Direct calculation of interfacial tensions from computer simulation: Results for freely jointed tangent hard sphere chains

We develop a methodology for the calculation of surface free energies based on the probability distribution of a wandering interface. Using a simple extension of the NpT sampling, we allow the interface area to randomly probe the available space and evaluate the surface free energy from histogram analysis and the corresponding average. The method is suitable for studying systems with either continuous or discontinuous potentials, as it does not require explicit evaluation of the virial. The proposed algorithm is compared with known results for the surface tension of Lennard--Jones and Square Well fluid, as well as for the interface tension of a bead--spring polymer model and good agreement is found. We also calculate interfacial tensions of freely jointed tangent hard sphere chains on athermal walls for a wide range of chain lengths and densities. The results are compared with three different theoretical approaches, Scaled Particle Theory, the Yu and Wu density functional theory and an analytical approximation based on the latter approach. Whereas SPT only yields qualitative results, the last two approaches are found to yield very good agreement with simulations.Comment: 20 pages, 6 figures, Phys. Rev. E in press

Surface tension of electrolytes: Hydrophilic and hydrophobic ions near an interface

We calculate the ion distributions around an interface in fluid mixtures of highly polar and less polar fluids (water and oil) for two and three ion species. We take into account the solvation and image interactions between ions and solvent. We show that hydrophilic and hydrophobic ions tend to undergo a microphase separation at an interface, giving rise to an enlarged electric double layer. We also derive a general expression for the surface tension of electrolyte systems, which contains a negative electrostatic contribution proportional to the square root of the bulk salt density. The amplitude of this square-root term is small for hydrophilic ion pairs, but is much increased for hydrophilic and hydrophobic ion pairs. For three ion species including hydrophilic and hydrophobic ions, we calculate the ion distributions to explain those obtained by x-ray reflectivity measurements.Comment: 8 figure

Role of the first coordination shell in determining the equilibrium structure and dynamics of simple liquids

The traditional view that the physical properties of a simple liquid are determined primarily by its repulsive forces was recently challenged by Berthier and Tarjus, who showed that in some cases ignoring the attractions leads to large errors in the dynamics [L. Berthier and G. Tarjus, Phys. Rev. Lett. 103, 170601 (2009); J. Chem. Phys. 134, 214503 (2011)]. We present simulations of the standard Lennard-Jones liquid at several condensed-fluid state points, including a fairly low density state and a very high density state, as well as simulations of the Kob-Andersen binary Lennard-Jones mixture at several temperatures. By varying the range of the forces, results for the thermodynamics, dynamics, and structure show that the determining factor for getting the correct statics and dynamics is not whether or not the attractive forces {\it per se} are included in the simulations. What matters is whether or not interactions are included from all particles within the first coordination shell (FCS) - the attractive forces can thus be ignored, but only at extremely high densities. The recognition of the importance of a local shell in condensed fluids goes back to van der Waals; our results confirm this idea and thereby the basic picture of the old hole- and cell theories for simple condensed fluids

Viscous coalescence of droplets: a Lattice Boltzmann study

The coalescence of two resting liquid droplets in a saturated vapor phase is investigated by Lattice Boltzmann simulations in two and three dimensions. We find that, in the viscous regime, the bridge radius obeys a t^{1/2}-scaling law in time with the characteristic time scale given by the viscous time. Our results differ significantly from the predictions of existing analytical theories of viscous coalescence as well as from experimental observations. While the underlying reason for these deviations is presently unknown, a simple scaling argument is given that describes our results well.Comment: 12 pages, 10 figures; as published in Phys. Fluid

Non-Equilibrium Surface Tension of the Vapour-Liquid Interface of Active Lennard-Jones Particles

We study a three-dimensional system of self-propelled Brownian particles interacting via the Lennard-Jones potential. Using Brownian Dynamics simulations in an elongated simulation box, we investigate the steady states of vapour-liquid phase coexistence of active Lennard-Jones particles with planar interfaces. We measure the normal and tangential components of the pressure tensor along the direction perpendicular to the interface and verify mechanical equilibrium of the two coexisting phases. In addition, we determine the non-equilibrium interfacial tension by integrating the difference of the normal and tangential component of the pressure tensor, and show that the surface tension as a function of strength of particle attractions is well-fitted by simple power laws. Finally, we measure the interfacial stiffness using capillary wave theory and the equipartition theorem, and find a simple linear relation between surface tension and interfacial stiffness with a proportionality constant characterized by an effective temperature.Comment: 12 pages, 5 figures (Corrected typos and References

Solvent-free coarse-grained lipid model for large-scale simulations

A coarse-grained molecular model, which consists of a spherical particle and an orientation vector, is proposed to simulate lipid membrane on a large length scale. The solvent is implicitly represented by an effective attractive interaction between particles. A bilayer structure is formed by orientation-dependent (tilt and bending) potentials. In this model, the membrane properties (bending rigidity, line tension of membrane edge, area compression modulus, lateral diffusion coefficient, and flip-flop rate) can be varied over broad ranges. The stability of the bilayer membrane is investigated via droplet-vesicle transition. The rupture of the bilayer and worm-like micelle formation can be induced by an increase in the spontaneous curvature of the monolayer membrane.Comment: 13 pages, 19 figure

Capillary Waves in a Colloid-Polymer Interface

The structure and the statistical fluctuations of interfaces between coexisting phases in the Asakura-Oosawa (AO) model for a colloid--polymer mixture are analyzed by extensive Monte Carlo simulations. We make use of a recently developed grand canonical cluster move with an additional constraint stabilizing the existence of two interfaces in the (rectangular) box that is simulated. Choosing very large systems, of size LxLxD with L=60 and D=120, measured in units of the colloid radius, the spectrum of capillary wave-type interfacial excitations is analyzed in detail. The local position of the interface is defined in terms of a (local) Gibbs surface concept. For small wavevectors capillary wave theory is verified quantitatively, while for larger wavevectors pronounced deviations show up. For wavevectors that correspond to the typical distance between colloids in the colloid-rich phase, the interfacial fluctuations exhibit the same structure as observed in the bulk structure factor. When one analyzes the data in terms of the concept of a wavevector-dependent interfacial tension, a monotonous decrease of this quantity with increasing wavevector is found. Limitations of our analysis are critically discussed.Comment: 12 pages, 15 figure

Description of the fluctuating colloid-polymer interface

To describe the full spectrum of surface fluctuations of the interface between phase-separated colloid-polymer mixtures from low scattering vector q (classical capillary wave theory) to high q (bulk-like fluctuations), one must take account of the interface's bending rigidity. We find that the bending rigidity is negative and that on approach to the critical point it vanishes proportionally to the interfacial tension. Both features are in agreement with Monte Carlo simulations.Comment: 5 pages, 3 figures, 1 table. Accepted for publication in Phys. Rev. Let

The Search for Signatures Of Transient Mass Loss in Active Stars

The habitability of an exoplanet depends on many factors. One such factor is the impact of stellar eruptive events on nearby exoplanets. Currently this is poorly constrained due to heavy reliance on solar scaling relationships and a lack of experimental evidence. Potential impacts of Coronal Mass Ejections (CMEs), which are a large eruption of magnetic field and plasma from a star, are space weather and atmospheric stripping. A method for observing CMEs as they travel though the stellar atmosphere is the type II radio burst, and the new LOw Frequency ARray (LOFAR) provides a means for detection. We report on 15 hours of observation of YZ Canis Minoris (YZ CMi), a nearby M dwarf flare star, taken in LOFAR's beam-formed observation mode for the purposes of measuring transient frequency-dependent low frequency radio emission. The observations utilized Low-Band Antenna (10-90 MHz) or High-Band Antenna (110-190 MHz) for five three-hour observation periods. In this data set, there were no confirmed type II events in this frequency range. We explore the range of parameter space for type II bursts constrained by our observations Assuming the rate of shocks is a lower limit to the rate at which CMEs occur, no detections in a total of 15 hours of observation places a limit of $\nu_{type II} < 0.0667$ shocks/hr $\leq \nu_{CME}$ for YZ CMi due to the stochastic nature of the events and limits of observational sensitivity. We propose a methodology to interpret jointly observed flares and CMEs which will provide greater constraints to CMEs and test the applicability of solar scaling relations

Undulation instabilities in the meniscus of smectic membranes

Using optical microscopy, phase shifting interferometry and atomic force microscopy, we demonstrate the existence of undulated structures in the meniscus of ferroelectric smectic-C* films. The meniscus is characterized by a periodic undulation of the smectic-air interface, which manifests itself in a striped pattern. The instability disappears in the untilted smectic-A phase. The modulation amplitude and wavelength both depend on meniscus thickness. We study the temperature evolution of the structure and propose a simple model that accounts for the observed undulations.Comment: Submitted to PR