Derivation of a microscopic theory of barriers and activated hopping transport in glassy liquids and suspensions.

A recently proposed microscopic activated barrier hopping theory [K. S. Schweizer and E. J. Saltzman, J. Chem. Phys. 119, 1181 (2003)] of slow single-particle dynamics in glassy liquids, suspensions, and gels is derived using nonequilibrium statistical mechanics. Fundamental elements underlying the stochastic nonlinear Langevin equation description include an inhomogeneous liquid or locally solid-state perspective, dynamic density-functional theory (DDFT), a local equilibrium closure, and a coarse-grained free-energy functional. A dynamic Gaussian approximation is not adopted which is the key for avoiding a kinetic ideal glass transition. The relevant excess free energy is of a nonequilibrium origin and is related to dynamic force correlations in the fluid. The simplicity of the approach allows external perturbations to be rather easily incorporated. Dynamic heterogeneity enters naturally via mobility fluctuations associated with the stochastic barrier-hopping process. The derivation both identifies the limitations of the theory and suggests new avenues for its systematic improvement. Comparisons with ideal mode-coupling theory, alternative DDFT approaches and a field theoretic path-integral formulation are presented.