A dynamical system approach to relaxation in glass-forming liquids†

Abstract

The “classical” thermodynamic and statistical mechanical theories of Gibbs and Boltzmann are both predicated on axiomatic assumptions whose applicability is hard to ascertain. Theoretical objections and an increasing number of observed deviations from these theories have led to sustained efforts to develop an improved mathematical and physical foundation for them, and the search for appropriate extensions that are generally applicable to condensed materials at low temperatures (T) and high material densities where the assumptions of these theories start to become particularly questionable. These theoretical efforts have largely focused on minimal models of condensed material systems, such as the Fermi–Ulam–Pasta–Tsingou model, and other simplified models of condensed materials that are amenable to numerical and analytic treatments and that can serve to illuminate essential features of relaxation processes in condensed materials under conditions approaching integrable dynamics where clear departures from classical thermodynamics and dynamics can be generally expected. These studies indicate an apparently general multi-step relaxation process, corresponding to an initial “fast” relaxation process (termed the fast β-relaxation in the context of cooled liquids), followed by a longer “equipartition time”, namely, the α-relaxation time τ_α in the context of cooled liquids. This relaxation timescale can be enormously longer than the fast β-relaxation time τ_β so that τ_α is the primary parameter governing the rate at which the material comes into equilibrium, and thus is a natural focus of theoretical attention. Since the dynamics of these simplified dynamical systems, originally intended as simplified models of real crystalline materials exhibiting anharmonic interactions, greatly resemble the observed relaxation dynamics of both heated crystals and cooled liquids, we adapt this dynamical system approach to the practical matter of estimating relaxation times in both cooled liquids and crystals at elevated temperatures, which we identify as weakly non-integrable dynamical systems.