Inverse melting and inverse freezing: a spin model

TL;DR

This paper reviews inverse melting and freezing phenomena, introduces a spin model to explain them analytically, and relates the phenomena to entropy rescaling and polymer melt theories.

Contribution

It presents a simple analytical spin model for inverse melting and freezing, linking these phenomena to entropy and interaction parameter rescaling.

Findings

The spin model exhibits inverse melting and freezing behaviors.

Analytic solutions relate inverse phenomena to entropy and interaction parameters.

The model's features resemble a broad class of inverse melting phenomena.

Abstract

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 phenomena 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. 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.