Description of hard-sphere crystals and crystal-fluid interfaces: a comparison between density functional approaches...

In materials science the phase-field crystal approach has become popular to model crystallization processes. Phase-field crystal models are in essence Landau-Ginzburg-type models, which should be derivable from the underlying microscopic description of the system in question. We present a study on classical density functional theory in three stages of approximation leading to a specific phase-field crystal model, and we discuss the limits of applicability of the models that result from these approximations. As a test system we have chosen the three-dimensional suspension of monodisperse hard spheres. The levels of density functional theory that we discuss are fundamental measure theory, a second-order Taylor expansion thereof, and a minimal phase-field crystal model. We have computed coexistence densities, vacancy concentrations in the crystalline phase, interfacial tensions, and interfacial order parameter profiles, and we compare these quantities to simulation results. We also suggest a procedure to fit the free parameters of the phase-field crystal model. Thereby it turns out that the order parameter of the phase-field crystal model is more consistent with a smeared density field (shifted and rescaled) than with the shifted and rescaled density itself. In brief, we conclude that fundamental measure theory is very accurate and can serve as a benchmark for the other theories. Taylor expansion strongly affects free energies, surface tensions, and vacancy concentrations. Furthermore it is phenomenologically misleading to interpret the phase-field crystal model as stemming directly from Taylor-expanded density functional theory.