Two hard spheres in a pore: Exact Statistical Mechanics for different shaped cavities

TL;DR

This paper provides an exact statistical mechanics analysis of two hard spheres confined in various shaped pores, deriving explicit thermodynamic properties and exploring geometric influences on system behavior.

Contribution

It introduces a framework for exact thermodynamic analysis of few-particle systems in arbitrary geometries using graph representations and thermodynamic measures.

Findings

Exact partition functions for three new pore geometries

Analytic expressions for pressure, surface tension, and line tension

Identification of geometric features influencing thermodynamic properties

Abstract

The Partition function of two Hard Spheres in a Hard Wall Pore is studied appealing to a graph representation. The exact evaluation of the canonical partition function, and the one-body distribution function, in three different shaped pores are achieved. The analyzed simple geometries are the cuboidal, cylindrical and ellipsoidal cavities. Results have been compared with two previously studied geometries, the spherical pore and the spherical pore with a hard core. The search of common features in the analytic structure of the partition functions in terms of their length parameters and their volumes, surface area, edges length and curvatures is addressed too. A general framework for the exact thermodynamic analysis of systems with few and many particles in terms of a set of thermodynamic measures is discussed. We found that an exact thermodynamic description is feasible based in the adoption of an adequate set of measures and the search of the free energy dependence on the adopted measure set. A relation similar to the Laplace equation for the fluid-vapor interface is obtained which express the equilibrium between magnitudes that in extended systems are intensive variables. This exact description is applied to study the thermodynamic behavior of the two Hard Spheres in a Hard Wall Pore for the analyzed different geometries. We obtain analytically the external work, the pressure on the wall, the pressure in the homogeneous zone, the wall-fluid surface tension, the line tension and other similar properties.