Generalization of the Wall theorem to out-of-equilibrium conditions.

The well-known Wall theorem states a simple and precise relation among temperature, pressure, and density of a fluid at contact with a confining hard wall in thermodynamic equilibrium. In this Communication, we develop an extension of the Wall theorem to out-of-equilibrium conditions, providing an exact relation between pressure, density, and temperature at the wall, valid for strong nonequilibrium situations. We derive analytically this nonequilibrium Wall theorem for stationary states and validate it with nonequilibrium event-driven molecular-dynamics simulations.

Properties of the hard-sphere fluid at a planar wall using virial series and molecular-dynamics simulation.

We study the hard-sphere fluid in contact with a planar hard wall. By combining the inhomogeneous virial series with simulation results, we achieve a new benchmark of accuracy for the calculation of surface thermodynamics properties such as surface adsorption Γ and the surface free energy (or surface tension), γ. We briefly introduce the problem of choosing a position for the dividing surface and avoid it by proposing the use of alternative functions to Γ and γ that are independent of the adopted frame of reference.

Virial series for inhomogeneous fluids applied to the Lennard-Jones wall-fluid surface tension at planar and curved walls.

We formulate a straightforward scheme of statistical mechanics for inhomogeneous systems that includes the virial series in powers of the activity for the grand free energy and density distributions. There, cluster integrals formulated for inhomogeneous systems play a main role. We center on second order terms that were analyzed in the case of hard-wall confinement, focusing in planar, spherical, and cylindrical walls.

Structure, thermodynamic properties, and phase diagrams of few colloids confined in a spherical pore.

We study a system of few colloids confined in a small spherical cavity with event driven molecular dynamics simulations in the canonical ensemble. The colloidal particles interact through a short range square-well potential that takes into account the basic elements of attraction and excluded-volume repulsion of the interaction among colloids. We analyze the structural and thermodynamic properties of this few-body confined system in the framework of inhomogeneous fluids theory.