The collective behavior of active semiflexible filaments is studied with a model of tangentially driven self-propelled worm-like chains. The combination of excluded-volume interactions and self-propulsion leads to several distinct dynamic phases as a function of bending rigidity, activity, and aspect ratio of individual filaments. We consider first the case of intermediate filament density. For high-aspect-ratio filaments, we identify a transition with increasing propulsion from a state of free-swimming filaments to a state of spiraled filaments with nearly frozen translational motion. For lower aspect ratios, this gas-of-spirals phase is suppressed with growing density due to filament collisions; instead, filaments form clusters similar to self-propelled rods. As activity increases, finite bending rigidity strongly effects the dynamics and phase behavior. Flexible filaments form small and transient clusters, while stiffer filaments organize into giant clusters, similarly to self-propelled rods, but with a reentrant phase behavior from giant to smaller clusters as activity becomes large enough to bend the filaments. For high filament densities, we identify a nearly frozen jamming state at low activities, a nematic laning state at intermediate activities, and an active-turbulence state at high activities. The latter state is characterized by a power-law decay of the energy spectrum as a function of wave number. The resulting phase diagrams encapsulate tunable non-equilibrium steady states that can be used in the organization of living matter.
Worm-like filaments, which are propelled by a tangential homogeneous force along their contour, are studied as they push loads of different shapes and sizes. The resulting dynamics is investigated using Langevin dynamics simulations. The effects of size and shape of the load, propulsion strength, and thermal noise are systematically explored. The propulsive force and hydrodynamic friction of the load cause a compression in the filament that results in a buckling instability and versatile motion. Distinct regimes of elongated filaments, curved filaments, beating filaments, and filaments with alternating beating and circular motion are identified, and a phase diagram depending on the propulsion strength and the size of the load is constructed. Characteristic features of the different phases, such as beating frequencies and rotational velocities, are demonstrated to have a power-law dependence on the propulsive force.
Molecular precursors, ultrathin films that precede spreading droplets, are still far from being understood, despite intensive study. The inherent microscopic length scales make small-scale experimental techniques and molecular simulation ideal methods to study this phenomenon. Previous work on molecular precursors using nanoscale droplets, however, consistently suffers from incorrect measurement of the dimensions of the precursor film. An alternative method to accurately characterize the precursor film is presented here. In contrast to previous measures, this method (i) allows for easy detection and characterization of precursors and (ii) yields wetting dynamics that agree with experimental observations. Finally, we briefly comment on previous studies whose conclusions may merit reconsideration in light of the present work.
While the mass transport mechanisms and dynamics of molecular precursors, ultrathin films that precede spreading droplets, are well understood, the requirements for their formation and the reasons for the occurrence of different precursor shapes remain unclear. In this work, we study these requirements using molecular dynamics simulations of spreading droplets and extensive free energy computations. For a simple simulation model, we demonstrate that with growing droplet-substrate attraction, spreading passes succesively through regimes with no precursor, a monolayer precursor, and a continuously growing precursor. We show that the onset of layer formation and the changes in the precursor shape correlate with the free energy of layer formation. On the basis of these findings, we show that a positive spreading coefficient is sufficient but not necessary for precursor formation.
Worm-like filaments that are propelled homogeneously along their tangent vector are studied by Brownian dynamics simulations. Systems in two dimensions are investigated, corresponding to filaments adsorbed to interfaces or surfaces. A large parameter space covering weak and strong propulsion, as well as flexible and stiff filaments is explored. For strongly propelled and flexible filaments, the free-swimming filaments spontaneously form stable spirals. The propulsion force has a strong impact on dynamic properties, such as the rotational and translational mean square displacement and the rate of conformational sampling. In particular, when the active self-propulsion dominates thermal diffusion, but is too weak for spiral formation, the rotational diffusion coefficient has an activity-induced contribution given by v(c)/ξ(P), where v(c) is the contour velocity and ξ(P) the persistence length. In contrast, structural properties are hardly affected by the activity of the system, as long as no spirals form. The model mimics common features of biological systems, such as microtubules and actin filaments on motility assays or slender bacteria, and artificially designed microswimmers.
Actin Cytoskeleton/metabolism , Microtubules/metabolism , Actin Cytoskeleton/chemistry , Microtubules/chemistry , Molecular Dynamics Simulation , Motion , Pliability
Superspreading, the greatly enhanced spreading of aqueous solutions of trisiloxane surfactants on hydrophobic substrates, is of great interest in fundamental physics and technical applications. Despite numerous studies in the last 20 years, the superspreading mechanism is still not well understood, largely because the molecular scale cannot be resolved appropriately either experimentally or using continuum simulations. The absence of molecular-scale knowledge has led to a series of conflicting hypotheses based on different assumptions of surfactant behavior. We report a series of large-scale molecular dynamics simulations of aqueous solutions of superspreading and non-superspreading surfactants on different substrates. We find that the transition from the liquid-vapor to the solid-liquid interface is smooth for superspreading conditions, allowing direct adsorption through the contact line. This finding complements a study [Karapetsas et al., J. Fluid Mech., 2011, 670, 5-37], which predicts that superspreading can occur if this adsorption path is possible. Based on the observed mechanism, we provide plausible explanations for the influence of the substrate hydrophobicity, the surfactant chain length, and the surfactant concentration on the superspreading phenomenon. We also briefly address that the observed droplet shape is a mechanism to overcome the Huh-Scriven paradox of infinite viscous dissipation at the contact line.
The mechanism of superspreading, the greatly enhanced spreading of water droplets facilitated by trisiloxane surfactants, is still under debate, largely because the role and behavior of the surfactants cannot be sufficiently resolved by experiments or continuum simulations. Previous molecular dynamics studies have been performed with simple model molecules or inaccurate models, strongly limiting their explanatory power. Here we present a force field dedicated to superspreading, extending existing quantum-chemistry-based models for the surfactant and the TIP4P/2005 water model ( Abascal et al. J. Chem. Phys. , 2005 , 123 , 234505 ). We apply the model to superspreading trisiloxane surfactants and nonsuperspreading alkyl ethoxylate and perfluoroalkane surfactants at various concentrations at the air-water interface. We show that the developed model accurately predicts surface tensions, which are typically assumed important for superspreading. Significant differences between superspreading and traditional surfactants are presented and their possible relation to superspreading discussed. Although the force field has been developed for superspreading problems, it should also perform well for other simulations involving polymers or copolymers with water.
Long-range dispersion interactions have a critical influence on physical quantities in simulations of inhomogeneous systems. However, the perceived computational overhead of long-range solvers has until recently discouraged their implementation in molecular dynamics packages. Here, we demonstrate that reducing the cutoff radius for local interactions in the recently introduced particle-particle particle-mesh (PPPM) method for dispersion [Isele-Holder et al., J. Chem. Phys., 2012, 137, 174107] can actually often be faster than truncating dispersion interactions. In addition, because all long-range dispersion interactions are incorporated, physical inaccuracies that arise from truncating the potential can be avoided. Simulations using PPPM or other mesh Ewald solvers for dispersion can provide results more accurately and more efficiently than simulations that truncate dispersion interactions. The use of mesh-based approaches for dispersion is now a viable alternative for all simulations containing dispersion interactions and not merely those where inhomogeneities were motivating factors for their use. We provide a set of parameters for the dispersion PPPM method using either ik or analytic differentiation that we recommend for future use and demonstrate increased simulation efficiency by using the long-range dispersion solver in a series of performance tests on massively parallel computers.
For inhomogeneous systems with interfaces, the inclusion of long-range dispersion interactions is necessary to achieve consistency between molecular simulation calculations and experimental results. For accurate and efficient incorporation of these contributions, we have implemented a particle-particle particle-mesh Ewald solver for dispersion (r(-6)) interactions into the LAMMPS molecular dynamics package. We demonstrate that the solver's O(N log N) scaling behavior allows its application to large-scale simulations. We carefully determine a set of parameters for the solver that provides accurate results and efficient computation. We perform a series of simulations with Lennard-Jones particles, SPC/E water, and hexane to show that with our choice of parameters the dependence of physical results on the chosen cutoff radius is removed. Physical results and computation time of these simulations are compared to results obtained using either a plain cutoff or a traditional Ewald sum for dispersion.
Models, Molecular , Hexanes/chemistry , Physical Phenomena , Surface Tension , Water/chemistry
We present a definition of intermolecular surface contact by applying weighted Voronoi tessellations to configurations of various organic liquids and water obtained from molecular dynamics simulations. This definition of surface contact is used to link the COSMO-RS model and molecular dynamics simulations. We demonstrate that additively weighted tessellation is the superior tessellation type to define intermolecular surface contact. Furthermore, we fit a set of weights for the elements C, H, O, N, F, and S for this tessellation type to obtain optimal agreement between the models. We use these radii to successfully predict contact statistics for compounds that were excluded from the fit and mixtures. The observed agreement between contact statistics from COSMO-RS and molecular dynamics simulations confirms the capability of the presented method to describe intermolecular contact. Furthermore, we observe that increasing polarity of the surfaces of the examined molecules leads to weaker agreement in the contact statistics. This is especially pronounced for pure water.
