Nonequilibrium adsorption of 2AnB patchy colloids on substrates

We study the irreversible adsorption of spherical $2AnB$ patchy colloids (with two $A$-patches on the poles and $n$ $B$-patches along the equator) on a substrate. In particular, we consider dissimilar $AA$, $AB$, and $BB$ binding probabilities. We characterize the patch-colloid network and its dependence on $n$ and on the binding probabilities. Two growth regimes are identified with different density profiles and we calculate a growth mode diagram as a function of the colloid parameters. We also find that, close to the substrate, the density of the network, which depends on the colloid parameters, is characterized by a depletion zone

Nonequilibrium self-organization of colloidal particles on substrates: adsorption, relaxation, and annealing

Colloidal particles are considered ideal building blocks to produce materials with enhanced physical properties. The state-of-the-art techniques for synthesizing these particles provide control over shape, size, and directionality of the interactions. In spite of these advances, there is still a huge gap between the synthesis of individual components and the management of their spontaneous organization towards the desired structures. The main challenge is the control over the dynamics of self-organization. In their kinetic route towards thermodynamically stable structures, colloidal particles self-organize into intermediate (mesoscopic) structures that are much larger than the individual particles and become the relevant units for the dynamics. To follow the dynamics and identify kinetically trapped structures, one needs to develop new theoretical and numerical tools. Here we discuss the self-organization of functionalized colloids (also known as patchy colloids) on attractive substrates. We review our recent results on the adsorption and relaxation and explore the use of annealing cycles to overcome kinetic barriers and drive the relaxation towards the targeted structures

Adsorbed films of three-patch colloids: Continuous and discontinuous transitions between thick and thin films

We investigate numerically the role of spatial arrangement of the patches on the irreversible adsorption of patchy colloids on a substrate. We consider spherical three-patch colloids and study the dependence of the kinetics on the opening angle between patches. We show that growth is suppressed below and above minimum and maximum opening angles, revealing two absorbing phase transitions between thick and thin film regimes. While the transition at the minimum angle is continuous, in the Directed Percolation class, that at the maximum angle is clearly discontinuous. For intermediate values of the opening angle, a rough colloidal network in the Kardar-Parisi-Zhang universality class grows indefinitely. The nature of the transitions was analyzed in detail by considering bond flexibility, defined as the dispersion of the angle between the bond and the center of the patch. For the range of flexibilities considered we always observe two phase transitions. However, the range of opening angles where growth is sustained increases with flexibility. At a tricritical flexibility, the discontinuous transition becomes continuous. The practical implications of our findings and the relation to other nonequilibrium transitions are discussed

Kinetic interfaces of patchy particles

We study the irreversible adsorption of patchy particles on substrates in the limit of advective mass transport. Recent numerical results show that the interface roughening depends strongly on the particle attributes, such as, patch-patch correlations, bond flexibility, and strength of the interactions, uncovering new absorbing phase transitions. Here, we revisit these results and discuss in detail the transitions. In particular, we present new evidence that the tricritical point, observed in systems of particles with flexible patches, is in the tricritical directed percolation universality class. A scaling analysis of the time evolution of the correlation length for the aggregation of patchy particles with distinct bonding energies confirms that the critical regime is in the Kardar-Parisi-Zhang with quenched disorder universality class

Annealing cycles and the self-organization of functionalized colloids

The self-assembly of functionalized (patchy) particles with directional interactions into target structures is still a challenge, despite the significant experimental advances on their synthesis. The self-assembly pathways are typically characterized by high energy barriers that hinder the access to stable (equilibrium) structures. A possible strategy to tackle this challenge is to perform annealing cycles. By periodically switching on and off the inter-particle bonds, one expects to smooth-out the kinetic pathways and favor the assembly of targeted structures. Preliminary results have shown that the efficiency of annealing cycles depends strongly on their frequency. Here, we study numerically how this frequency-dependence scales with the strength of the directional interactions (size of the patch $\sigma$). We use analytical arguments to show that the scaling results from the statistics of a random walk in configurational space

Dynamics of patchy particles in and out of equilibrium

We combine particle-based simulations, mean-field rate equations, and Wertheim's theory to study the dynamics of patchy particles in and out of equilibrium, at different temperatures and densities. We consider an initial random distribution of non-overlapping three-patch particles, with no bonds, and analyze the time evolution of the breaking and bonding rates of a single bond. We find that the asymptotic (equilibrium) dynamics differs from the initial (out of equilibrium) one. These differences are expected to depend on the initial conditions, temperature, and density

Active nematic-isotropic interfaces in channels

We use numerical simulations to investigate the hydrodynamic behavior of the interface between nematic (N) and isotropic (I) phases of a confined active liquid crystal. At low activities, a stable interface with constant shape and velocity is observed separating the two phases. For nematics in homeotropic channels, the velocity of the interface at the NI transition increases from zero (i) linearly with the activity for contractile systems and (ii) quadratically for extensile ones. Interestingly, the nematic phase expands for contractile systems while it contracts for extensile ones, as a result of the active forces at the interface. Since both activity and temperature affect the stability of the nematic, for active nematics in the stable regime the temperature can be tuned to observe static interfaces, providing an operational definition for the coexistence of active nematic and isotropic phases. At higher activities, beyond the stable regime, an interfacial instability is observed for extensile nematics. In this regime defects are nucleated at the interface and move away from it. The dynamics of these defects is regular and persists asymptotically for a finite range of activities. We used an improved hybrid model of finite differences and lattice Boltzmann method with multi-relaxation-time collision operator, the accuracy of which allowed us to characterize the dynamics of the distinct interfacial regimes.Comment: 11 pages, 13 figure

Optimal number of linkers per monomer in linker-mediated aggregation

We study the dynamics of diffusion-limited irreversible aggregation of monomers, where bonds are mediated by linkers. We combine kinetic Monte Carlo simulations of a lattice model with a mean-field theory to study the dynamics when the diffusion of aggregates is negligible and only monomers diffuse. We find two values of the number of linkers per monomer which maximize the size of the largest aggregate. We explain the existence of the two maxima based on the distribution of linkers per monomer. This observation is well described by a simple mean-field model. We also show that a relevant parameter is the ratio of the diffusion coefficients of monomers and linkers. In particular, when this ratio is close to ten, the two maxima merge at a single maximum

The random field Blume-Capel model revisited

We have revisited the mean-field treatment for the Blume-Capel model under the presence of a discrete random magnetic field as introduced by Kaufman and Kanner. The magnetic field ($H$) versus temperature ($T$) phase diagrams for given values of the crystal field $D$ were recovered in accordance to Kaufman and Kanner original work. However, our main goal in the present work was to investigate the distinct structures of the crystal field versus temperature phase diagrams as the random magnetic field is varied because similar models have presented reentrant phenomenon due to randomness. Following previous works we have classified the distinct phase diagrams according to five different topologies. The topological structure of the phase diagrams is maintained for both $H-T$ and $D-T$ cases. Althoug the phase diagrams exhibit a richness of multicritical phenomena we did not found any reentrant effect as have been seen in similar models.Comment: 21 pages, 5 figure

Field-driven dynamical demixing of binary mixtures

We consider mixtures of two species of spherical colloidal particles that differ in their hydrodynamic radii, but are otherwise identical, in the presence of an external field. Since the particle-particle and particle-field interactions are the same for both species, they are completely mixed in the thermodynamic limit in the presence of any static field. Here, we combine Brownian Dynamics and Dynamic Density Functional theory of fluids to show that for sufficiently large differences in the hydrodynamic radius of the particles (and corresponding differences in their electrophoretic mobilities) dynamical demixing is observed. These demixed states are transient but, under certain conditions, packing effects compromise the relaxation towards the thermodynamic states and the lifetime of the demixed phases increases significantly