arXiv subjects

Erik Luijten

Publications and source records attributed to Erik Luijten.

At least 19 recordsLinked to original sources

arXiv2023

Phase Separation and Ripening in a Viscoelastic Gel

The process of phase separation in elastic solids and viscous fluids is of fundamental importance to the stability and function of soft materials. We explore the dynamics of phase separation and domain growth in a viscoelastic material such as a polymer gel. Using analytical theory and Monte Carlo simulations we report a new domain growth regime, in which the domain size increases algebraically with a ripening exponent $α$ that depends on the viscoelastic properties of the material. For a prototypical Maxwell material, we obtain $α=1$, which is markedly different from the well-known Ostwald ripening process with $α=1/3$. We generalize our theory to systems with arbitrary power-law relaxation behavior and discuss our findings in the context of the long-term stability of materials as well as recent experimental results on phase separation in cross-linked networks and cytoskeleton.

cond-mat.soft↗

arXiv2022

Accelerated simulation method for charge regulation effects

The net charge of solvated entities, ranging from polyelectrolytes and biomolecules to charged nanoparticles and membranes, depends on the local dissociation equilibrium of individual ionizable groups. Incorporation of this phenomenon, \emph{charge regulation}, in theoretical and computational models requires dynamic, configuration-dependent recalculation of surface charges and is therefore typically approximated by assuming constant net charge on particles. Various computational methods exist that address this. We present an alternative, particularly efficient charge regulation Monte Carlo method (CR-MC), which explicitly models the redistribution of individual charges and accurately samples the correct grand-canonical charge distribution. In addition, we provide an open-source implementation in the LAMMPS molecular dynamics (MD) simulation package, resulting in a hybrid MD/CR-MC simulation method. This implementation is designed to handle a wide range of implicit-solvent systems that model discreet ionizable groups or surface sites. The computational cost of the method scales linearly with the number of ionizable groups, thereby allowing accurate simulations of systems containing thousands of individual ionizable sites. By matter of illustration, we use the CR-MC method to quantify the effects of charge regulation on the nature of the polyelectrolyte coil--globule transition and on the effective interaction between oppositely charged nanoparticles.

cond-mat.soft↗

arXiv2021

Charge-regulation effects in nanoparticle self-assembly

Nanoparticles in solution acquire charge through dissociation or association of surface groups. Thus, a proper description of their electrostatic interactions requires the use of charge-regulating boundary conditions rather than the commonly employed constant-charge approximation. We implement a hybrid Monte Carlo/Molecular Dynamics scheme that dynamically adjusts the charges of individual surface groups of objects while evolving their trajectories. Charge-regulation effects are shown to qualitatively change self-assembled structures due to global charge redistribution, stabilizing asymmetric constructs. We delineate under which conditions the conventional constant-charge approximation may be employed and clarify the interplay between charge regulation and dielectric polarization.

cond-mat.soft↗

arXiv2018

Asymmetric electrolytes near structured dielectric interfaces

The ion distribution of electrolytes near interfaces with dielectric contrast has important consequences for electrochemical processes and many other applications. To date, most studies of such systems have focused on geometrically simple interfaces, for which dielectric effects are analytically solvable or computationally tractable. However, all real surfaces display nontrivial structure at the nanoscale and have, in particular, nonuniform local curvature. Using a recently developed, highly efficient computational method, we investigate the effect of surface geometry on ion distribution and interface polarization. We consider an asymmetric 2:1 electrolyte bounded by a sinusoidally deformed solid surface. We demonstrate that even when the surface is neutral, the electrolyte acquires a nonuniform ion density profile near the surface. This profile is asymmetric and leads to an effective charging of the surface. We furthermore show that the induced charge is modulated by the local curvature. The effective charge is opposite in sign to the multivalent ions and is larger in concave regions of the surface.

cond-mat.soft↗

arXiv2018

Dielectric modulation of ion transport near interfaces

Ion mobility and ionic conductance in nanodevices are known to deviate from bulk behavior, a phenomenon often attributed to surface effects. We demonstrate that dielectric mismatch between the electrolyte and the surface can qualitatively alter ionic transport in a counterintuitive manner. Instead of following the polarization-induced modulation of the concentration profile, mobility is enhanced or reduced by changes in the ionic atmosphere near the interface and affected by a polarization force parallel to the surface. In addition to revealing this mechanism, we explore the effect of salt concentration and electrostatic coupling.

cond-mat.soft↗

arXiv2018

Accurate and Efficient Numerical Simulation of Dielectrically Anisotropic Particles

A variety of electrostatic phenomena, including the structure of electric double layers and the aggregation of charged colloids and proteins, are affected by nonuniform electric permittivity. These effects are frequently ignored in analytical and computational studies, and particularly difficult to handle in situations where multiple dielectric contrasts are present, such as in colloids that are heterogeneous in permittivity. We present an extension to the Iterative Dielectric Solver developed by Barros and Luijten [Phys. Rev. Lett. 113, 017801 (2014)] that makes it possible to accurately compute the polarization of anisotropic particles with multiple dielectric contrasts. This efficient boundary-element method-based approach is applicable to geometries that are not amenable to other solvers, opening the possibility of studying collective phenomena of dielectrically anisotropic particles. We provide insight into the underlying physical reasons for this efficiency.

cond-mat.soft↗

arXiv2016

The Effective Temperature Concept Tested in an Active Colloid Mixture

Thermal energy agitates all matter and its competition with ordering tendencies is one of the most fundamental organizing principles in the physical world. Thus, it is natural to enquire if an effective temperature could result when external energy input enhances agitation. Potentially this could extend the insights of statistical thermodynamics to nonequilibrium systems, but despite proposals that the effective temperature concept may apply to synthetic active matter, biological motors, granular materials and turbulent fluids, its predictive value remains unclear. Here, combining computer simulations and imaging experiments, we design a two-component system of driven Janus colloids such that collisions produced by external energy sources play the role of temperature, and in this system we demonstrate quantitative agreement with hallmarks of statistical thermodynamics for binary phase behavior: the archetypal phase diagram with equilibrium critical exponents, Gaussian displacement distributions, fluctuation-dissipation relations, and capillarity. These quantitative analogies to equilibrium expectations, observed in this decidedly nonequilibrium system, constitute an existence proof from which to compare future theories of nonequilibrium, but limitations of this concept are also highlighted.

cond-mat.stat-mech↗

arXiv2016

Electric double layer of anisotropic dielectric colloids under electric fields

Anisotropic colloidal particles constitute an important class of building blocks for self-assembly directed by electrical fields. The aggregation of these building blocks is driven by induced dipole moments, which arise from an interplay between dielectric effects and the electric double layer. For particles that are anisotropic in shape, charge distribution, and dielectric properties, calculation of the electric double layer requires coupling of the ionic dynamics to a Poisson solver. We apply recently proposed methods to solve this problem for experimentally employed colloids in static and time-dependent electric fields. This allows us to predict the effects of field strength and frequency on the colloidal properties.

cond-mat.soft↗

arXiv2014

Orientationally Glassy Crystals of Janus Spheres

Colloidal Janus spheres in water (one hemisphere attractive and the other repulsive) assemble into two-dimensional hexagonal crystals with orientational order controlled by anisotropic interactions. We exploit the decoupled translational and rotational order to quantify the orientational dynamics. Via imaging experiments and Monte Carlo simulations we demonstrate that the correlations in the orientation of individual Janus spheres exhibit glasslike dynamics that can be controlled via the ionic strength. Thus, these colloidal building blocks provide a particularly suitable model glass system for elucidating nontrivial dynamics arising from directional interactions, not captured by the consideration of just translational order.

cond-mat.soft↗

arXiv2014

Dielectric effects in the self-assembly of binary colloidal aggregates

Electrostatic interactions play an important role in numerous self-assembly phenomena, including colloidal aggregation. Although colloids typically have a dielectric constant that differs from the surrounding solvent, the effective interactions that arise from inhomogeneous polarization charge distributions are generally neglected in theoretical and computational studies. We introduce an efficient technique to resolve polarization charges in dynamical dielectric geometries, and demonstrate that dielectric effects \emph{qualitatively} alter the predicted self-assembled structures, with surprising colloidal strings arising from many-body effects.

cond-mat.soft↗

arXiv2014

Efficient and accurate simulation of dynamic dielectric objects

Electrostatic interactions between dielectric objects are complex and of a many-body nature, owing to induced surface bound charge. We present a collection of techniques to simulate dynamical dielectric objects. We calculate the surface bound charge from a matrix equation using the Generalized Minimal Residue method (GMRES). Empirically, we find that GMRES converges very quickly. Indeed, our detailed analysis suggests that the relevant matrix has a very compact spectrum for all non-degenerate dielectric geometries. Each GMRES iteration can be evaluated using a fast Ewald solver with cost that scales linearly or near-linearly in the number of surface charge elements. We analyze several previously proposed methods for calculating the bound charge, and show that our approach compares favorably.

cond-mat.soft↗

arXiv2013

Efficient Estimation of Highly Structured Posteriors of Gravitational-Wave Signals with Markov-Chain Monte Carlo

We introduce a new Markov-Chain Monte Carlo (MCMC) approach designed for efficient sampling of highly correlated and multimodal posteriors. Parallel tempering, though effective, is a costly technique for sampling such posteriors. Our approach minimizes the use of parallel tempering, only using it for a short time to tune a new jump proposal. For complex posteriors we find efficiency improvements up to a factor of ~13. The estimation of parameters of gravitational-wave signals measured by ground-based detectors is currently done through Bayesian inference with MCMC one of the leading sampling methods. Posteriors for these signals are typically multimodal with strong non-linear correlations, making sampling difficult. As we enter the advanced-detector era, improved sensitivities and wider bandwidths will drastically increase the computational cost of analyses, demanding more efficient search algorithms to meet these challenges.

astro-ph.IM↗

arXiv2010

Monte Carlo cluster algorithm for fluid phase transitions in highly size-asymmetrical binary mixtures

Highly size-asymmetrical fluid mixtures arise in a variety of physical contexts, notably in suspensions of colloidal particles to which much smaller particles have been added in the form of polymers or nanoparticles. Conventional schemes for simulating models of such systems are hamstrung by the difficulty of relaxing the large species in the presence of the small one. Here we describe how the rejection-free geometrical cluster algorithm (GCA) of Liu and Luijten [Phys. Rev. Lett 92, 035504 (2004)] can be embedded within a restricted Gibbs ensemble to facilitate efficient and accurate studies of fluid phase behavior of highly size-asymmetrical mixtures. After providing a detailed description of the algorithm, we summarize the bespoke analysis techniques of Ashton et al. [J. Chem. Phys. 132, 074111 (2010)] that permit accurate estimates of coexisting densities and critical-point parameters. We apply our methods to study the liquid--vapor phase diagram of a particular mixture of Lennard-Jones particles having a 10:1 size ratio. As the reservoir volume fraction of small particles is increased in the range 0--5%, the critical temperature decreases by approximately 50%, while the critical density drops by some 30%. These trends imply that in our system, adding small particles decreases the net attraction between large particles, a situation that contrasts with hard-sphere mixtures where an attractive depletion force occurs.

cond-mat.soft↗

arXiv2007

Quantum criticality, lines of fixed points, and phase separation in doped two-dimensional quantum dimer models

We study phase diagrams of a class of doped quantum dimer models on the square lattice with ground-state wave functions whose amplitudes have the form of the Gibbs weights of a classical doped dimer model. In this dimer model, parallel neighboring dimers have attractive interactions, whereas neighboring holes either do not interact or have a repulsive interaction. We investigate the behavior of this system via analytic methods and by Monte Carlo simulations. At zero doping, we confirm the existence of a Kosterlitz-Thouless transition from a quantum critical phase to a columnar phase. At low hole densities we find a dimer-hole liquid phase and a columnar phase, separated by a phase boundary which is a line of critical points with varying exponents. We demonstrate that this line ends at a multicritical point where the transition becomes first order and the system phase separates. The first-order transition coexistence curve is shown to become unstable with respect to more complex inhomogeneous phases in the presence of direct hole-hole interactions. We also use a variational approach to determine the spectrum of low-lying density fluctuations in the dimer-hole fluid phase.

cond-mat.str-el↗

arXiv2007

Polyelectrolyte Condensation Induced by Linear Cations

We examine the role of the condensing agent in the formation of polyelectrolyte bundles, via grand-canonical Monte Carlo simulations. Following recent experiments we use linear, rigid divalent cations of various lengths to induce condensation. Our results clarify and explain the experimental results for short cations. For longer cations we observe novel condensation behavior owing to alignment of the cations. We also study the role of the polyelectrolyte surface charge density, and find a nonmonotonic variation in bundle stability. This nonmonotonicity captures two trends that have been observed in separate experiments.

cond-mat.soft↗

arXiv2006

Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes

We study the salt-dependent conformations of dilute flexible polyelectrolytes in solution via computer simulations. Low concentrations of multivalent salt induce the known conformational collapse of individual polyelectrolyte chains, but as the salt concentration is increased further this is followed by a reexpansion. We explicitly demonstrate that multivalent counterions can overcompensate the bare charge of the chain in the reexpansion regime. Both the degree of reexpansion and the occurrence of overcharging sensitively depend on ion size. Our findings are relevant for a wide range of salt-induced complexation phenomena.

cond-mat.soft↗

arXiv2006

Simulation of phase transitions in highly asymmetric fluid mixtures

We present a novel method for the accurate numerical determination of the phase behavior of fluid mixtures having large particle size asymmetries. By incorporating the recently developed geometric cluster algorithm within a restricted Gibbs ensemble, we are able to probe directly the density and concentration fluctuations that drive phase transitions, but that are inaccessible to conventional simulation algorithms. We develop a finite-size scaling theory that relates these density fluctuations to those of the grand-canonical ensemble, thereby enabling accurate location of critical points and coexistence curves of multicomponent fluids. Several illustrative examples are presented.

cond-mat.soft↗

arXiv2006

Confinement-driven translocation of a flexible polymer

We consider the escape of a flexible, self-avoiding polymer chain out of a confined geometry. By means of simulations, we demonstrate that the translocation time can be described by a simple scaling law that exhibits a nonlinear dependence on the degree of polymerization and that is sensitive to the nature of the confining geometry. These results contradict earlier predictions but are in agreement with recently confirmed geometry-dependent expressions for the free energy of confinement.

cond-mat.soft↗