Transport and phase separation of active Brownian particles in fluctuating environments.

In this work, we study the dynamics of a single active Brownian particle, as well as the collective behavior of interacting active Brownian particles, in a fluctuating heterogeneous environment. We employ a variant of the diffusing diffusivity model where the equation of motion of the active particle involves a time-dependent motility and diffusivities. Within our model, those fluctuations are coupled to each other. Using analytical methods, we obtain the probability distribution function of particle displacement and its moments for a single particle. We then investigate the impact of the environmental fluctuations on the collective behavior of the active Brownian particles by means of extensive numerical simulations. Our results show that the fluctuations hinder the motility-induced phase separation, accompanied by a significant change of the density dependence of particle velocities. These effects are interpreted using our analytical results for the dynamics of a single particle.

Limits of size scalability of diffusion and growth: Atoms versus molecules versus colloids.

Understanding fundamental growth processes is key to the control of nonequilibrium structure formation for a wide range of materials on all length scales, from atomic to molecular and even colloidal systems. While atomic systems are relatively well studied, molecular and colloidal growth are currently moving more into the focus. This poses the question to what extent growth laws are size scalable between different material systems. We study this question by analyzing the potential energy landscape and performing kinetic Monte Carlo simulations for three representative systems. While submonolayer (island) growth is found to be essentially scalable, we find marked differences when moving into the third (vertical) dimension.

Lane formation in a driven attractive fluid.

We investigate nonequilibrium lane formation in a generic model of a fluid with attractive interactions, that is, a two-dimensional Lennard-Jones fluid composed of two particle species driven in opposite directions. Performing Brownian dynamics simulations for a wide range of parameters, supplemented by a stability analysis based on dynamical density functional theory, we identify generic features of lane formation in the presence of attraction, including structural properties. In fact, we find a variety of states (as compared to purely repulsive systems), as well as a close relation between laning and long-wavelength instabilities of the homogeneous phase such as demixing and condensation.

Shear banding in nematogenic fluids with oscillating orientational dynamics.

We investigate the occurrence of shear banding in nematogenic fluids under planar Couette flow, based on mesoscopic dynamical equations for the orientational order parameter and the shear stress. We focus on parameter values where the sheared homogeneous system exhibits regular oscillatory orientational dynamics, whereas the equilibrium system is either isotropic (albeit close to the isotropic-nematic transition) or deep in its nematic phase. The numerical calculations are restricted to spatial variations in shear gradient direction. We find several new types of shear-banded states characterized by regions with regular oscillatory orientational dynamics. In all cases shear banding is accompanied by a non-monotonicity of the flow curve of the homogeneous system; however, only in the case of the initially isotropic system this curve has the typical S-like shape. We also analyze the influence of different orientational boundary conditions and of the spatial correlation length.

Effects of magnetic field gradients on the aggregation dynamics of colloidal magnetic nanoparticles.

We have used low-field (1)H nuclear-magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) to investigate the aggregation dynamics of magnetic particles in ionic ferrofluids (IFFs) in the presence of magnetic field gradients. At the beginning of the experiments, the measured NMR spectra were broad and asymmetric, exhibiting two features attributed to different dynamical environments of water protons, depending on the local strength of the field gradients. Hence, the spatial redistribution of the magnetic particles in the ferrofluid caused by the presence of an external magnetic field in a time scale of minutes can be monitored in real time, following the changes in the features of the NMR spectra during a period of about an hour. As previously reported [Heinrich et al., Phys. Rev. Lett., 2011, 106, 208301], in the homogeneous magnetic field of a NMR spectrometer, the aggregation of the particles of the IFF proceeds in two stages. The first stage corresponds to the gradual aggregation of monomers prior to and during the formation of chain-like structures. The second stage proceeds after the chains have reached a critical average length, favoring lateral association of the strings into hexagonal zipped-chain superstructures or bundles. In this work, we focus on the influence of a strongly inhomogeneous magnetic field on the aforementioned aggregation dynamics. The main observation is that, as the sample is immersed in a certain magnetic field gradient and kept there for a time τinh, magnetophoresis rapidly converts the ferrofluid into an aggregation state which finds its correspondence to a state on the evolution curve of the pristine sample in a homogeneous field. From the degree of aggregation reached at the time τinh, the IFF sample just evolves thereafter in the homogeneous field of the NMR spectrometer in exactly the same way as the pristine sample. The final equilibrium state always consists of a colloidal suspension of zipped-chain bundles with the chain axes aligned along the magnetic field direction.

Unravelling the multilayer growth of the fullerene C60 in real time.

Molecular semiconductors are increasingly used in devices, but understanding of elementary nanoscopic processes in molecular film growth is in its infancy. Here we use real-time in situ specular and diffuse X-ray scattering in combination with kinetic Monte Carlo simulations to study C60 nucleation and multilayer growth. We determine a self-consistent set of energy parameters describing both intra- and interlayer diffusion processes in C60 growth. This approach yields an effective Ehrlich-Schwoebel barrier of EES=110 meV, diffusion barrier of ED=540 meV and binding energy of EB=130 meV. Analysing the particle-resolved dynamics, we find that the lateral diffusion is similar to colloids, but characterized by an atom-like Schwoebel barrier. Our results contribute to a fundamental understanding of molecular growth processes in a system, which forms an important intermediate case between atoms and colloids.

Spinodal decomposition of a binary magnetic fluid confined to a surface.

In our previous work [J. Chem. Phys. 136, 024502 (2012)], we reported a demixing phase transition of a quasi-two-dimensional, binary Heisenberg fluid mixture driven by the ferromagnetic interactions of the magnetic species. Here, we present a theoretical study for the time-dependent coarsening occurring within the two-phase region in the density-concentration plane, also known as spinodal decomposition. Our investigations are based on dynamical density functional theory (DDFT). The particles in the mixture are modeled as Gaussian soft spheres on a two-dimensional surface, where one component carries a classical spin of Heisenberg type. To investigate the two-phase region, we first present a linear stability analysis with respect to small, harmonic density perturbations. Second, to capture nonlinear effects, we calculate time-dependent structure factors by combining DDFT with Percus' test particle method. For the growth of the average domain size l during spinodal decomposition with time t, we observe a power-law behavior l∝t^{δ_{α}} with δ_{m}≃0.333 for the magnetic species and δ_{n}≃0.323 for the nonmagnetic species.

Feedback-induced oscillations in one-dimensional colloidal transport.

We investigate a driven, one-dimensional system of colloidal particles in a periodically corrugated narrow channel subject to a time-delayed feedback control. Our goal is to identify conditions under which the control induces oscillatory, time-periodic states. The investigations are based on the Fokker-Planck equation involving the density distribution of the system. First, by using the numerical continuation technique, we determine the linear stability of a stationary density. Second, the nonlinear regimes are analyzed by studying numerically the temporal evolution of the first moment of the density distribution. In this way we construct a bifurcation diagram revealing the nature of the instability. Apart from the case of a system with periodic boundary conditions, we also consider a microchannel of finite length. Finally, we study the influence of (repulsive) particle interactions based on dynamical density functional theory.

Phase separation dynamics in a two-dimensional magnetic mixture.

Based on classical density functional theory (DFT), we investigate the demixing phase transition of a two-dimensional, binary Heisenberg fluid mixture. The particles in the mixture are modeled as Gaussian soft spheres, where one component is characterized by an additional classical spin-spin interaction of Heisenberg type. Within the DFT we treat the particle interactions using a mean-field approximation. For certain magnetic coupling strengths, we calculate phase diagrams in the density-concentration plane. For sufficiently large coupling strengths and densities, we find a demixing phase transition driven by the ferromagnetic interactions of the magnetic species. We also provide a microscopic description (i.e., density profiles) of the resulting non-magnetic/magnetic fluid-fluid interface. Finally, we investigate the phase separation using dynamical density functional theory, considering both nucleation processes and spinodal demixing.

Dynamics of the field-induced formation of hexagonal zipped-chain superstructures in magnetic colloids.

Combining nuclear magnetic resonance and molecular dynamics simulations, we unravel the long-time dynamics of a paradigmatic colloid with strong dipole-dipole interactions. In a homogeneous magnetic field, ionic ferrofluids exhibit a stepwise association process from ensembles of monomers over stringlike chains to bundles of hexagonal zipped-chain patches. We demonstrate that attractive van der Waals interactions due to charge-density fluctuations in the magnetic particles play the key role for the dynamical stabilization of the hexagonal superstructures against thermal dissociation. Our results give insight into the dynamics of self-organization in systems dominated by dipolar interactions.

Structure formation in layered ferrofluid nanofilms.

We present Monte Carlo simulation results for strongly coupled dipolar fluids, such as ferrofluids, confined to a narrow slit pore accommodating only a few layers of particles. Our results show that the ferromagnetic ordering observed in dense bulk systems and in thick fluid films persists down to nanoscopic wall separations where the system consists of only 3 monolayers. The ferromagnetic transition density in these systems approaches experimentally accessible values. For even smaller wall separations, we observe stripelike defects and finally the breakdown of orientational ordering for systems close to the two-dimensional limit. Our results for the liquid phase are supported by simulations starting from quasicrystalline soft-sphere configurations.

Coarse graining of nonbonded degrees of freedom.

We investigate the physical meaning of coarse-grained beads generated by coarse graining of nonbonded particles such as solvent molecules in a solution. Starting from the partition function, we analytically coarse grain an N-particle fluid to a system containing N-2 of the original particles plus a bead representing the two remaining particles. As a direct consequence of the lack of bonding interactions, the resulting effective potential becomes independent of the bead coordinates, i.e., ideal-gas-like, in the thermodynamic limit. Thus, there are no conservative forces between coarse-grained beads representing assemblies of nonbonded molecules nor between these beads and any other species in the system.

Polar nano-rods under shear: from equilibrium to chaos.

The orientational dynamics of rod-like particles with permanent (electric or magnetic) dipole moments in a plane Couette shear flow is investigated using mesoscopic relaxation equations combined with a generalized Landau free energy. The free energy contribution due to the coupling between average alignment and dipole orientation is derived on a microscopic basis. Numerical results of the resulting eight-dimensional dynamical system are presented for the case of longitudinal dipoles and thermodynamic conditions where the equilibrium state is a (polar or non-polar) nematic. Solution diagrams reveal presence of a large variety of periodic, transient chaotic, and chaotic dynamic states of the average alignment and dipole moment, respectively, appearing as a function of Deborah number and tumbling parameter. Compared to rods without dipoles we observe a significant preference of out-of-plane kayaking-tumbling states and, generally, a higher sensitivity to the initial conditions including bistability. We also demonstrate that the average (electric) dipole moment characterizing most of the observed states yields electrodynamic (magnetic) fields of measurable strength.

Vapor-liquid transitions of dipolar fluids in disordered porous media: performance of angle-averaged potentials.

Using replica integral equations in the reference hypernetted-chain (RHNC) approximation we calculate vapor-liquid spinodals, chemical potentials, and compressibilities of fluids with angle-averaged dipolar interactions adsorbed to various disordered porous media. Comparison with previous RHNC results for systems with true angle-dependent Stockmayer (dipolar plus Lennard-Jones) interactions indicate that, for a dilute hard sphere matrix, the angle-averaged fluid-fluid (ff) potential is a reasonable alternative for reduced fluid dipole moments m( *2)=mu(2)/(epsilon(0)sigma(3))< or =2.0. This range is comparable to that estimated in bulk fluids, for which RHNC results are presented as well. Finally, results for weakly polar matrices suggest that angle-averaged fluid-matrix (fm) interactions can reproduce main features observed for true dipolar (fm) interactions such as the shift of the vapor-liquid spinodals towards lower temperatures and higher densities. However, the effective attraction induced by dipolar (fm) interaction is underestimated rather than overestimated as in the case of angle-averaged ff interactions.

Integral equation study of a Stockmayer fluid adsorbed in polar disordered matrices.

Based on replica integral equations in the (reference) hypernetted chain approximation we investigate the structural features and phase properties of a dipolar Stockmayer fluid confined to a disordered dipolar matrix. The integral equations are applied to the homogeneous high-temperature phase where the system is globally isotropic. At low densities we find the influence of dipolar interactions between fluid (f) and matrix (m) particles to be surprisingly similar to the previously investigated effect of attractive isotropic (fm) interactions: the critical temperature of the vapor-liquid transition decreases with increasing (fm) coupling, while the critical density increases. The anisotropic nature of the dipolar (fm) interactions turns out to play a more dominant role at high fluid densities where we observe a pronounced sensitivity in the dielectric constant and a strong degree of local orientational ordering of the fluid particles along the local fields generated by the matrix. Moreover, an instability of the dielectric constant, which is a precursor of ferroelectric ordering occurring both in bulk Stockmayer fluids and in fluids in nonpolar matrices, is observed only for very small dipolar (fm) couplings.