Nonequilibrium thermodynamics of glasses

Abstract

We consider the nonequilibrium thermodynamics of glasses from various perspectives. For the commonly used equilibriumlike approach based on Gibbs' fundamental form with an additional pair of conjugate variables, we discuss possible choices of the independent out-of-equilibrium variable and we illustrate some implications by concrete results for a well-known exactly solvable lattice model. The choice of variables is further illuminated from the complementary atomistic perspective offered by the inherent-structure formalism. A general formalism of nonequilibrium thermodynamics is employed (i) to derive the standard equilibriumlike approach, (ii) to formulate two self-contained levels to describe glassy dynamics and thermodynamics, and (iii) to offer guidance for future simulations of glasses. The thermodynamic approach suggests to introduce four-point correlation functions associated with structural rearrangements after imposed deformations, which might offer a possibility to detect a growing length scale at the glass transition without employing any dynamic information.