arXiv subjects

Marjolein Dijkstra

Publications and source records attributed to Marjolein Dijkstra.

At least 109 records · Page 6Linked to original sources

arXiv2012

Phase diagram of colloidal hard superballs: from cubes via spheres to octahedra

The phase diagram of colloidal hard superballs, of which the shape interpolates between cubes and octahedra via spheres, is determined by free-energy calculations in Monte Carlo simulations. We discover not only a stable face-centered cubic (fcc) plastic crystal phase for near-spherical particles, but also a stable body-centered cubic (bcc) plastic crystal close to the octahedron shape, and in fact even coexistence of these two plastic crystals with a substantial density gap. The plastic fcc and bcc crystals are, however, unstable in the cube and octahedron limit, suggesting that the rounded corners of superballs play an important role in stablizing the rotator phases. In addition, we observe a two-step melting phenomenon for hard octahedra, in which the Minkowski crystal melts into a metastable bcc plastic crystal before melting into the fluid phase.

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arXiv2011

Frustration of the isotropic-columnar phase transition of colloidal hard platelets by a transient cubatic phase

Using simulations and theory, we show that the cubatic phase is metastable for three model hard platelets. The locally favored structures of perpendicular particle stacks in the fluid prevent the formation of the columnar phase through geometric frustration resulting in vitrification. Also, we find a direct link between structure and dynamic heterogeneities in the cooperative rotation of particle stacks, which is crucial for the devitrification process. Finally, we show that the life time of the glassy cubatic phase can be tuned by surprisingly small differences in particle shape.

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arXiv2011

Ion association in low-polarity solvents: comparisons between theory, simulation, and experiment

The association of ions in electrolyte solutions at very low concentration and low temperature is studied using computer simulations and quasi-chemical ion-pairing theory. The specific case of the restricted primitive model (charged hard spheres) is considered. Specialised simulation techniques are employed that lead to efficient sampling of the arrangements and distributions of clusters and free ions, even at conditions corresponding to nanomolar solutions of simple salts in solvents with dielectric constants in the range 5-10, as used in recent experimental work on charged-colloid sus- pensions. A direct comparison is effected between theory and simulation using a variety of clustering criteria and theoretical approximations. It is shown that conventional distance-based cluster criteria can give erroneous results. A reliable set of theoretical and simulation estimators for the degree of association is proposed. The ion-pairing theory is then compared to experimental results for salt solutions in low-polarity solvents. The agreement is excellent, and on this basis some calculations are made for the screening lengths which will figure in the treatment of colloid-colloid interactions in such solutions. The accord with available experimental results is complete.

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arXiv2011

Dense Regular Packings of Irregular Non-Convex Particles

We present a new numerical scheme to study systems of non-convex, irregular, and punctured particles in an efficient manner. We employ this method to analyze regular packings of odd-shaped bodies, not only from a nanoparticle but also both from a computational geometry perspective. Besides determining close-packed structures for many shapes, we also discover a new denser configuration for Truncated Tetrahedra. Moreover, we consider recently synthesized nanoparticles and colloids, where we focus on the excluded volume interactions, to show the applicability of our method in the investigation of their crystal structures and phase behavior. Extensions to the presented scheme include the incorporation of soft particle-particle interactions, the study of quasicrystalline systems, and random packings.

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arXiv2011

Measuring Colloidal Forces from Particle Position Deviations inside an Optical Trap

We measure interaction forces between pairs of charged PMMA colloidal particles suspended in a relatively low-polar medium (5 $\lesssim ε\lesssim$ 8) directly from the deviations of particle positions inside two time-shared optical traps. The particles are confined to optical point traps; one is held in a stationary trap and the other particle is brought closer in small steps while tracking the particle positions using confocal microscopy. From the observed particle positions inside the traps we calculate the interparticle forces using an ensemble-averaged particle displacement-force relationship. The force measurements are confirmed by independent measurements of the different parameters using electrophoresis and a scaling law for the liquid-solid phase transition. When increasing the salt concentration by exposing the sample to UV light, the force measurements agree well with the classical DLVO theory assuming a constant surface potential. On the other hand, when adding tetrabutylammonium chloride (TBAC) to vary the salt concentration, surface charge regulation seems to play an important role.

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arXiv2011

Phase diagram and effective shape of semi-flexible colloidal rods and biopolymers

We study suspensions of semi-flexible colloidal rods and biopolymers using an Onsager-type second-virial functional for a segmented-chain model. For suspensions of thin and thick fd virus particles we calculate phase diagrams in quantitative agreement with experimental observations, and we find their effective state-point dependent shape to be much shorter and thicker than the actual shape. We also calculate the stretching of worm-like micelles in a host fd virus solution, again finding agreement with experiments. For both systems, our results show that the fd virus stiffness can play a key role in system behavior.

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arXiv2010

Crystal nucleation of colloidal hard dumbbells

Using computer simulations we investigate the homogeneous crystal nucleation in suspensions of colloidal hard dumbbells. The free energy barriers are determined by Monte Carlo simulations using the umbrella sampling technique. We calculate the nucleation rates for the plastic crystal and the aperiodic crystal phase using the kinetic prefactor as determined from event driven molecular dynamics simulations. We find good agreement with the nucleation rates determined from spontaneous nucleation events observed in event driven molecular dynamics simulations within error bars of one order of magnitude. We study the effect of aspect ratio of the dumbbells on the nucleation of plastic and aperiodic crystal phases and we also determine the structure of the critical nuclei. Moreover, we find that the nucleation of the aligned CP1 crystal phase is strongly suppressed by a high free energy barrier at low supersaturations and slow dynamics at high supersaturations.

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arXiv2010

Phase diagrams of colloidal spheres with a constant zeta-potential

We study suspensions of colloidal spheres with a constant zeta-potential within Poisson-Boltzmann theory, quantifying the discharging of the spheres with increasing colloid density and decreasing salt concentration. We use the calculated renormalized charge of the colloids to determine their pairwise effective screened-Coulomb repulsions. Bulk phase diagrams in the colloid concentration-salt concentration representation follow, for various zeta-potentials, by a mapping onto published fits of phase boundaries of point-Yukawa systems. Although the resulting phase diagrams do feature face-centered cubic (fcc) and body-centered cubic (bcc) phases, they are dominated by the (re-entrant) fluid phase due to the colloidal discharging with increasing colloid concentration and decreasing salt concentration.

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arXiv2010

Heterogeneous Dynamics in Columnar Liquid Crystals of Parallel Hard Rods

In the wake of previous studies on the rattling-and-jumping diffusion in smectic liquid crystal phases of colloidal rods, we analyze here for the first time the heterogeneous dynamics in columnar phases. More specifically, we perform computer simulations to investigate the relaxation dynamics of a binary mixture of perfectly aligned hard spherocylinders. We detect that the columnar arrangement of the system produces free-energy barriers the particles should overcome to jump from one column to another, thus determining a hopping-type diffusion. This phenomenon accounts for the non-Gaussian inter-column diffusion and shows a two-step structural relaxation which is remarkably analogous to that of out-of-equilibrium glass-forming systems and gels. Surprisingly enough, slight deviations from the behavior of simple liquids due to transient cages is also observed in the direction perpendicular to this plane, where the system is usually referred to as liquid-like.

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arXiv2010

Glassy dynamics, spinodal fluctuations, and the kinetic limit of hard-rod nucleation

Using simulations we identify three dynamic regimes in supersaturated isotropic fluid states of short hard rods: (i) for moderate supersaturations we observe nucleation of multi-layered crystalline clusters; (ii) at higher supersaturation, we find nucleation of small crystallites which arrange into long-lived locally favored structures that get kinetically arrested, while (iii) at even higher supersaturation the dynamic arrest is due to the conventional cage-trapping glass transition. For longer rods we find that the formation of the (stable) smectic phase out of a supersaturated isotropic state is strongly suppressed by an isotropic-nematic spinodal instability that causes huge spinodal-like orientation fluctuations with nematic clusters diverging in size. Our results show that glassy dynamics and spinodal instabilities set kinetic limits to nucleation in a highly supersaturated hard-rod fluids.

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arXiv2010

Phase behavior and structure of colloidal bowl-shaped particles: simulations

We study the phase behavior of bowl-shaped particles using computer simulations. These particles were found experimentally to form a meta-stable worm-like fluid phase in which the bowl-shaped particles have a strong tendency to stack on top of each other [M.Marechal et al, Nano Letters 10, 1907 (2010)]. In this work, we show that the transition from the low-density fluid to the worm-like phase has an interesting effect on the equation of state. The simulation results also show that the worm-like fluid phase transforms spontaneously into a columnar phase for bowls that are sufficiently deep. Furthermore, we describe the phase behavior as obtained from free energy calculations employing Monte Carlo simulations. The columnar phase is stable for bowl shapes ranging from infinitely thin bowls to surprisingly shallow bowls. Aside from a large region of stability for the columnar phase, the phase diagram features four novel crystal phases and a region where the stable fluid contains worm-like stacks.

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arXiv2010

Crystal nucleation of hard spheres using molecular dynamics, umbrella sampling and forward flux sampling: A comparison of simulation techniques

Over the last number of years several simulation methods have been introduced to study rare events such as nucleation. In this paper we examine the crystal nucleation rate of hard spheres using three such numerical techniques: molecular dynamics, forward flux sampling and a Bennett-Chandler type theory where the nucleation barrier is determined using umbrella sampling simulations. The resulting nucleation rates are compared with the experimental rates of Harland and Van Megen [J. L. Harland and W. van Megen, Phys. Rev. E 55, 3054 (1997)], Sinn et al. [C. Sinn et al., Prog. Colloid Polym. Sci. 118, 266 (2001)] and Schatzel and Ackerson [K. Schatzel and B.J. Ackerson, Phys. Rev. E, 48, 3766 (1993)] and the predicted rates for monodisperse and 5% polydisperse hard spheres of Auer and Frenkel [S. Auer and D. Frenkel, Nature 409, 1020 (2001)]. When the rates are examined in long-time diffusion units, we find agreement between all the theoretically predicted nucleation rates, however, the experimental results display a markedly different behaviour for low supersaturation. Additionally, we examined the pre-critical nuclei arising in the molecular dynamics, forward flux sampling, and umbrella sampling simulations. The structure of the nuclei appear independent of the simulation method, and in all cases, the nuclei contain on average significantly more face-centered-cubic ordered particles than hexagonal-close-packed ordered particles.

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arXiv2010

Phase Diagrams of Binary Mixtures of Oppositely Charged Colloids

Phase diagrams of binary mixtures of oppositely charged colloids are calculated theoretically. The proposed mean-field-like formalism interpolates between the limits of a hard-sphere system at high temperatures and the colloidal crystals which minimize Madelung-like energy sums at low temperatures. Comparison with computer simulations of an equimolar mixture of oppositely charged, equally sized spheres indicate semi-quantitative accuracy of the proposed formalism. We calculate global phase diagrams of binary mixtures of equally sized spheres with opposite charges and equal charge magnitude in terms of temperature, pressure, and composition. The influence of the screening of the Coulomb interaction upon the topology of the phase diagram is discussed. Insight into the topology of the global phase diagram as a function of the system parameters leads to predictions on the preparation conditions for specific binary colloidal crystals.

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arXiv2010

Collective Diffusion of Colloidal Hard Rods in Smectic Liquid Crystals: Effect of Particle Anisotropy

We study the layer-to-layer diffusion in smectic-A liquid crystals of colloidal hard rods with different length-to-diameter ratios using computer simulations. The layered arrangement of the smectic phase yields a hopping-type diffusion due to the presence of permanent barriers and transient cages. Remarkably, we detect stringlike clusters composed of inter-layer rods moving cooperatively along the nematic director. Furthermore, we find that the structural relaxation in equilibrium smectic phases shows interesting similarities with that of out-of-equilibrium supercooled liquids, although there the particles are kinetically trapped in transient rather than permanent cages. Additionally, at fixed packing fraction we find that the barrier height increases with increasing particle anisotropy, and hence the dynamics is more heterogeneous and non-Gaussian for longer rods, yielding a lower diffusion coefficient along the nematic director and smaller clusters of inter-layer particles that move less cooperatively. At fixed barrier height, the dynamics becomes more non-Gaussian and heterogeneous for longer rods that move more collectively giving rise to a higher diffusion coefficient along the nematic director.

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arXiv2010

Computer simulations of the restricted primitive model at very low temperature and density

The problem of successfully simulating ionic fluids at low temperature and low density states is well known in the simulation literature: using conventional methods, the system is not able to equilibrate rapidly due to the presence of strongly associated cation-anion pairs. In this manuscript we present a numerical method for speeding up computer simulations of the restricted primitive model (RPM) at low temperatures (around the critical temperature) and at very low densities (down to $10^{-10}σ^{-3}$, where $σ$ is the ion diameter). Experimentally, this regime corresponds to typical concentrations of electrolytes in nonaqueous solvents. As far as we are aware, this is the first time that the RPM has been equilibrated at such extremely low concentrations. More generally, this method could be used to equilibrate other systems that form aggregates at low concentrations.

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arXiv2009

Non-Gaussian Dynamics in Smectic Liquid Crystals of Parallel Hard Rods

Using computer simulations, we studied the diffusion and structural relaxation in equilibrium smectic liquid crystal bulk phases of parallel hard spherocylinders. These systems exhibit a non-Gaussian layer-to-layer diffusion due to the presence of periodic barriers and transient cages, and show remarkable similarities with the behavior of out-of-equilibrium supercooled liquids. We detect a very slow inter-layer relaxation dynamics over the whole density range of the stable smectic phase which spans a time interval of four time decades. The intrinsic nature of the layered structure yields a hopping-type diffusion which becomes more heterogeneous for higher packing fractions. In contrast, the in-layer dynamics is typical of a dense fluid with a relatively fast decay. Our results on the dynamic behavior agree well with that observed in systems of freely rotating hard rods, but differ quantitavely, as the height of the periodic barriers reduces to zero at the nematic-smectic transition for aligned rods, while it remains finite for freely rotating rods.

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arXiv2009

A Triangular Tessellation Scheme for the Adsorption Free Energy at the Liquid-Liquid Interface: Towards Non-Convex Patterned Colloids

We introduce a new numerical technique, namely triangular tessellation, to calculate the free energy associated with the adsorption of a colloidal particle at a flat interface. The theory and numerical scheme presented here are sufficiently general to handle non-convex patchy colloids with arbitrary surface patterns characterized by a wetting angle, e.g., amphiphilicity. We ignore interfacial deformation due to capillary, electrostatic, or gravitational forces, but the method can be extended to take such effects into account. It is verified that the numerical method presented is accurate and sufficiently stable to be applied to more general situations than presented in this paper. The merits of the tessellation method prove to outweigh those of traditionally used semi-analytic approaches, especially when it comes to generality and applicability.

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arXiv2009

Out-of-equilibrium processes in suspensions of oppositely charged colloids: liquid-to-crystal nucleation and gel formation

We study the kinetics of the liquid-to-crystal transformation and of gel formation in colloidal suspensions of oppositely charged particles. We analyse, by means of both computer simulations and experiments, the evolution of a fluid quenched to a state point of the phase diagram where the most stable state is either a homogeneous crystalline solid or a solid phase in contact with a dilute gas. On the one hand, at high temperatures and high packing fractions, close to an ordered-solid/disordered-solid coexistence line, we find that the fluid-to-crystal pathway does not follow the minimum free energy route. On the other hand, a quench to a state point far from the ordered-crystal/disordered-crystal coexistence border is followed by a fluid-to-solid transition through the minimum free energy pathway. At low temperatures and packing fractions we observe that the system undergoes a gas-liquid spinodal decomposition that, at some point, arrests giving rise to a gel-like structure. Both our simulations and experiments suggest that increasing the interaction range favors crystallization over vitrification in gel-like structures.

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