Thermodynamic properties of quasi-one-dimensional fluids

Abstract

We calculate thermodynamic and structural quantities of a fluid of hard spheres of diameter σ in a quasi-one-dimensional pore with accessible pore width W smaller than σ by applying a perturbative method worked out earlier for a confined fluid in a slit pore [Franosch et al. Phys. Rev. Lett. 109, 240601 (2012)]. In a first step, we prove that the thermodynamic and a certain class of structural quantities of the hard-sphere fluid in the pore can be obtained from a purely one-dimensional fluid of rods of length σ with a central hard core of size σW=σ2−W2 and a soft part at both ends of length (σ − σW)/2. These rods interact via effective k-body potentials veff(k) (k ≥ 2). The two- and the three-body potential will be calculated explicitly. In a second step, the free energy of this effective one-dimensional fluid is calculated up to leading order in (W/σ)2. Explicit results for, e.g., the perpendicular pressure, surface tension, and the density profile as a function of density, temperature, and pore width are presented and partly compared with results from Monte-Carlo simulations and standard virial expansions. Despite the perturbative character of our approach, it encompasses the singularity of the thermodynamic quantities at the jamming transition point.