Non-equilibrium theory of the linear viscoelasticity of glass and gel forming liquids

Abstract

We propose a first-principles theoretical approach for the description of the aging of the linear viscoelastic properties of a colloidal liquid after a sudden quench into a dynamically arrested (glass or gel) state. Specifically, we couple a general expression for the time-evolving shear-stress relaxation function $\eta(\tau;t)$ (whose $\tau$-integral is the instantaneous viscosity $\eta(t)$), written in terms of the non-equilibrium structure factor $S(k;t)$ and intermediate scattering function $F(k,\tau;t)$, with the equations that determine $S(k;t)$ and $F(k,\tau;t)$, provided by the non-equilibrium self-consistent generalized Langevin equation (NE-SCGLE) theory. In this manner, we obtain a closed theoretical scheme that directly connects inter-particle forces with experimentally accessible rheological properties of non-equilibrium amorphous states of matter. The predictive capability of the resulting theoretical formalism is illustrated here with its concrete application to the Weeks-Chandler-Andersen (WCA) model of a soft-sphere fluid.