arXiv subjects

René van Roij

Publications and source records attributed to René van Roij.

At least 37 records · Page 2Linked to original sources

arXiv2022

Absence of anomalous underscreening in highly concentrated aqueous electrolytes confined between smooth silica surfaces

Recent experiments and a series of subsequent theoretical studies suggest the occurrence of universal underscreening in highly concentrated electrolyte solutions. We performed a set of systematic Atomic Force Spectroscopy measurements for aqueous salt solutions in a concentration range from 1 mM to 5 M using chloride salts of various alkali metals as well as mixed concentrated salt solutions (involving both mono- and divalent cations and anions), that mimic concentrated brines typically encountered in geological formations. Experiments were carried out using flat substrates and submicrometer-sized colloidal probes made of smooth oxidized silicon immersed in salt solutions at pH values of 6 and 9 and temperatures of 25 °C and 45 °C. While strong repulsive forces were observed for the smallest tip-sample separations, none of the conditions explored displayed any indication of anomalous long range electrostatic forces as reported for macroscopic mica surfaces. Instead, forces are universally dominated by attractive van der Waals interactions at tip-sample separations of $\approx$2nm and beyond for salt concentrations of 1 M and higher. Complementary calculations based on classical density functional theory for the primitive model support these experimental observations and display a consistent decrease in screening length with increasing ion concentration.

cond-mat.soft↗

arXiv2021

The Differential Capacitance as a probe for the electric double layer structure and the electrolyte bulk composition

In this work we theoretically study the differential capacitance of an aqueous electrolyte in contact with a planar electrode, using classical Density Functional Theory, and show how this measurable quantity can be used as a probe to better understand the structure and composition of the electric double layer at play. Specifically, we show how small trace amounts of divalent ions can influence the differential capacitance greatly, and also how small ions dominate its behaviour for high electrode potentials. In this study, we consider primitive model electrolytes, and not only use the standard definition of the differential capacitance, but also derive a new expression from mechanical equilibrium in a planar geometry. This expression reveals explicitly that the first layer of ions near the charged surface is key to its understanding. Our insights might be used as a guide in experiments to better understand the electrolyte-electrode interface as well as the (composition of the) bulk electrolyte.

cond-mat.soft↗

arXiv2021

Liquid Flow Reversibly Creates a Macroscopic Surface Charge Gradient

The charging and dissolution of mineral surfaces in contact with flowing liquids are ubiquitous in nature, as most minerals in water spontaneously acquire charge and dissolve. Mineral dissolution has been studied extensively under equilibrium conditions, even though non-equilibrium phenomena are pervasive and substantially affect the mineral-water interface. Here we demonstrate using interface-specific spectroscopy that liquid flow along a calcium fluoride surface creates a reversible, spatial charge gradient, with decreasing surface charge downstream of the flow. The surface charge gradient can be quantitatively accounted for by a reaction-diffusion-advection model, which reveals that the charge gradient results from a delicate interplay between diffusion, advection, dissolution, and desorption/adsorption. The underlying mechanism is expected to be valid for a wide variety of systems, including groundwater flows in nature and microfluidic systems.

cond-mat.soft↗

arXiv2021

Machine-learning free-energy functionals using density profiles from simulations

The formally exact framework of equilibrium Density Functional Theory (DFT) is capable of simultaneously and consistently describing thermodynamic and structural properties of interacting many-body systems in arbitrary external potentials. In practice, however, DFT hinges on approximate (free-)energy functionals from which density profiles (and hence the thermodynamic potential) follow via an Euler-Lagrange equation. Here we explore a relatively simple Machine Learning (ML) approach to improve the standard mean-field approximation of the excess Helmholtz free energy functional of a 3D Lennard-Jones system at a supercritical temperature. The learning set consists of density profiles from grand-canonical Monte Carlo simulations of this system at varying chemical potentials and external potentials in a planar geometry only. Using the DFT formalism we nevertheless can extract not only very accurate 3D bulk equations of state but also radial distribution functions using the Percus test-particle method. Unfortunately, our ML approach did not provide very reliable Ornstein-Zernike direct correlation functions for small distances.

cond-mat.soft↗

arXiv2021

Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory

We present a study of the structure and differential capacitance of electric double layers of aqueous electrolytes. We consider Electric Double Layer Capacitors (EDLC) composed of spherical cations and anions in a dielectric continuum confined between a planar cathode and anode. The model system includes steric as well as Coulombic ion-ion and ion-electrode interactions. We compare results of computationally expensive, but "exact", Brownian Dynamics (BD) simulations with approximate, but cheap, calculations based on classical Density Functional Theory (DFT). Excellent overall agreement is found for a large set of system parameters $-$ including variations in concentrations, ionic size- and valency-asymmetries, applied voltages, and electrode separation $-$ provided the differences between the canonical ensemble of the BD simulations and the grand-canonical ensemble of DFT are properly taken into account. In particular a careful distinction is made between the differential capacitance $C_N$ at fixed number of ions and $C_μ$ at fixed ionic chemical potential. Furthermore, we derive and exploit their thermodynamic relations. In the future these relations are also useful for comparing and contrasting.

cond-mat.soft↗

arXiv2021

Statistical-physics-inspired model for intrinsic fluctuations driving supply and demand in markets

We propose a simple statistical-physics-inspired model for the effect of intrinsic fluctuations on supply and demand in markets. The model consists of agents that trade in two types of goods of which the total number is separately conserved. The relative preference of an individual agent for the two types of goods is determined by a utility that is identical for all agents. Market supply and demand curves are computed and compared for various motivated choices of the distribution of goods over the agents. In particular, we compare the "mean-field" case, in which all agents have the same number of goods and that is akin to the economics textbook case, to the case of Boltzmann-Gibbs distributed goods, in which agents have a fluctuating number of goods. We find that the resulting equilibrium prices are not equal for these two approaches, especially when a large fraction of the agents can neither buy nor sell.

physics.soc-ph↗

arXiv2020

A Blessing and a Curse: How a Supercapacitor's Large Capacitance Causes its Slow Charging

The development of novel electrolytes and electrodes for supercapacitors is hindered by a gap of several orders of magnitude between experimentally measured and theoretically predicted charging timescales. Here, we propose an electrode model, containing many parallel stacked electrodes, that explains the slow charging dynamics of supercapacitors. At low applied potentials, the charging behavior of this model is described well by an equivalent circuit model. Conversely, at high potentials, charging dynamics slow down and evolve on two relaxation time scales: a generalized $RC$ time and a diffusion time, which, interestingly, become similar for porous electrodes. The charging behavior of the stack-electrode model presented here helps to understand the charging dynamics of porous electrodes and qualitatively agrees with experimental time scales measured with porous electrodes.

physics.chem-ph↗

arXiv2019

Interparticle torques suppress motility-induced phase separation for rodlike particles

To study the role of torque in motility-induced phase separation (MIPS), we simulate a system of self-propelled particles whose shape varies smoothly from isotropic (disks/spheres) to weakly elongated (rods). We construct the phase diagrams of 2D active disks, 3D active spheres and 2D/3D active rods of aspect ratio $l/σ=2$. A stability analysis of the homogeneous isotropic phase allows us to predict the onset of MIPS based on the effective swimming speed and rotational diffusion of the particles. Both methods find suppression of MIPS as the particle shape is elongated. We propose a suppression mechanism based on the duration of collisions, and argue that this mechanism can explain both the suppression of MIPS found here for rodlike particles and the enhancement of MIPS found for particles with Vicsek interactions.

cond-mat.stat-mech↗

arXiv2018

Ratchet-induced variations in bulk states of an active ideal gas

We study the distribution of active, noninteracting particles over two bulk states separated by a ratchet potential. By solving the steady-state Smoluchowski equations in a flux-free setting, we show that the ratchet potential affects the distribution of particles over the bulks, and thus exerts an influence of infinitely long range. As we show, crucial for having such a long-range influence is an external potential that is nonlinear. We characterize how the difference in bulk densities depends on activity and on the ratchet potential, and we identify power law dependencies on system parameters in several limiting cases. While weakly active systems are often understood in terms of an effective temperature, we present an analytical solution that explicitly shows that this is not possible in the current setting. Instead, we rationalize our results by a simple transition state model, that presumes particles to cross the potential barrier by Arrhenius rates modified for activity. While this model does not quantitatively describe the difference in bulk densities for feasible parameter values, it does reproduce - in its regime of applicability - the complete power law behavior correctly.

cond-mat.soft↗

arXiv2018

Dynamic Stern layers in charge-regulating electrokinetic systems: three regimes from an analytical approach

We present analytical solutions for the electrokinetics at a charged surface with both non-zero Stern-layer conductance and finite chemical reaction rates. We have recently studied the same system numerically [Werkhoven {\em et al.}, Phys. Rev. Lett. {\bf 120}, 264502 (2018)], and have shown that an applied pressure drop across the surface leads to a non-trivial, laterally heterogeneous surface charge distribution at steady state. In this work, we linearise the governing electrokinetic equations to find closed expressions for the surface charge profile and the generated streaming electric field. The main results of our calculations are the identification of three important length and time scales that govern the charge distribution, and consequently the classification of electrokinetic systems into three distinct regimes. The three governing time scales can be associated to (i) the chemical reaction, (ii) diffusion in the Stern layer, and (iii) conduction in the Stern layer, where the dominating (smallest) time scale characterises the regime. In the reaction-dominated regime we find a constant surface charge with an edge effect, and recover the Helmholtz-Smoluchowski equation. In the other two regimes, we find that the surface charge heterogeneity extends over the entire surface, either linearly (diffusion-dominated regime) or nonlinearly (conduction-dominated regime).

cond-mat.soft↗

arXiv2018

Connectedness percolation of hard convex polygonal rods and platelets

The properties of polymer composites with nanofiller particles change drastically above a critical filler density known as the percolation threshold. Real nanofillers, such as graphene flakes and cellulose nanocrystals, are not idealized disks and rods but are often modeled as such. Here we investigate the effect of the shape of the particle cross section on the geometric percolation threshold. Using connectedness percolation theory and the second-virial approximation, we analytically calculate the percolation threshold of hard convex particles in terms of three single-particle measures. We apply this method to polygonal rods and platelets and find that the universal scaling of the percolation threshold is lowered by decreasing the number of sides of the particle cross section. This is caused by the increase of the surface area to volume ratio with decreasing number of sides.

cond-mat.soft↗

arXiv2018

The effect of flexibility and bend angle on the phase diagram of hard colloidal boomerangs

We study the effect of flexibility and bend angle on systems of hard semiflexible boomerangs. These are modelled as two rodlike segments joined at one end with an angle that can fluctuate about a preferred angle. We use a second-virial theory for semiflexible chains with two segments, and numerically solve for the full orientation distribution function as a function of the four angles that determine the boomerang's orientation. We plot the single segment distributions as a function of two angles as well as the interarm angle distribution. For stiff boomerangs, we find prolate, oblate, and biaxial nematic phases depending on the bend angle and density, in partial agreement with previous results on rigid boomerangs. For the case that the preferred interarm angle is $90^\circ$, however, we find that the biaxial nematic phase has four-fold rather than two-fold rotational symmetry, and thus requires fourth-rank order parameters to describe it. In addition, we find that flexibility drastically reduces the region of stability for the biaxial nematic phase, with the prolate nematic becoming more favourable.

cond-mat.soft↗

arXiv2018

Anomalous system-size dependence of electrolytic cells with an electrified oil-water interface

Manipulation of the charge of the dielectric interface between two bulk liquids not only enables the adjustment of the interfacial tension but also controls the storage capacity of ions in the ionic double layers adjacent to each side of the interface. However, adjusting this interfacial charge by static external electric fields is difficult since the external electric fields are readily screened by ionic double layers that form in the vicinity of the external electrodes. This leaves the liquid-liquid interface, which is at a macroscopic distance from the electrodes, unaffected. In this study we show theoretically, in agreement with recent experiments, that control over this surface charge at the liquid-liquid interface is nonetheless possible for macroscopically large but finite closed systems in equilibrium, even when the distance between the electrode and interface is orders of magnitude larger than the Debye screening lengths of the two liquids. We identify a crossover system-size below which the interface and the electrodes are effectively coupled. Our calculations of the interfacial tension for various electrode potentials are in good agreement with recent experimental data.

cond-mat.soft↗

arXiv2018

Hard competition: stabilizing the elusive biaxial nematic phase in suspensions of colloidal particles with extreme lengths

We use computer simulations to study the existence and stability of a biaxial nematic $N_b$ phase in systems of hard polyhedral cuboids, triangular prisms, and rhombic platelets, characterized by a long ($L$), medium ($M$), and short ($S$) particle axis. For all three shape families, we find stable $N_b$ states provided the shape is not only close to the so-called dual shape with $M = \sqrt{LS}$ but also sufficiently anisotropic with $L/S>9,11,14, 23$ for rhombi, prisms, and cuboids, respectively, corresponding to anisotropies not considered before. Surprisingly, a direct isotropic-$N_b$ transition does not occur in these systems due to a destabilization of $N_b$ by a smectic (for cuboids and prisms) or a columnar (for platelets) phase at small $L/S$, or by an intervening uniaxial nematic phase at large $L/S$. Our results are confirmed by a density functional theory provided the third virial coefficient is included and a continuous rather than a discrete (Zwanzig) set of particle orientations is taken into account.

cond-mat.soft↗

arXiv2018

Chemical potential in active systems: predicting phase equilibrium from bulk equations of state?

We derive a microscopic expression for a quantity $μ$ that plays the role of chemical potential of Active Brownian Particles (ABPs) in a steady state in the absence of vortices. We show that $μ$ consists of (i) an intrinsic chemical potential similar to passive systems, which depends on density and self-propulsion speed, but not on the external potential, (ii) the external potential, and (iii) a newly derived one-body swim potential due to the activity of the particles. Our simulations on active Brownian particles show good agreement with our Fokker-Planck calculations, and confirm that $μ(z)$ is spatially constant for several inhomogeneous active fluids in their steady states in a planar geometry. Finally, we show that phase coexistence of ABPs with a planar interface satisfies not only mechanical but also diffusive equilibrium. The coexistence can be well-described by equating the bulk chemical potential and bulk pressure obtained from bulk simulations for systems with low activity but requires explicit evaluation of the interfacial contributions at high activity.

cond-mat.soft↗

arXiv2017

Connectedness percolation of hard deformed rods

Nanofiller particles, such as carbon nanotubes or metal wires, are used in functional polymer composites to make them conduct electricity. They are often not perfectly straight cylinders, but may be tortuous or exhibit kinks. Therefore we investigate the effect of shape deformations of the rodlike nanofillers on the geometric percolation threshold of the dispersion. We do this by using connectedness percolation theory within a Parsons-Lee type of approximation, in combination with Monte Carlo integration for the average overlap volume in the isotropic fluid phase. We find that a deviation from a perfect rodlike shape has very little effect on the percolation threshold, unless the particles are strongly deformed. This demonstrates that idealized rod models are useful even for nanofillers that superficially seem imperfect. In addition, we show that for small or moderate rod deformations, the universal scaling of the percolation threshold is only weakly affected by the precise particle shape.

cond-mat.soft↗

arXiv2017

Van't Hoff's law for active suspensions: the role of the solvent chemical potential

We extend Van't Hoff's law for the osmotic pressure to a suspension of active Brownian particles. The propelled particles exert a net reaction force on the solvent, and thereby either drive a measurable solvent flow from the connecting solvent reservoir through the semipermeable membrane, or increase the osmotic pressure and cause the suspension to rise to heights as large as micrometers for experimentally realized microswimmers described in the literature. The increase in osmotic pressure is caused by the background solvent being, in contrast to passive suspensions, no longer at the chemical potential of the solvent reservoir. The difference in solvent chemical potentials depends on the colloid-membrane interaction potential, which implies that the osmotic pressure is a state function of a state that itself is influenced by the membrane potential.

cond-mat.soft↗

arXiv2017

Tuning the motility and directionality of self-propelled colloids

Microorganisms are able to overcome the thermal randomness of their surroundings by harvesting energy to navigate in viscous fluid environments. In a similar manner, synthetic colloidal microswimmers are capable of mimicking complex biolocomotion by means of simple self-propulsion mechanisms. Although experimentally the speed of active particles can be controlled by e.g. self-generated chemical and thermal gradients, an in-situ change of swimming direction remains a challenge. In this work, we study self-propulsion of half-coated spherical colloids in critical binary mixtures and show that the coupling of local body forces, induced by laser illumination, and the wetting properties of the colloid, can be used to finely tune both the colloid's swimming speed and its directionality. We experimentally and numerically demonstrate that the direction of motion can be reversibly switched by means of the size and shape of the droplet(s) nucleated around the colloid, depending on the particle radius and the fluid's ambient temperature. Moreover, the aforementioned features enable the possibility to realize both negative and positive phototaxis in light intensity gradients. Our results can be extended to other types of half-coated microswimmers, provided that both of their hemispheres are selectively made active but with distinct physical properties.

cond-mat.soft↗