Pressure Profile for an Associating Lennard-Jones Fluid Confined in a Spherical Cavity.

Abstract

We present the pressure tensor of an associating Lennard-Jones (LJ) fluid confined in a spherical cavity of hard wall, where a high-order density correlation has been taken into account. To give the two-body association potential for calculating the pressure tensor, an angle-average of site-site attraction over all orientations of two particles is performed. Furthermore, the classical density functional theory is employed to obtain the density profile of the confined fluid, by which the normal and tangential pressure profiles are illustrated under various conditions to show the dependence of the pressure tensor on the association strength, number of associating sites, radius of cavity, and bulk density. As an application, the corresponding surface tension is calculated. It is shown that under a strong association interaction (both association strength and the number of associating sites are large), the pressure profiles are depleted from the wall of the cavity instead of the oscillatory behavior under a weak association interaction. Such a tendency is mainly determined by the competition between association interaction and excluded volume interaction. Therefore, the aggregation state and related properties of an associating LJ fluid within a confinement of nanoscale can be efficiently regulated by the association interaction.