Fluids confined in wedges and by edges: virial series for the line-thermodynamic properties of hard spheres

TL;DR

This paper analytically investigates the thermodynamic properties of hard sphere fluids confined in wedges and by edges, deriving expressions for cluster integrals and exploring effects of vessel shape on low-density behavior.

Contribution

It provides the first analytical study of the second cluster integral for confined hard sphere fluids in wedge and edge geometries, including corrugated walls.

Findings

Analytic expression for the second cluster integral as a function of dihedral angle.

Unified approach to wedges and edges in confined fluids.

Insights into shape-dependent low-density thermodynamics.

Abstract

This work is devoted to analyze the relation between the thermodynamic properties of a confined fluid and the shape of its confining vessel. Recently, new insights in this topic were found through the study of cluster integrals for inhomogeneous fluids, that revealed the dependence on the vessel shape of the low density behavior of the system. Here, the statistical mechanics and thermodynamics of fluids confined in wedges or by edges is revisited, focusing on their cluster integrals. In particular, the well known hard sphere fluid, which was not studied in this framework so far, is analyzed under confinement and its thermodynamic properties are analytically studied up to order two in the density. Furthermore, the analysis is extended to the confinement produced by a corrugated wall. These results rely on the obtained analytic expression for the second cluster integral of the confined hard sphere system as a function of the opening dihedral angle $0<\beta<2\pi$. It enables a unified approach to both wedges and edges.