Thermodynamics of dipolar hard spheres with low-to-intermediate coupling constants

The thermodynamic properties of the dipolar hard-sphere fluid are studied using theory and simulation. A new theory is derived using a convenient mathematical approximation for the Helmholtz free energy relative to that for the hard-sphere fluid. The approximation is designed to give the correct low-density virial expansion. New theoretical and numerical results for the fourth virial coefficient are given. Predictions of thermodynamic functions for dipolar coupling constants lambda = 1 and 2 show excellent agreement with simulation results, even at the highest value of the particle volume fraction phi. For higher values of lambda, there are deviations at high volume fractions, but the correct low-density behavior is retained. The theory is compared critically against the established thermodynamic perturbation theory; it gives significant improvements at low densities and is more convenient in terms of the required numerics. Dipolar hard spheres provide a basic model for ferrofluids, and the theory is accurate for typical experimental parameters. lambda less than or similar to 2 and phi less than or similar to 0.1. This is demonstrated explicitly by fitting osmotic equations of state for real ferrofluids measured recently by analytical centrifugation.