arXiv subjects

Frank Smallenburg

Publications and source records attributed to Frank Smallenburg.

At least 55 records · Page 3Linked to original sources

arXiv2019

Pressure, surface tension and curvature in active systems: A touch of equilibrium

We explore the pressure of active particles on curved surfaces and its relation to other interfacial properties. We use both direct simulations of the active systems as well as simulations of an equilibrium system with effective (pair) interactions designed to capture the effects of activity. Comparing the active and effective passive systems in terms of their bulk pressure, we elaborate that the most useful theoretical route to this quantity is via the density profile at a flat wall. This is corroborated by extending the study to curved surfaces and establishing a connection to the particle adsorption and integrated surface excess pressure (surface tension). In the ideal-gas limit, the effect of curvature on the mechanical properties can be calculated analytically in the passive system with effective interactions, and shows good (but not exact) agreement with simulations of the active models. It turns out that even the linear correction to the pressure is model specific and equals the planar adsorption in each case, which means that a known equilibrium sum rule can be extended to a regime at small but nonzero activity. In turn, the relation between the planar adsorption and the surface tension is reminiscent of the Gibbs adsorption theorem at an effective temperature. At finite densities, where particle interactions play a role, the presented effective-potential approximation captures the effect of density on the dependence of the pressure on curvature.

cond-mat.soft↗

arXiv2019

Designing slower glasses by manipulating their local structure

Glasses remain an elusive and poorly understood state of matter. For example, it is not clear how we can design an efficient macroscopic glass former by tuning the properties of its microscopic building blocks. In this paper, we propose a simple directional colloidal model that reinforces the optimal icosahedral local structure of binary hard-sphere glasses. We show that only this specific symmetry results in a dramatic slowing down of the dynamics. Our results open the door to controlling the dynamics of dense glassy systems by selectively promoting specific local structural environments.

cond-mat.soft↗

arXiv2017

Static Structure of Active Brownian Hard Disks

We explore the changes in static structure of a two-dimensional system of active Brownian particles (ABP) with hard-disk interactions, using event-driven Brownian dynamics simulations. In particular, the effect of the self-propulsion velocity and the rotational diffusivity on the orientationally-averaged fluid structure factor is discussed. Typically activity increases structural ordering and generates a structure factor peak at zero wave vector which is a precursor of motility-induced phase separation. Our results provide reference data to test future statistical theories for the fluid structure of active Brownian systems.

cond-mat.stat-mech↗

arXiv2017

Low-temperature crystal structures of the hard core square shoulder model

In many cases, the stability of complex structures in colloidal systems is enhanced by a competition between different length scales. Inspired by recent experiments on nanoparticles coated with polymers, we use Monte Carlo simulations to explore the types of crystal structures that can form in a simple hard-core square shoulder model which explicitly incorporates two favored distances between the particles. To this end, we combine Monte Carlo-based crystal structure finding algorithms with free energies obtained using a mean-field cell theory approach, and draw phase diagrams for two different values of the square shoulder width as a function of the density and temperature. Moreover, we map out the zero-temperature phase diagram for a broad range of shoulder widths. Our results show the stability of a rich variety of crystal phases, such as body-centered orthogonal (BCO) lattices, not previously considered for the square shoulder model.

cond-mat.soft↗

arXiv2017

Liquid crystals of hard rectangles on flat and cylindrical manifolds

Using the classical density functional theory of freezing and Monte Carlo computer simulations, we explore the liquid-crystalline phase behavior of hard rectangles on flat and cylindrical manifolds. Moreover, we study the effect of a static external field which couples to the rectangles' orientations, aligning them towards a preferred direction. In the flat and field-free case, the bulk phase diagram involves stable isotropic, nematic, tetratic, and smectic phases depending on the aspect ratio and number density of the particles. The external field shifts the transition lines significantly and generates a binematic phase at the expense of the tetratic phase. On a cylindrical manifold, we observe tilted smectic-like order, as obtained by wrapping a smectic layer around a cylinder. We find in general good agreement between our density functional calculations and particle-resolved computer simulations and mention possible setups to verify our predictions in experiments.

cond-mat.soft↗

arXiv2017

Phase diagram of two-dimensional hard rods from fundamental mixed measure density functional theory

A density functional theory for the bulk phase diagram of two-dimensional orientable hard rods is proposed and tested against Monte Carlo computer simulation data. In detail, an explicit density functional is derived from fundamental mixed measure theory and freely minimized numerically for hard discorectangles. The phase diagram, which involves stable isotropic, nematic, smectic and crystalline phases, is obtained and shows good agreement with the simulation data. Our functional is valid for a multicomponent mixture of hard particles with arbitrary convex shapes and provides a reliable starting point to explore various inhomogeneous situations of two-dimensional hard rods and their Brownian dynamics.

cond-mat.soft↗

arXiv2017

Phase and vacancy behaviour of hard "slanted" cubes

We use computer simulations to study the phase behaviour for hard, right rhombic prisms as a function of the angle of their rhombic face (the "slant" angle). More specifically, using a combination of event-driven molecular dynamics simulations, Monte Carlo simulations, and free-energy calculations, we determine and characterize the equilibrium phases formed by these particles for various slant angles and densities. Surprisingly, we find that the equilibrium crystal structure for a large range of slant angles and densities is the simple cubic crystal - despite the fact that the particles do not have cubic symmetry. Moreover, we find that the equilibrium vacancy concentration in this simple cubic phase is extremely high and depends only on the packing fraction, and not the particle shape. At higher densities, a rhombic crystal appears as the equilibrium phase. We summarize the phase behaviour of this system by drawing a phase diagram in the slant angle - packing fraction plane.

cond-mat.soft↗

arXiv2016

Hard rectangles near curved hard walls: tuning the sign of the Tolman length

Combining analytic calculations, computer simulations, and classical density functional theory we determine the interfacial tension of orientable two-dimensional hard rectangles near a curved hard wall. Both a circular cavity holding the particles and a hard circular obstacle surrounded by particles are considered. We focus on moderate bulk densities (corresponding to area fractions up to 50 percent) where the bulk phase is isotropic and vary the aspect ratio of the rectangles and the curvature of the wall. The Tolman length, which gives the leading curvature correction of the interfacial tension, is found to change sign at a finite density, which can be tuned via the aspect ratio of the rectangles.

cond-mat.soft↗

arXiv2016

Close packing of rods on spherical surfaces

We study the optimal packing of short, hard spherocylinders confined to lie tangential to a spherical surface, using simulated annealing and molecular dynamics simulations. For clusters of up to twelve particles, we map out the changes in the geometry of the closest-packed configuration as a function of the aspect ratio $L/D$, where $L$ is the cylinder length and $D$ the diameter of the rods. We find a rich variety of cluster structures. For larger clusters, we find that the best-packed configurations up to around 100 particles are highly dependent on the exact number of particles and aspect ratio. For even larger clusters, we find largely disordered clusters for very short rods ($L/D = 0.25$), while slightly longer rods ($L/D = 0.5$ or $1$) prefer a global baseball-like geometry of smectic-like domains, similar to the behavior of large-scale nematic shells. Our results provide predictions for experimentally realizable systems of colloidal rods trapped at the interface of emulsion droplets.

cond-mat.soft↗

arXiv2015

Flow of colloidal solids and fluids through constrictions: dynamical density functional theory versus simulation

Using both dynamical density functional theory and particle-resolved Brownian dynamics simulations, we explore the flow of two-dimensional colloidal solids and fluids driven through a linear channel with a geometric constriction. The flow is generated by a constant external force acting on all colloids. The initial configuration is equilibrated in the absence of flow and then the external force is switched on instantaneously. Upon starting the flow, we observe four different scenarios: a complete blockade, a monotonic decay to a constant particle flux (typical for a fluid), a damped oscillatory behaviour in the particle flux, and a long-lived stop-and-go behaviour in the flow (typical for a solid). The dynamical density functional theory describes all four situations but predicts infinitely long undamped oscillations in the flow which are always damped in the simulations. We attribute the mechanisms of the underlying stop-and-go flow to symmetry conditions on the flowing solid. Our predictions are verifiable in real-space experiments on magnetic colloidal monolayers which are driven through structured microchannels and can be exploited to steer the flow throughput in microfluidics.

cond-mat.soft↗

arXiv2015

Swim pressure on walls with curves and corners

The concept of swim pressure quantifies the average force exerted by microswimmers on confining walls in non-equilibrium. Here we explore how the swim pressure depends on the wall curvature and on the presence of sharp corners in the wall. For active Brownian particles at high dilution, we present a coherent framework which describes the force and torque on passive particles of arbitrary shape, in the limit of large particles compared to the persistence length of the swimmer trajectories. The resulting forces can be used to derive, for example, the activity-induced depletion interaction between two disks, as well as to optimize the shape of a tracer particle for high swimming velocity. Our predictions are verifiable in experiments on passive obstacles exposed to a bath of bacteria or artificial microswimmers.

cond-mat.soft↗

arXiv2015

Tuning the liquid-liquid transition by modulating the hydrogen bond angular flexibility in a model for water

We propose a simple extension of the well known ST2 model for water [F.H. Stillinger and A. Rahman, J. Chem. Phys. {\bf 60}, 1545 (1974)] that allows for a continuous modification of the hydrogen bond angular flexibility. We show that the bond flexibility affects the relative thermodynamic stability of the liquid and of the hexagonal (or cubic) ice. On increasing flexibility, the liquid-liquid critical point, which in the original ST2 model is located in the no-man's land (i. e. the region where ice is the thermodynamically stable phase) progressively moves to a temperature where the liquid is more stable than ice. Our study definitively proves that the liquid-liquid transition in ST2 is a genuine phenomenon, of high relevance in all tetrahedral network-forming liquids, including water.

cond-mat.stat-mech↗

arXiv2015

Phase diagram of the ST2 model of water

We evaluate the free energy of the fluid and crystal phases for the ST2 potential [F.H. Stillinger and A. Rahman, J. Chem. Phys. 60, 1545 (1974)] with reaction field corrections for the long-range interactions. We estimate the phase coexistence boundaries in the temperature-pressure plane, as well as the gas-liquid critical point and gas-liquid coexistence conditions. Our study frames the location of the previously identified liquid-liquid critical point relative to the crystalline phase boundaries, and opens the way for exploring crystal nucleation in a model where the metastable liquid-liquid critical point is computationally accessible.

cond-mat.stat-mech↗

arXiv2013

Phase Diagram of a Reentrant Gel of Patchy Particles

We study the phase diagram of a binary mixture of patchy particles which has been designed to form a reversible gel. For this we perform Monte Carlo and molecular dynamics simulations to investigate the thermodynamics of such a system and compare our numerical results with predictions based on the analytical parameter-free Wertheim theory. We explore a wide range of the temperature-density-composition space that defines the three-dimensional phase diagram of the system. As a result, we delimit the region of thermodynamic stability of the fluid. We find that for a large region of the phase diagram the Wertheim theory is able to give a quantitative description of the system. For higher densities our simulations show that the system is crystallizing into a BCC structure. Finally we study the relaxation dynamics of the system by means of the density and temperature dependences of the diffusion coefficient. We show that there exists a density range where the system passes reversibly from a gel to a fluid upon both heating and cooling, encountering neither demixing nor phase separation.

cond-mat.soft↗

arXiv2013

Understanding tetrahedral liquids through patchy colloids

We investigate the structural properties of a simple model for tetrahedral patchy colloids in which the patch width and the patch range can be tuned independently. For wide bond angles, a fully bonded network can be generated by standard Monte Carlo or molecular dynamics simulations of the model, providing a neat method for generating defect-free random tetrahedral networks. This offers the possibility of focusing on the role of the patch angular width on the structure of the fully bonded network. The analysis of the fully bonded configurations as a function of the bonding angle shows how the bonding angle controls the system compressibility, the strength of the pre-peak in the structure factor and ring size distribution. Comparison with models of liquid water and silica allows us to find the best mapping between these continuous potentials and the colloidal one. Building on previous studies focused on the connection between angular range and crystallization, the mapping makes it possible to shed new light on the glass-forming ability of network-forming tetrahedral liquids.

cond-mat.soft↗

arXiv2013

Liquids more stable than crystals

All liquids (except helium due to quantum effects) crystallize at low temperatures, forming ordered structures. The competition between disorder, which stabilizes the liquid phase, and energy, which favors the ordered crystalline structure, inevitably turns in favor of the latter when temperature is lowered and the entropic contribution to the free energy becomes progressively less and less relevant. The "liquid" state survives at low temperatures only as a glass, an out-of-equilibrium arrested state of matter. This textbook description holds inevitably for atomic and molecular systems, where the interaction between particles is set by quantum mechanical laws. The question remains whether the same physics hold for colloidal particles, where inter-particle interactions are usually short-ranged and tunable. Here we show that for patchy colloids with limited valence, conditions can be found for which the disordered liquid phase is stable all the way down to the zero-temperature limit. Our results offer interesting cues for understanding the stability of gels and the glass forming ability of atomic and molecular network glasses.

cond-mat.soft↗

arXiv2013

Gelling by Heating

We introduce a simple model, a binary mixture of patchy particles, which has been designed to form a gel upon heating. Due to the specific nature of the particle interactions, notably the number and geometry of the patches as well as their interaction energies, the system is a fluid both at high and at low temperatures, whereas at intermediate temperatures the system forms a solid-like disordered open network structure, i.e. a gel. Using molecular dynamics we investigate the static and dynamic properties of this system.

cond-mat.soft↗

arXiv2012

Vacancy-stabilized crystalline order in hard cubes

We examine the effect of vacancies on the phase behavior and structure of systems consisting of hard cubes using event-driven molecular dynamics and Monte Carlo simulations. We find a first-order phase transition between a fluid and a simple cubic crystal phase that is stabilized by a surprisingly large number of vacancies, reaching a net vacancy concentration of ~6.4% near bulk coexistence. Remarkably, we find that vacancies increase the positional order in the system. Finally, we show that the vacancies are delocalized and therefore hard to detect.

cond-mat.soft↗