2 - The freezing transition

Summary

In this chapter we discuss a theory for the freezing of an isotropic liquid into a crystalline solid state with long-range order. The transformation is a first-order phase transition with finite latent heat absorbed in the process. We focus on a first-principles orderparameter theory of freezing that originated from the pioneering work of Ramakrishnan and Yussouff (1979). The theory approaches the problem from the liquid side and views the crystal as a liquid with grossly inhomogeneous density characterized by a lower symmetry of the corresponding lattice. This is in contrast to description of the crystal in terms of phonons. The crucial quantity characterizing the physical state of the system in this non-phonon-based model is the average one-particle density function n(x). The thermodynamic description of either phase involves a corresponding extremum principle for a relevant potential. The latter, obtained as a functional of the one-particle density n(x) and the stable thermodynamic state of the system, is identified by the corresponding density required for invoking the extremum principle. This approach, which is generally referred to as the density-functional theory (DFT) of freezing (Haymet, 1987; Baus, 1987, 1990; Singh, 1991; Löwen, 1994; Ashcroft 1996), has been improved over the years and successfully applied for the study of liquid-to-crystal transitions in various simple liquids, the solid–liquid interface, two-dimensional systems, metastable glassy states, etc. For applications of density-functional methods in statistical mechanics there exist general reviews (Evans, 1979; Henderson, 1992).