Systems of highly degenerate ordered or frozen state may exhibit inverse melting (reversible crystallization upon heating) or inverse freezing (reversible glass transition upon heating). This phenomenon is reviewed, and a list of experimental demonstrations and theoretical models is presented. A simple spin model for inverse melting is introduced and solved analytically for infinite range, constant paramagnetic exchange interaction. The random exchange analogue of this model yields inverse freezing, as implied by the analytic solution based on the replica trick. The qualitative features of this system (generalized Blume-Capel spin model) are shown to resemble a large class of inverse melting phenomena. The appearance of inverse melting is related to an exact rescaling of one of the interaction parameters that measures the entropy of the system. For the case of almost degenerate spin states, perturbative expansion is presented, and the first three terms correspond to the empiric formula for the Flory-Huggins $\chi$ parameter in the theory of polymer melts. The possible microscopic origin of this $\chi$ parameter and the limitations of the Flory-Huggins theory where the state degeneracy is associated with the different conformations of a single polymer or with the spatial structures of two interacting molecules are discussed.

• Received 22 February 2005

DOI:https://doi.org/10.1103/PhysRevE.72.046107