Three-body correlations and conditional forces in suspensions of active hard disks
Self-propelled Brownian particles show rich out-of-equilibrium physics, for instance, the motility-induced phase separation (MIPS). While decades of studying the structure of liquids have established a deep understanding of passive systems, not much is known about correlations in active suspensions. In this work we derive an approximate analytic theory for three-body correlations and forces in systems of active Brownian disks starting from the many-body Smoluchowski equation. We use our theory to predict the conditional forces that act on a tagged particle and their dependence on the propulsion speed of self-propelled disks. We identify preferred directions of these forces in relation to th…
Free energies, vacancy concentrations, and density distribution anisotropies in hard-sphere crystals: A combined density functional and simulation study
We perform a comparative study of the free energies and the density distributions in hard sphere crystals using Monte Carlo simulations and density functional theory (employing Fundamental Measure functionals). Using a recently introduced technique (Schilling and Schmid, J. Chem. Phys 131, 231102 (2009)) we obtain crystal free energies to a high precision. The free energies from Fundamental Measure theory are in good agreement with the simulation results and demonstrate the applicability of these functionals to the treatment of other problems involving crystallization. The agreement between FMT and simulations on the level of the free energies is also reflected in the density distributions …
Dense ionic fluids confined in planar capacitors: in- and out-of-plane structure from classical density functional theory
The ongoing scientific interest in the properties and structure of electric double layers (EDLs) stems from their pivotal role in (super)capacitive energy storage, energy harvesting, and water treatment technologies. Classical density functional theory (DFT) is a promising framework for the study of the in- and out-of-plane structural properties of double layers. Supported by molecular dynamics simulations, we demonstrate the adequate performance of DFT for analyzing charge layering in the EDL perpendicular to the electrodes. We discuss charge storage and capacitance of the EDL and the impact of screening due to dielectric solvents. We further calculate, for the first time, the in-plane str…
Anisotropic pair correlations in binary and multicomponent hard-sphere mixtures in the vicinity of a hard wall: A combined density functional theory and simulation study
The fundamental measure approach to classical density functional theory has been shown to be a powerful tool to predict various thermodynamic properties of hard-sphere systems. We employ this approach to determine not only one-particle densities but also two-particle correlations in binary and six-component mixtures of hard spheres in the vicinity of a hard wall. The broken isotropy enables us to carefully test a large variety of theoretically predicted two-particle features by quantitatively comparing them to the results of Brownian dynamics simulations. Specifically, we determine and compare the one-particle density, the total correlation functions, their contact values, and the force dis…
Charged colloidal particles in a charged wedge: do they go in or out?
Using real-space microscopy experiments, theory and computer simulation, we study the behaviour of highly charged colloidal particles which are confined between two highly charged plates forming a wedge geometry. Under low salt conditions it is experimentally observed that colloidal particles accumulate in the cusp of a wedge to form dense fluid or crystalline ordered structures. This behaviour is found for various cell geometries, salt concentrations and gravitational strengths, and even stays stable when additional convection is present in the system. An effort is made to understand this effect qualitatively on the basis of linear screening theory. For a single macro-ion, linear screening…
Heat-to-current conversion of low-grade heat from a thermocapacitive cycle by supercapacitors
Thermal energy is abundantly available, and especially low-grade heat is often wasted in industrial processes as a by-product. Tapping into this vast energy reservoir with cost-attractive technologies may become a key element for the transition to an energy-sustainable economy and society. We propose a novel heat-to-current converter which is based on the temperature dependence of the cell voltage of charged supercapacitors. Using a commercially available supercapacitor, we observed a thermal cell-voltage rise of around 0.6 mV K-1 over a temperature window of 0 degrees C to 65 degrees C. Within our theoretical model, this can be used to operate a Stirling-like charge-voltage cycle whose eff…
Anisotropy and memory during cage breaking events close to a wall
The slow dynamics in a glassy hard-sphere system is dominated by cage breaking events, i.e., rearrangements where a particle escapes from the cage formed by its neighboring particles. We study such events for an overdamped colloidal system by the means of Brownian dynamics simulations. While it is difficult to relate cage breaking events to structural mean field results in bulk, we show that the microscopic dynamics of particles close to a wall can be related to the anisotropic two-particle density. In particular, we study cage-breaking trajectories, mean forces on a tracked particle, and the impact of the history of trajectories. Based on our simulation results, we further construct two di…