Parallel Emergence of Rigidity and Collective Motion in a Family of Simulated Glass-Forming Polymer Fluids

Abstract

The emergence of the solid state in glass-forming materials upon cooling is accompanied by changes in both thermodynamic and viscoelastic properties and by a precipitous drop in fluidity. Here, we investigate changes in basic elastic properties upon cooling in a family of simulated polymer fluids, as characterized by a number of stiffness measures. We show that $τ_α$ can be expressed quantitatively both in terms of measures of the material ``stiffness'', $G_p$ and $\langle u^2 \rangle$, and the extent $L$ of cooperative particle exchange motion in the form of strings, establishing a direct relation between the growth of emergent elasticity and collective motion. Moreover, the macroscopic stiffness parameters, $G_p$, $B$, and $f_{s, q^*}$, can all be expressed quantitatively in terms of the molecular scale stiffness parameter, $k_{\mathrm{B}}T / \langle u^2 \rangle$ with $k_{\mathrm{B}}$ being Boltzmann's constant, and we discuss the thermodynamic scaling of these properties. We also find that $G_p$ is related to the cohesive energy density $Π_{\mathrm{CED}}$, pointing to the critical importance of attractive interactions in the elasticity and dynamics of glass-forming liquids. Finally, we discuss fluctuations in the local stiffness parameter as a quantitative measure of elastic heterogeneity and their significance for understanding both the linear and nonlinear elastic properties of glassy materials.