Thermodynamic and structural properties of finely discretized on-lattice hard-sphere fluids: Virial coefficients, free energies, and direct correlation functions.
Using both molecular simulation and theory, we examine fluid-phase thermodynamic and structural properties of on-lattice hard-sphere fluids. Our purpose in this work is to provide reference data for on-lattice density functional theories [D. W. Siderius and L. D. Gelb, Langmuir 25, 1296 (2009)] and related perturbation theories. In this model, hard spheres are located at sites on a finely discretized cubic lattice where the spacing between lattice sites is between one-tenth and one-third the hard-sphere diameter. We calculate exactly the second, third, and fourth virial coefficients as functions of the lattice spacing. Via Monte Carlo simulation, we measure the excess chemical potential as a function of density for several lattice spacings. These results are then parametrized with a convenient functional form and can immediately be used in on-lattice density functional theories. Of particular interest is to identify those lattice spacings that yield properties similar to those of the off-lattice fluid. We find that the properties of the on-lattice fluid are strongly dependent on lattice spacing, generally approaching those of the off-lattice fluid with increasing lattice resolution, but not smoothly. These observations are consistent with results for larger lattice spacings [A. Z. Panagiotopoulos, J. Chem. Phys. 123, 104504 (2005)]. Certain lattice spacings are found to yield fluid properties in particularly good agreement with the off-lattice fluid. We also find that the agreement of many different on- and off-lattice hard-sphere fluid properties is predicted quite well by that of the virial coefficients, suggesting that they may be used to identify favorable lattice spacings. The direct correlation function at a few lattice spacings and a single density is obtained from simulation. The on-lattice fluid is structurally anisotropic, exhibiting spherical asymmetry in correlation functions. Interestingly, the anisotropies are properly captured in the Percus-Yevick-based calculation of the direct correlation function. Lastly, we speculate on the possibility of obtaining a theoretical equation of state of the on-lattice hard-sphere fluid computed in the Percus-Yevick approximation.
Siderius
Daniel W
DW
Department of Chemistry and Center for Materials Innovation, Washington University in St. Louis, St. Louis, Missouri 63130, USA.
Gelb
Lev D
LD