Impact of surface roughness on diffusion of confined fluids

Using event-driven molecular dynamics simulations, we quantify how the self diffusivity of confined hard-sphere fluids depends on the nature of the confining boundaries. We explore systems with featureless confining boundaries that treat particle-boundary collisions in different ways and also various types of physically (i.e., geometrically) rough boundaries. We show that, for moderately dense fluids, the ratio of the self diffusivity of a rough wall system to that of an appropriate smooth-wall reference system is a linear function of the reciprocal wall separation, with the slope depending on the nature of the roughness. We also discuss some simple practical ways to use this information to predict confined hard-sphere fluid behavior in different rough-wall systems.     

Tuning density profiles and mobility of inhomogeneous fluids

Density profiles are the most common measure of inhomogeneous structure in confined fluids, but their connection to transport coefficients is poorly understood. We explore via simulation how tuning particle-wall interactions to flatten or enhance the particle layering of a model confined fluid impacts its self-diffusivity, viscosity, and entropy. Interestingly, interactions that eliminate particle layering significantly reduce confined fluid mobility, whereas those that enhance layering can have the opposite effect. Excess entropy helps to understand and predict these trends.     

Model for the free-volume distributions of equilibrium fluids

We introduce and test via molecular simulation a simple model for predicting the manner in which interparticle interactions and thermodynamic conditions impact the single-particle free-volume distributions of equilibrium fluids. The model suggests a scaling relationship for the density-dependent behavior of the hard-sphere system. It also predicts how the second virial coefficients of fluids with short-range attractions affect their free-volume distributions.     

Volatile diffusional character of cytoplasm

The fluctuating extracellular environment of microbial organisms influences diffusional mobility of macromolecules in the cytoplasm. This effect may be measured experimentally on the one hand by directly tracking the trajectories of individual macromolecules. We discuss how it may also be indirectly estimated from fluctuations in the amount of cytoplasmic water and from the varying patterns of protein expression seen in 2d gel analysis.     

Osmotic virial coefficients for model protein and colloidal solutions: importance of ensemble constraints in the analysis of light scattering data

Protein-protein interactions in solution may be quantified by the osmotic second virial coefficient (OSVC), which can be measured by various experimental techniques including light scattering. Analysis of Rayleigh light scattering measurements from such experiments requires identification of a scattering volume and the thermodynamic constraints imposed on that volume, i.e., the statistical mechanical ensemble in which light scattering occurs. Depending on the set of constraints imposed on the scattering volume, one can obtain either an apparent OSVC, A(2,app), or the true thermodynamic OSVC, B(22)(osm), that is rigorously defined in solution theory [M. A. Blanco, E. Sahin, Y. Li, and C. J. Roberts, J. Chem. Phys. 134, 225103 (2011)]. However, it is unclear to what extent A(2,app) and B(22)(osm) differ, which may have implications on the physical interpretation of OSVC measurements from light scattering experiments. In this paper, we use the multicomponent hard-sphere model and a well-known equation of state to directly compare A(2,app) and B(22)(osm). Our results from the hard-sphere equation of state indicate that A(2,app) underestimates B(22)(osm), but in a systematic manner that may be explained using fundamental thermodynamic expressions for the two OSVCs. The difference between A(2,app) and B(22)(osm) may be quantitatively significant, but may also be obscured in experimental application by statistical uncertainty or non-steric interactions. Consequently, the two OSVCs that arise in the analysis of light scattering measurements do formally differ, but in a manner that may not be detectable in actual application.     

Free volumes and the anomalous self-diffusivity of attractive colloids

Free volume theories for the dynamics of dense fluids commonly assume (i) that diffusivity increases with average free volume per particle and (ii) that the size distribution of free volumes can be approximated by that of an equivalent hard-sphere reference system. We use molecular simulations to demonstrate that these assumptions break down when one considers concentrated suspensions of particles with short-range attractions. In these systems, self-diffusivity shows nonmonotonic dependencies on both average free volume and the strength of the interparticle attraction. Moreover, when interparticle attractions are strong, the shape of the free volume distribution is qualitatively different than that of the corresponding hard-sphere reference fluid. We propose a conceptual revision to the traditional free volume perspective that takes into account both the size distribution and the persistence time of the free volumes, and we demonstrate that it can qualitatively capture the disparate behaviors of a model fluid with short-range attractions and its hard-sphere reference fluid.     

Residual multiparticle entropy does not generally change sign near freezing

The residual multiparticle entropy (RMPE) of two- and three-dimensional fluids changes sign near the freezing line, providing a quasiuniversal "one-phase" rule for the location of the liquid-solid transition. We present new simulation results for d-dimensional hard-sphere fluids (d=1-5) which show, however, that this freezing criterion fails in other spatial dimensions. The results also call into question the idea that a change in sign of the RMPE implies the emergence of a new kind of local structural order in the fluid.