Phase Separation and Self-Assembly in a Fluid of Mickey Mouse Particles

Recent developments in the synthesis of colloidal particles allow for control over shape and inter-particle interaction. One example, among others, is the so-called "Mickey Mouse" (MM) particle for which the self-assembly properties have been previously studied yielding a stable cluster phase together with elongated, tube-like structures. Here, we investigate under which conditions a fluid of Mickey Mouse particles can yield phase separation and how the self-assembly behaviour affects the gas-liquid coexistence. We vary the distance between the repulsive and the attractive lobes (bond length), and the interaction range, and follow the evolution of the gas-liquid (GL) coexistence curve. We find that upon increasing the bond length distance the binodal line shifts to lower temperatures, and that the interaction range controls the transition between phase separation and self-assembly of clusters. Upon further reduction of the interaction range and temperature, the clusters assume an increasingly ordered tube-like shape, ultimately matching the one previously reported in literature. These results are of interest when designing particle shape and particle-particle interaction for self-assembly processes

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.Comment: Accepted by J. Chem. Phy

Fabrication of colloidal Laves phases via hard tetramers and hard spheres: bulk phase diagram and sedimentation behaviour

Colloidal photonic crystals display peculiar optical properties which make them particularly suitable for application in different fields. However, the low packing fraction of the targeted structures usually poses a real challenge in the fabrication stage. Here, we propose a novel route to colloidal photonic crystals via a binary mixture of hard tetramers and hard spheres. By combining theory and computer simulations, we calculate the phase diagram as well as the stacking diagram of the mixture, and show that a colloidal analogue of the MgCu2 Laves phase -- which can serve as a precursor of a photonic bandgap structure -- is a thermodynamically stable phase in a large region of the phase diagram. Our findings show a relatively large coexistence region between the fluid and the Laves phase, which is potentially accessible by experiments. Furthermore, we determine the sedimentation behaviour of the suggested mixture, by identifying several stacking sequences. Our work uncovers a new self-assembly path towards a photonic structure with a band gap in the visible region

Gas-liquid phase separation in oppositely charged colloids: stability and interfacial tension

We study the phase behavior and the interfacial tension of the screened Coulomb (Yukawa) restricted primitive model (YRPM) of oppositely charged hard spheres with diameter s using Monte Carlo simulations. We determine the gas-liquid and gas-solid phase transition using free energy calculations and grand-canonical Monte Carlo simulations for varying inverse Debye screening length k. We find that the gas-liquid phase separation is stable for k s <= 4, and that the critical temperature decreases upon increasing the screening of the interaction (decreasing the range of the interaction). In addition, we determine the gas-liquid interfacial tension using grand-canonical Monte Carlo simulations. The interfacial tension decreases upon increasing the range of the interaction. In particular, we find that simple scaling can be used to relate the interfacial tension of the YRPM to that of the restricted primitive model, where particles interact with bare Coulomb interactions.Comment: 17 pages, 6 Figures, accepted for publication in J. Chem. Phy

Isotropic-Nematic transition of long thin hard spherocylinders confined in a quasi-two-dimensional planar geometry

We present computer simulations of long thin hard spherocylinders in a narrow planar slit. We observe a transition from the isotropic to a nematic phase with quasi-long-range orientational order upon increasing the density. This phase transition is intrinsically two dimensional and of the Kosterlitz-Thouless type. The effective two-dimensional density at which this transition occurs increases with plate separation. We qualitatively compare some of our results with experiments where microtubules are confined in a thin slit, which gave the original inspiration for this work.Comment: 8 pages, 10 figure

A Novel Chiral Phase of Achiral Hard Triangles and an Entropy-Driven Demixing of Enantiomers

We investigate the phase behavior of a system of hard equilateral and right-angled triangles in two dimensions using Monte Carlo simulations. Hard equilateral triangles undergo a continuous isotropic-triatic liquid crystal phase transition at packing fraction $\phi=0.7$. Similarly, hard right-angled isosceles triangles exhibit a first-order phase transition from an isotropic fluid phase to a rhombic liquid crystal phase with a coexistence region $\phi \in \left[0.733,0.782\right]$. Both these liquid crystal phases undergo a continuous phase transition to their respective close-packed crystal structures at high pressures. Although the particles and their close-packed crystals are both achiral, the solid phases of equilateral and right-angled triangles exhibit spontaneous chiral symmetry breaking at sufficiently high packing fractions. The colloidal triangles rotate either in clockwise or anti-clockwise direction with respect to one of the lattice vectors for packing fractions higher than $\phi_\chi$. As a consequence, these triangles spontaneously form a regular lattice of left- or right-handed chiral holes which are surrounded by six triangles in the case of equilateral triangles and four or eight triangles for right-angled triangles. Moreover, our simulations show a spontaneous entropy-driven demixing transition of the right- and left-handed "enantiomers".Comment: 9 pages, 10 figure

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.Comment: Submitte

Vapour-Liquid Coexistence of an Active Lennard-Jones fluid

We study a three-dimensional system of self-propelled Lennard-Jones particles using Brownian Dynamics simulations. Using recent theoretical results for active matter, we calculate the pressure and report equations of state for the system. Additionally, we chart the vapour-liquid coexistence and show that the coexistence densities can be well described using simple power laws. Lastly, we demonstrate that our out-of-equilibrium system shows deviations from both the law of rectilinear diameters and the law of corresponding states.Comment: 8 pages, 8 figure