Although numerical simulations of rheological measurements typically focus on homogeneous systems, heterogeneity can profoundly impact material properties. We report on the rheological properties of a suspension of two-dimensional Lennard-Jones particles across the gas/liquid and the gas/solid coexistence lines of the system. We show how the presence of multiple coexisting states has a significant impact on the mechanical properties of these systems when compared with their homogeneous reference counterparts. Our results establish an extended map to navigate a landscape where not only density and temperature, but also phase coexistence, dictate the transition from viscous to elastic-dominated behavior under shear. These results provides a benchmark for future research into heterogeneous fluids where the coexistence of complex dynamic states is frequently observed.

A remarkable property of flexible self-avoiding elastic surfaces (membranes) is that they remain flat at all temperatures, even in the absence of a bending rigidity or in the presence of active fluctuations. Here, we report numerical results of these surfaces wherein we alter their topology by systematically cleaving internal bonds. While it is known that a random removal of membrane bonds does not disrupt the overall extended shape of the membrane, we find that cleaving an elastic surface with longitudinal parallel cuts leads to its systematic collapse into a number of complex morphologies that can be controlled by altering the number and length of the inserted cuts. For the simpler case of membranes with bending rigidity but in the absence of self-avoidance, we find that the radius of gyration of the surface as a function of number of cuts is represented by a universal master curve when the variables are appropriately rescaled.

Understanding the mechanical properties of active suspensions is crucial for their potential applications in materials engineering. Among active phenomena with no analog in equilibrium systems, motility-induced phase separation (MIPS) in active colloidal suspensions is one of the most extensively studied. However, the mechanical properties of MIPS remain poorly understood. This Letter investigates the rheology of a suspension of active colloidal particles under constant and oscillatory shear. Systems consisting of pseudohard active Brownian particles exhibiting coexistence of dense and dilute phases behave as a viscoelastic Maxwell-like fluid at low and high frequencies, displaying exclusively shear thinning across a wide range of densities and activities. Remarkably, the crossover frequency between the storage and loss moduli is nonmonotonic, increasing with activity before the MIPS transition but decreasing with activity after the transition, in contrast to a passive analog system of attractive particles in liquid-gas phase coexistence, revealing the subtleties of how active forces and intrinsically out-of-equilibrium phases affect the mechanical properties.

Understanding the mechanical properties of active suspensions is crucial for their potential applications in materials engineering. Among the various phenomena in active matter that have no analogue in equilibrium systems, motility-induced phase separation (MIPS) in active colloidal suspensions is one of the most extensively studied. However, the mechanical properties of this fundamental active state of matter remain poorly understood. This study investigates the rheology of a suspension of active colloidal particles under constant and oscillatory shear. Systems consisting of pseudo-hard active Brownian particles exhibiting co-existence of dense and dilute phases behave as a viscoelastic Maxwell fluid at low and high frequencies, displaying exclusively shear thinning across a wide range of densities and activities. Remarkably, the cross-over point between the storage and loss moduli is non-monotonic, rising with activity before the MIPS transition but falling with activity after the transition, revealing the subtleties of how active forces and intrinsically out-of-equilibrium phases affect the mechanical properties of these systems.

The existence of a crumpled phase for self-avoiding elastic surfaces was postulated more than three decades ago using simple Flory-like scaling arguments. Despite much effort, its stability in a microscopic environment has been the subject of much debate. In this paper we show how a crumpled phase develops reliably and consistently upon subjecting a thin spherical shell to active fluctuations. We find a master curve describing how the relative volume of a shell changes with the strength of the active forces, that applies for every shell independent of size and elastic constants. Furthermore, we extract a general expression for the onset active force beyond which a shell begins to crumple. Finally, we calculate how the size exponent varies along the crumpling curve.

We perform numerical simulations of active ideal and self-avoiding tethered membranes. Passive ideal membranes with bending interactions are known to exhibit a continuous crumpling transition between a low temperature flat phase and a high temperature crumpled phase. Conversely, self-avoiding membranes remain in an extended (flat) phase for all temperatures even in the absence of a bending energy. We find that the introduction of active fluctuations into the system produces a phase behavior that is overall consistent with that observed for passive membranes. The phases and the nature of the transition for ideal membranes is unchanged and active fluctuations can be remarkably accounted for by a simple rescaling of the temperature. For the self-avoiding membrane, we find that the extended phase is preserved even in the presence of very large active fluctuations.

Singlet fission and triplet-triplet annihilation upconversion are two multiexciton processes intimately related to the dynamic interaction between one high-lying energy singlet and two low-lying energy triplet excitons. Here, we introduce a series of dendritic macromolecules that serve as platform to study the effect of interchromophore interactions on the dynamics of multiexciton generation and decay as a function of dendrimer generation. The dendrimers (generations 1–4) consist of trimethylolpropane core and 2,2-bis(methylol)propionic acid (bis-MPA) dendrons that provide exponential growth of the branches, leading to a corona decorated with pentacenes for SF or anthracenes for TTA-UC. The findings reveal a trend where a few highly ordered sites emerge as the dendrimer generation grows, dominating the multiexciton dynamics, as deduced from optical spectra, and transient absorption spectroscopy. While the dendritic structures enhance TTA-UC at low annihilator concentrations in the largest dendrimers, the paired chromophore interactions induce a broadened and red-shifted excimer emission. In SF dendrimers of higher generations, the triplet dynamics become increasingly dominated by pairwise sites exhibiting strong coupling (Type II), which can be readily distinguished from sites with weaker coupling (Type I) by their spectral dynamics and decay kinetics.

One of the most promising features of active systems is that they can extract energy from their environment and convert it to mechanical work. Self propelled particles enable rectification when in contact with rigid boundaries. They can rectify their own motion when confined in asymmetric channels and that of microgears. In this paper, we study the shape fluctuations of two dimensional flexible vesicles containing active Brownian particles. We show how these fluctuations not only are capable of easily squeezing a vesicle through narrow openings, but are also responsible for its rectification when placed within asymmetric confining channels (ratchetaxis). We detail the conditions under which this process can be optimized, and sort out the complex interplay between elastic and active forces responsible for the directed motion of the vesicle across these channels.

Can active forces be exploited to drive the consistent collapse of an active polymer into a folded structure? In this paper, we introduce and perform numerical simulations of a simple model of active colloidal folders and show that a judicious inclusion of active forces into a stiff colloidal chain can generate designable and reconfigurable two-dimensional folded structures. The key feature is to organize the forces perpendicular to the chain backbone according to specific patterns (sequences). We characterize the physical properties of this model and perform, using a number of numerical techniques, an in-depth statistical analysis of structure and dynamics of the emerging conformations. We discovered a number of interesting features, including the existence of a direct correspondence between the sequence of the active forces and the structure of folded conformations, and we discover the existence of an ensemble of highly mobile compact structures capable of moving from conformation to conformation. Finally, akin to protein design problems, we discuss a method that is capable of designing specific target folds by sampling over sequences of active forces.

The characterization of the interactions between two fully flexible self-avoiding polymers is one of the classic and most important problems in polymer physics. In this paper we measure these interactions in the presence of active fluctuations. We introduce activity into the problem using two of the most popular models in this field, one where activity is effectively embedded into the monomers' dynamics, and the other where passive polymers fluctuate in an explicit bath of active particles. We establish the conditions under which the interaction between active polymers can be mapped into the classical passive problem. We observe that the active bath can drive the development of strong attractive interactions between the polymers and that, upon enforcing a significant degree of overlap, they come together to form a single double-stranded unit. A phase diagram tracing this change in conformational behavior is also reported.

Colloids that interact via a short-range attraction serve as the primary building blocks for a broad range of self-assembled materials. However, one of the well-known drawbacks to this strategy is that these building blocks rapidly and readily condense into a metastable colloidal gel. Using computer simulations, we illustrate how the addition of a small fraction of purely repulsive self-propelled colloids, a technique referred to as active doping, can prevent the formation of this metastable gel state and drive the system toward its thermodynamically favored crystalline target structure. The simplicity and robust nature of this strategy offers a systematic and generic pathway to improving the self-assembly of a large number of complex colloidal structures. We discuss in detail the process by which this feat is accomplished and provide quantitative metrics for exploiting it to modulate the self-assembly. We provide evidence for the generic nature of this approach by demonstrating that it remains robust under a number of different anisotropic short-ranged pair interactions in both two and three dimensions. In addition, we report on a novel microphase in mixtures of passive and active colloids. For a broad range of self-propelling velocities, it is possible to stabilize a suspension of fairly monodisperse finite-size crystallites. Surprisingly, this microphase is also insensitive to the underlying pair interaction between building blocks. The active stabilization of these moderately sized monodisperse clusters is quite remarkable and should be of great utility in the design of hierarchical self-assembly strategies. This work further bolsters the notion that active forces can play a pivotal role in directing colloidal self-assembly.

We perform numerical simulations of an active fully flexible self-avoiding polymer as a function of the quality of the embedding solvent described in terms of an effective monomer-monomer interaction. Specifically, by extracting the Flory exponent of the active polymer under different conditions, we are able to pin down the location of the coil-globule transition for different strengths of the active forces. Remarkably, we find that a simple rescaling of the temperature is capable of qualitatively capturing the dependence of the Θ-point of the polymer on the amplitude of active fluctuations. We discuss the limits of this mapping and suggest that a negative active pressure between the monomers, not unlike the one that has already been found in suspensions of active hard spheres, may also be present in active polymers.

We perform numerical simulations of active semiflexible filaments inside a rigid spherical cavity. We study the problem as a function of the bending rigidity, degree of confinement, and strength of the active forces. For passive filaments, the multispool conformations already established in previous studies are recovered, yet even small amounts of activity, when aligned along the direction of the filament backbone, destabilize these passive conformations. What emerges from our study is a highly dynamic scenario, where a filament is capable of escaping local and global energy minima and sample, in a quasiperiodic fashion, an ensemble of conformations usually associated with higher bending energies, and previously observed for passive filaments only under very different degrees of confinement or identified as glassy metastable states. We detail the structural properties of the different states and uncover a new dynamic pathway associated with their formation.

Singlet fission has emerged as a key mechanism of exciton multiplication in organic chromophores, generating two triplet excitons from a single photon. Singlet fission is typically studied in crystalline films or in isolated dimers. Here, we investigate an intermediate regime where through-space interactions mediate singlet fission and triplet pair recombination within isolated polymer chains. Specifically, we investigate how appending pentacenes to a polynorbornene backbone can lead to macromolecules that take advantage of through-space π-π interactions for fast singlet fission and rapid triplet pair dissociation. Singlet fission in these systems is affected by molecular dynamics, and triplet-triplet recombination is a geminate process where the rate of recombination scales with molecular-weight. We find that these pendent pentacene polymers yield free triplets with lifetimes that surpass those of crystalline chromophores in both solution as isolated polymers and in thin films.

The development of colloidal particles that can become self-propelled when exposed to a source of light of a given frequency represents one of the most exciting new developments in the field of active matter. In this paper, we perform numerical simulations to explore several properties of crystalline colloidal aggregates in the presence of such external light fields. We show how permanent gaps of tunable size can be carved into these crystals as a result of a solid-gas transition that occurs above a threshold light intensity. We compare this phenomenon to that occurring in a parent system obtained by replacing self-propulsion with an effective temperature and discuss the main differences between the two setups. Finally, we show how moving the light field across a solid-fluid boundary allows us to transfer or transport the fluid component into or across the solid one. We discuss the dynamics of this process and set limits associated with its performance.

Scaling arguments used to predict the radius of gyration of passive self-avoiding flexible polymers have been shown to hold for polymers under the influence of active fluctuations. In this Letter, we establish how the standard blob scaling theory representation of a polymer, capable of capturing the essential physics of passive polymers under a variety of settings, breaks down when dealing with active polymers under confinement. Using numerical simulations, we show how the predicted exponents associated to the forces applied by a polymer when restricted within cavities of different geometries hold only whenever the persistence length generated on the polymer by the active forces is much smaller than the size of the characteristic blob in the scaling theory.

We present systematic numerical simulations to understand the behavior of colloidal swimmers near a wall. We extend previous theoretical calculations based on lubrication theory to include walls with arbitrary curvature, and show how to extract from simulations a set of parameters crucial to accurately estimate the leading hydrodynamic contributions associated with the curvature of a wall. Our results show explicitly how introducing curvature to the wall not only affects the average incident angle the swimmer acquires when swimming near it, but it also leads to much broader angular distributions. This suggests an increasingly leading role of thermal fluctuations with curvature, which in turn results in significantly different motility of the swimmers. We also show how the backwards motion previously reported for pushers also extends to puller-like swimmers under the appropriate conditions. Finally, aiming at understanding the behavior of colloidal swimmers near a colloidal crystal, we also considered the case of a wall built from colloidal particles that are either free to rotate, representing a crystal held together by isotropic forces, or have their rotational degrees of freedom locked-in, representing a crystal held together by directional interactions. In both cases, we find that puller-like swimmers follow a stochastic run-and-tumble-like dynamics.

Here, we describe a method for the enhanced self-assembly of triblock Janus colloids targeted to form a kagome lattice. Using computer simulations, we demonstrate that the formation of this elusive structure can be significantly improved by self-propelling or activating the colloids along the axis connecting their hydrophobic hemispheres. The process by which metastable aggregates are destabilized and transformed into the favored kagome lattice is quite general, and we argue this active approach provides a systematic pathway to improving the self-assembly of a large number of colloidal structures.

Colloids grafted with a corona layer of polymers show glassy behavior that covers a wide range of fragilities, with this behavior being tunable through variations in grafting density and grafting chain length. We find that the corona roughness, which is maximized for long chain lengths and sparse grafting, is directly correlated to the concentration-dependence of the system relaxation time (fragility). Relatively rougher colloids result in stronger liquids because their rotational motions become orientationally correlated across the whole system even at low particle loadings leading to an essentially Arrhenius-like concentration-dependence of the relaxation times near the glass transition. The smoother colloids do not show as much orientational correlation except at higher densities leading to fragile behavior. We therefore propose that these materials are an ideal model to study the physical properties of the glass transition.