Conceptual aspects of line tensions

We analyze two representative systems containing a three-phase-contact line: a liquid lens at a fluid--fluid interface and a liquid drop in contact with a gas phase residing on a solid substrate. We discuss to which extent the decomposition of the grand canonical free energy of such systems into volume, surface, and line contributions is unique in spite of the freedom one has in positioning the Gibbs dividing interfaces. In the case of a lens it is found that the line tension is independent of arbitrary choices of the Gibbs dividing interfaces. In the case of a drop, however, one arrives at two different possible definitions of the line tension. One of them corresponds seamlessly to that applicable to the lens. The line tension defined this way turns out to be independent of choices of the Gibbs dividing interfaces. In the case of the second definition,however, the line tension does depend on the choice of the Gibbs dividing interfaces. We provide equations for the equilibrium contact angles which are form-invariant with respect to notional shifts of dividing interfaces which only change the description of the system. Conceptual consistency requires to introduce additional stiffness constants attributed to the line. We show how these constants transform as a function of the relative displacements of the dividing interfaces. The dependences of the contact angles on lens or drop volumes do not render the line tension alone but a combination of the line tension, the Tolman length, and the stiffness constants of the line.Comment: 34 pages, 9 figure

Microcanonical Determination of the Interface Tension of Flat and Curved Interfaces from Monte Carlo Simulations

The investigation of phase coexistence in systems with multi-component order parameters in finite systems is discussed, and as a generic example, Monte Carlo simulations of the two-dimensional q-state Potts model (q=30) on LxL square lattices (40<=L<=100) are presented. It is shown that the microcanonical ensemble is well-suited both to find the precise location of the first order phase transition and to obtain an accurate estimate for the interfacial free energy between coexisting ordered and disordered phases. For this purpose, a microcanonical version of the heatbath algorithm is implemented. The finite size behaviour of the loop in the curve describing the inverse temperature versus energy density is discussed, emphasizing that the extrema do not have the meaning of van der Waals-like "spinodal points" separating metastable from unstable states, but rather describe the onset of heterophase states: droplet/bubble evaporation/condensation transitions. Thus all parts of these loops, including the parts that correspond to a negative specific heat, describe phase coexistence in full thermal equilibrium. However, the estimates for the curvature-dependent interface tension of the droplets and bubbles suffer from unexpected and unexplained large finite size effects which need further study.Comment: submitted to special issue "Liquid Matter" of Journal of Physics C: Condensed Matter on occasion of the 8th Liquid Matter Conference held Sept. 6-10, 2011 in Vienna, Austri

Phase-field-crystal models for condensed matter dynamics on atomic length and diffusive time scales: an overview

Here, we review the basic concepts and applications of the phase-field-crystal (PFC) method, which is one of the latest simulation methodologies in materials science for problems, where atomic- and microscales are tightly coupled. The PFC method operates on atomic length and diffusive time scales, and thus constitutes a computationally efficient alternative to molecular simulation methods. Its intense development in materials science started fairly recently following the work by Elder et al. [Phys. Rev. Lett. 88 (2002), p. 245701]. Since these initial studies, dynamical density functional theory and thermodynamic concepts have been linked to the PFC approach to serve as further theoretical fundaments for the latter. In this review, we summarize these methodological development steps as well as the most important applications of the PFC method with a special focus on the interaction of development steps taken in hard and soft matter physics, respectively. Doing so, we hope to present today's state of the art in PFC modelling as well as the potential, which might still arise from this method in physics and materials science in the nearby future.Comment: 95 pages, 48 figure

Magnetization of ferrofluids with dipolar interactions - a Born--Mayer expansion

For ferrofluids that are described by a system of hard spheres interacting via dipolar forces we evaluate the magnetization as a function of the internal magnetic field with a Born--Mayer technique and an expansion in the dipolar coupling strength. Two different approximations are presented for the magnetization considering different contributions to a series expansion in terms of the volume fraction of the particles and the dipolar coupling strength.Comment: 19 pages, 11 figures submitted to PR

Local Anisotropy of Fluids using Minkowski Tensors

Statistics of the free volume available to individual particles have previously been studied for simple and complex fluids, granular matter, amorphous solids, and structural glasses. Minkowski tensors provide a set of shape measures that are based on strong mathematical theorems and easily computed for polygonal and polyhedral bodies such as free volume cells (Voronoi cells). They characterize the local structure beyond the two-point correlation function and are suitable to define indices $0\leq \beta_\nu^{a,b}\leq 1$ of local anisotropy. Here, we analyze the statistics of Minkowski tensors for configurations of simple liquid models, including the ideal gas (Poisson point process), the hard disks and hard spheres ensemble, and the Lennard-Jones fluid. We show that Minkowski tensors provide a robust characterization of local anisotropy, which ranges from $\beta_\nu^{a,b}\approx 0.3$ for vapor phases to $\beta_\nu^{a,b}\to 1$ for ordered solids. We find that for fluids, local anisotropy decreases monotonously with increasing free volume and randomness of particle positions. Furthermore, the local anisotropy indices $\beta_\nu^{a,b}$ are sensitive to structural transitions in these simple fluids, as has been previously shown in granular systems for the transition from loose to jammed bead packs

NaCl nucleation from brine in seeded simulations: Sources of uncertainty in rate estimates

This work reexamines seeded simulation results for NaCl nucleation from a supersaturated aqueous solution at 298.15 K and 1 bar pressure. We present a linear regression approach for analyzing seeded simulation data that provides both nucleation rates and uncertainty estimates. Our results show that rates obtained from seeded simulations rely critically on a precise driving force for the model system. The driving force vs. solute concentration curve need not exactly reproduce that of the real system, but it should accurately describe the thermodynamic properties of the model system. We also show that rate estimates depend strongly on the nucleus size metric. We show that the rate estimates systematically increase as more stringent local order parameters are used to count members of a cluster and provide tentative suggestions for appropriate clustering criteria