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.

The crystallization of a metastable melt is one of the most important non-equilibrium phenomena in condensed matter physics, and hard sphere colloidal model systems have been used for several decades to investigate this process by experimental observation and computer simulation. Nevertheless, there is still an unexplained discrepancy between the simulation data and experimental nucleation rate densities. In this paper we examine the nucleation process in hard spheres using molecular dynamics and Monte Carlo simulation. We show that the crystallization process is mediated by precursors of low orientational bond-order and that our simulation data fairly match the experimental data sets.

Entropy production is one of the most important characteristics of non-equilibrium steady states.We study here the steady-state entropy production, both at short times as well as in the long-time limit, of two important classes of non-equilibrium systems: transport systems and reaction-diffusion systems. The usefulness of the mean entropy production rate and of the large deviation function of the entropy production for characterizing non-equilibrium steady states of interacting manybody systems is discussed. We show that the large deviation function displays a kink-like feature at zero entropy production that is similar to that observed for a single particle driven along a periodic potential. This kink is a direct consequence of the detailed fluctuation theorem fulfilled by the probability distribution of the entropy production and is therefore a generic feature of the corresponding large deviation function.

We consider the distribution P (φ) of the Hatano-Sasa entropy, φ, in reversible and irreversible processes, finding that the Crook's relation for the ratio of the pdf's of the forward and backward processes, P F (φ)/P R (−φ) = e φ , is satisfied not only for reversible, but also for irreversible processes, in general, in the adiabatic limit of "slow processes." Focusing on systems with a finite set of discrete states (and no absorbing states), we observe that two-state systems always fulfill detailed balance, and obey Crook's relation. We also identify a wide class of systems, with more than two states, that can be "coarse-grained" into two-state systems and obey Crook's relation despite their irreversibility and violation of detailed balance. We verify these results in selected cases numerically.