Virial series expansion and Monte Carlo studies of equation of state for hard spheres in narrow cylindrical pores.

Abstract

In this paper, the virial series expansion and constant pressure Monte Carlo method are used to study the longitudinal pressure equation of state for hard spheres in narrow cylindrical pores. We invoke dimensional reduction and map the model into an effective one-dimensional fluid model with interacting internal degrees of freedom. The one-dimensional model is extensive. The Euler relation holds, and longitudinal pressure can be probed with the standard virial series expansion method. Virial coefficients B_{2} and B_{3} were obtained analytically, and numerical quadrature was used for B_{4}. A range of narrow pore widths (2R_{p}), R_{p}<(sqrt[3]+2)/4=0.9330... (in units of the hard sphere diameter) was used, corresponding to fluids in the important single-file formations. We have also computed the virial pressure series coefficients B_{2}^{'}, B_{3}^{'}, and B_{4}^{'} to compare a truncated virial pressure series equation of state with accurate constant pressure Monte Carlo data. We find very good agreement for a wide range of pressures for narrow pores. These results contribute toward increasing the rather limited understanding of virial coefficients and the equation of state of hard sphere fluids in narrow cylindrical pores.