater forms below, and freezing proceeds undetectably beneath the droplet. Our approach is a general framework that naturally models freezing close to three phase coexistence and provides a first principle theory of ice growth and melting which may prove useful in the geosciences.

physics.chem-ph↗

arXiv2020

Snaking without subcriticality: grain boundaries as non-topological defects

Non-topological defects such as grain boundaries abound in pattern forming systems, arising from local variations of pattern properties such as amplitude, wavelength, orientation, etc. We introduce the idea of treating such non-topological defects as spatially localised structures that are embedded in a background pattern, instead of treating them in an amplitude-phase decomposition. Using the two-dimensional quadratic-cubic Swift--Hohenberg equation as an example we obtain fully nonlinear equilibria that contain grain boundaries which are closed curves containing multiple penta-hepta defects separating regions of hexagons with different orientations. These states arise from local orientation mismatch between two stable hexagon patterns, one of which forms the localised grain and the other its background, and do not require a subcritical bifurcation connecting them. Multiple robust isolas that span a wide range of parameters are obtained even in the absence of a unique Maxwell point, underlining the importance of retaining pinning when analysing patterns with defects, an effect omitted from the amplitude-phase description.

nlin.PS↗

arXiv2020

Localized states in passive and active phase-field-crystal models

The passive conserved Swift-Hohenberg equation (or phase-field-crystal [PFC] model) corresponds to a gradient dynamics for a single order parameter field related to density. It provides a simple microscopic description of the thermodynamic transition between liquid and crystalline states. In addition to spatially extended periodic structures, the model describes a large variety of steady spatially localized structures. In appropriate bifurcation diagrams the corresponding solution branches exhibit characteristic slanted homoclinic snaking. In an active PFC model, encoding for instance the active motion of self-propelled colloidal particles, the gradient dynamics structure is broken by a coupling between density and an additional polarization field. Then, resting and traveling localized states are found with transitions characterized by parity-breaking drift bifurcations. Here, we first briefly review the snaking behavior of localized states in passive and active PFC models before discussing the bifurcation behavior of localized states in systems of (i) two coupled passive PFC equations described by common gradient dynamics, (ii) two coupled passive PFC where the coupling breaks the gradient dynamics structure, and (iii) a passive PFC coupled to an active PFC.

cond-mat.soft↗

arXiv2020

Adaptive stochastic continuation with a modified lifting procedure applied to complex systems

Many complex systems occurring in the natural or social sciences or economics are frequently described on a microscopic level, e.g., by lattice- or agent-based models. To analyze the states of such systems and their bifurcation structure on the level of macroscopic observables, one has to rely on equation-free methods like stochastic continuation. Here, we investigate how to improve stochastic continuation techniques by adaptively choosing the parameters of the algorithm. This allows one to obtain bifurcation diagrams quite accurately, especially near bifurcation points. We introduce lifting techniques which generate microscopic states with a naturally grown structure, which can be crucial for a reliable evaluation of macroscopic quantities. We show how to calculate fixed points of fluctuating functions by employing suitable linear fits. This procedure offers a simple measure of the statistical error. We demonstrate these improvements by applying the approach in analyses of (i) the Ising model in two dimensions, (ii) an active Ising model, and (iii) a stochastic Swift-Hohenberg model. We conclude by discussing the abilities and remaining problems of the technique.

nlin.AO↗

arXiv2020

Efficient calculation of phase coexistence and phase diagrams: application to a binary phase-field crystal model

We show that one can employ well-established numerical continuation methods to efficiently calculate the phase diagram for thermodynamic systems. In particular, this involves the determination of lines of phase coexistence related to first order phase transitions and the continuation of triple points. To illustrate the method we apply it to a binary Phase-Field-Crystal model for the crystallisation of a mixture of two types of particles. The resulting phase diagram is determined for one- and two-dimensional domains. In the former case it is compared to the diagram obtained from a one-mode approximation. The various observed liquid and crystalline phases and their stable and metastable coexistence are discussed as well as the temperature-dependence of the phase diagrams. This includes the (dis)appearance of critical points and triple points. We also relate bifurcation diagrams for finite-size systems to the thermodynamics of phase transitions in the infinite-size limit.

cond-mat.soft↗