Manipulation of Contact Angle Hysteresis at Electrified Ionic Liquid-Solid Interfaces.

Room-temperature ionic liquids (RTILs) are intriguing fluids that have drawn much attention in applications ranging from tribology and catalysis to energy storage. With strong electrostatic interaction between ions, their interfacial behaviors can be modulated by controlling energetics of the electrified interface. In this work, we report atomic-force-microscope measurements of contact angle hysteresis (CAH) of a circular contact line formed on a micron-sized fiber, which is coated with a thin layer of conductive film and intersects an RTIL-air interface. The measured CAH shows a distinct change by increasing the voltage U applied on the fiber surface. Molecular dynamics simulations were performed to illustrate variations of the solidlike layer in the RTIL adsorbed at the electrified interface. The integrated experiments and computations demonstrate a new mechanism to manipulate the CAH by rearrangement of interfacial layers of RTILs induced by the surface energetics.

Heterogeneous Nanostructures Cause Anomalous Diffusion in Lipid Monolayers.

The diffusion and mobility in biomembranes are crucial for various cell functions; however, the mechanisms involved in such processes remain ambiguous due to the complex membrane structures. Herein, we investigate how the heterogeneous nanostructures cause anomalous diffusion in dipalmitoylphosphatidylcholine (DPPC) monolayers. By identifying the existence of condensed nanodomains and clarifying their impact, our findings renew the understanding of the hydrodynamic description and the statistical feature of the diffusion in the monolayers. We find a universal characteristic of the multistage mean square displacement (MSD) with an intermediate crossover, signifying two membrane viscosities at different scales: the short-time scale describes the local fluidity and is independent of the nominal DPPC density, and the long-time scale represents the global continuous phase taking into account nanodomains and increases with DPPC density. The constant short-time viscosity reflects a dynamic equilibrium between the continuous fluid phase and the condensed nanodomains in the molecular scale. Notably, we observe an "anomalous yet Brownian" phenomenon exhibiting an unusual double-peaked displacement probability distribution (DPD), which is attributed to the net dipolar repulsive force from the heterogeneous nanodomains around the microdomains. The findings provide physical insights into the transport of membrane inclusions that underpin various biological functions and drug deliveries.

Non-monotonic variation of flow strength in nanochannels grafted with end-charged polyelectrolyte layers.

The electrokinetic transport of fluids, also called the electroosmotic flow (EOF), in micro/nanoscale devices occurs in promising applications such as electrokinetic energy conversion (EKEC) systems. Recently, EKEC systems grafted with end-charged polyelectrolyte (PE) layers (PELs) have been reported to exhibit higher efficiencies than those of intrinsic systems. Understanding the interplay between the end-charged PELs and electrical double layers (EDLs) on the EOF is crucial for designing highly efficient EKEC systems. The interplay between the end-charged PELs and EDLs on the strength of the EOF (V 0) is studied by explicitly modeling the EOF through nanochannels grafted with end-charged PELs using atomic simulations. The variation of V 0 is examined for nanochannels grafted with PELs at various separations (d = 3.5-0.4 nm) to cover various conformations of PEs, inlcuding mushroom, semi-dilute brushes, and concentrated brushes. We find that V 0 follows a non-monotonic variation as d decreases and this is correlated with the conformation of the PEs. Specifically, as d decreases, V 0 decreases first in the mushroom regime (d = 3.5-2.0 nm), and then V 0 increases in the concentrated brush regime (d = 0.75-0.4 nm). Navigated by the continuum Navier-Stokes-Brinkman model, the above observations are rationalized by the competition between the driving effect from the spatial shift of ions in EDLs and the drag effect from PELs. The insights obtained in this work are important to guide the design of highly efficient EKEC systems by grafting end-charged PELs onto channel surfaces.

Electric-Field-Driven Ion Emission from the Free Surface of Room Temperature Ionic Liquids.

Electric-field-driven ion emission from the free surface of a planar room-temperature ionic liquid (RTIL) film was studied by using molecular dynamics simulations. We calculated ion emission rate (je) as a function of the electric field normal to the RTIL/vacuum surface (En) and found that the logarithm of je over the charge density on the surface (σ) is proportional to En1/2, in agreement with classical ion evaporation theories. The composition of emitted ions includes monomers and dimers. It was found that the monomer has to move across two barriers before emission. The fraction of dimers was found to depend on the external field and ion-ion interactions. We further performed replica exchange molecular dynamics simulations and identified different metastable states of the emitting ion near the liquid film. Our results showed that En and molecular details of ion/surface determine the rate and composition of ion emission from RTIL/vacuum surfaces. Fundamental insights revealed in this study form the basis to improve ion evaporation theories and performance of electrospray applications ranging from space propulsion to nanomanufacturing.

Structure and dynamics of hydrodynamically interacting finite-size Brownian particles in a spherical cavity: Spheres and cylinders.

The structure and dynamics of confined suspensions of particles of arbitrary shape are of interest in multiple disciplines from biology to engineering. Theoretical studies are often limited by the complexity of long-range particle-particle and particle-wall forces, including many-body fluctuating hydrodynamic interactions. Here, we report a computational study on the diffusion of spherical and cylindrical particles confined in a spherical cavity. We rely on an immersed-boundary general geometry Ewald-like method to capture lubrication and long-range hydrodynamics and include appropriate non-slip conditions at the confining walls. A Chebyshev polynomial approximation is used to satisfy the fluctuation-dissipation theorem for the Brownian suspension. We explore how lubrication, long-range hydrodynamics, particle volume fraction, and shape affect the equilibrium structure and the diffusion of the particles. It is found that once the particle volume fraction is greater than 10%, the particles start to form layered aggregates that greatly influence particle dynamics. Hydrodynamic interactions strongly influence the particle diffusion by inducing spatially dependent short-time diffusion coefficients, stronger wall effects on the particle diffusion toward the walls, and a sub-diffusive regime-caused by crowding-in the long-time particle mobility. The level of asymmetry of the cylindrical particles considered here is enough to induce an orientational order in the layered structure, decreasing the diffusion rate and facilitating a transition to the crowded mobility regime at low particle concentrations. Our results offer fundamental insights into the diffusion and distribution of globular and fibrillar proteins inside cells.

Hydrodynamic Properties of Polymers Screening the Electrokinetic Flow: Insights from a Computational Study.

Understanding the hydrodynamic properties of polymeric coatings is crucial for the rational design of molecular transport involving polymeric surfaces and is relevant to drug delivery, sieving, molecular separations, etc. It has been found that the hydrodynamic radius of a polymer segment is an order of magnitude smaller than its physical size, but the origin of this effect does not seem to be well understood. Herein, we study the hydrodynamic properties of polymeric coatings by using molecular dynamics simulations, navigated by the continuous Navier-Stokes-Brinkman model. We confirm that the averaged hydrodynamic radius of a polymer bead is about one order of magnitude smaller than its physical radius, and, in addition, we show that it exhibits a strong dependence on the degree of polymerization. We relate this variation of the hydrodynamic radius to the structural properties and hydrodynamic shielding by surrounding polymer beads. This is done by separating the effects originating from near and far beads. For the near beads, shielding is mainly due to the two nearest beads (of the same polymer) and leads to about a 5-fold reduction in the hydrodynamic radius. Assuming the additivity of the hydrodynamic shielding by far beads, we suggest a simple model, which captures correctly the qualitative behaviour of the hydrodynamic radius with the degree of polymerization. The revealed shielding effects provide important insights relevant to the advanced modelling of hydrodynamic properties of polymeric coatings.

Evolutionary strategy for inverse charge measurements of dielectric particles.

We report a computational strategy to obtain the charges of individual dielectric particles from experimental observation of their interactions as a function of time. This strategy uses evolutionary optimization to minimize the difference between trajectories extracted from the experiment and simulated trajectories based on many-particle force fields. The force fields include both Coulombic interactions and dielectric polarization effects that arise due to particle-particle charge mismatch and particle-environment dielectric contrast. The strategy was applied to systems of free falling charged granular particles in a vacuum, where electrostatic interactions are the only driving forces that influence the particles' motion. We show that when the particles' initial positions and velocities are known, the optimizer requires only an initial and final particle configuration of a short trajectory in order to accurately infer the particles' charges; when the initial velocities are unknown and only the initial positions are given, the optimizer can learn from multiple frames along the trajectory to determine the particles' initial velocities and charges. While the results presented here offer a proof-of-concept demonstration of the proposed ideas, the proposed strategy could be extended to more complex systems of electrostatically charged granular matter.

SSAGES: Software Suite for Advanced General Ensemble Simulations.

Molecular simulation has emerged as an essential tool for modern-day research, but obtaining proper results and making reliable conclusions from simulations requires adequate sampling of the system under consideration. To this end, a variety of methods exist in the literature that can enhance sampling considerably, and increasingly sophisticated, effective algorithms continue to be developed at a rapid pace. Implementation of these techniques, however, can be challenging for experts and non-experts alike. There is a clear need for software that provides rapid, reliable, and easy access to a wide range of advanced sampling methods and that facilitates implementation of new techniques as they emerge. Here we present SSAGES, a publicly available Software Suite for Advanced General Ensemble Simulations designed to interface with multiple widely used molecular dynamics simulations packages. SSAGES allows facile application of a variety of enhanced sampling techniques-including adaptive biasing force, string methods, and forward flux sampling-that extract meaningful free energy and transition path data from all-atom and coarse-grained simulations. A noteworthy feature of SSAGES is a user-friendly framework that facilitates further development and implementation of new methods and collective variables. In this work, the use of SSAGES is illustrated in the context of simple representative applications involving distinct methods and different collective variables that are available in the current release of the suite. The code may be found at: https://github.com/MICCoM/SSAGES-public.

Parallel O(N) Stokes' solver towards scalable Brownian dynamics of hydrodynamically interacting objects in general geometries.

An efficient parallel Stokes' solver has been developed for complete description of hydrodynamic interactions between Brownian particles in bulk and confined geometries. A Langevin description of the particle dynamics is adopted, where the long-range interactions are included using a Green's function formalism. A scalable parallel computational approach is presented, where the general geometry Stokeslet is calculated following a matrix-free algorithm using the general geometry Ewald-like method. Our approach employs a highly efficient iterative finite-element Stokes' solver for the accurate treatment of long-range hydrodynamic interactions in arbitrary confined geometries. A combination of mid-point time integration of the Brownian stochastic differential equation, the parallel Stokes' solver, and a Chebyshev polynomial approximation for the fluctuation-dissipation theorem leads to an O(N) parallel algorithm. We illustrate the new algorithm in the context of the dynamics of confined polymer solutions under equilibrium and non-equilibrium conditions. The method is then extended to treat suspended finite size particles of arbitrary shape in any geometry using an immersed boundary approach.

Water in ionic liquids at electrified interfaces: the anatomy of electrosorption.

Complete removal of water from room-temperature ionic liquids is nearly impossible. For the electrochemical applications of ionic liquids, how water is distributed in the electrical double layers when the bulk liquids are not perfectly dry can potentially determine whether key advantages of ionic liquids, such as a wide electrochemical window, can be harnessed in practical systems. In this paper, we study the adsorption of water on electrode surfaces in contact with humid, imidazolium-based ionic liquids using molecular dynamics simulations. The results revealed that water molecules tend to accumulate within sub-nanometer distance from charged electrodes. At low amount of water in the bulk, the distributions of ions and of electrostatic potential in the double layer are affected weakly by the presence of water, but the spatial distribution of water molecules is strongly dependent on both. The preferential positions of water molecules in double layers are determined by the balance of several factors: the tendency to follow the positions of the maximal absolute value of the electrical field, the association with their ionic surroundings, and the propensity to settle at positions where more free space is available. The balance between these factors changes with charging the electrode, but the adsorption of water generally increases with voltage. The ion specificity of water electrosorption is manifested in the stronger presence of water near positive electrodes (where anions are the counterions) than near negative electrodes (where cations are counterions). These predictions await experimental verification.

Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions.

We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.