A molecular dynamics simulations study on the relations between dynamical heterogeneity, structural relaxation, and self-diffusion in viscous liquids.

We perform molecular dynamics simulations for viscous liquids to study the relations between dynamical heterogeneity, structural (α) relaxation, and self-diffusion. For atomistic models of supercooled water, polymer melts, and an ionic liquid, we characterize the space-time characteristics of dynamical heterogeneity by the degree of deviations from Gaussian displacement statistics (α2), the size of clusters comprising highly mobile particles (S(w)), and the length of strings consisting of cooperatively moving particles (L(w)). Comparison of our findings with previous simulation results for a large variety of viscous liquids, ranging from monoatomic liquids to silica melt, reveals a nearly universal decoupling between the time scales of maximum non-Gaussian parameter (τ(α2)) and the time constant of the α relaxation (τ(α)) upon cooling, explicitly, τ(α2) ∝τ(α)(3/4). Such uniform relation was not observed between the peak times of S(w) or L(w) and τ(α). On the other hand, the temperature-dependent time scale of maximum string length (τ(L)) follows the inverse of the self-diffusion coefficient (D) for various systems at sufficiently low temperatures, i.e., τ(L) ∝ D(-1). These observations are discussed in view of a breakdown of the Stokes-Einstein relation for the studied systems. It is found that the degree of deviation from this relation is correlated with the stretching of the α relaxation.

Effect of the hydroaffinity and topology of pore walls on the structure and dynamics of confined water.

We perform molecular dynamics simulations to observe the structure and dynamics of SPC/E water in amorphous silica pores and amorphous ice pores with radii slightly larger than 10 Å. In addition to atomically rough pores, we construct completely smooth pores such that the potential felt at a given distance from the pore wall is an averaged atomic potential. As compared to rough walls, smooth walls induce stronger distortions of water structure for both silica and ice confinements. On the other hand, unlike the smooth pores, the rough pores strongly slow down water dynamics at the pore wall. The slowdown vanishes when reducing the atomic charges in the wall, i.e., when varying the hydroaffinity, while keeping the surface topology, indicating that it is not a geometric effect. Rather, it is due to the fact that the wall atoms provide a static energy landscape along the surface, e.g., fixed anchor-points for hydrogen bonds, to which the water molecules need to adapt, blocking channels for structural rearrangement. In the smooth pores, water dynamics can be faster than in the bulk liquid not only at the pore wall but also in the pore center. Changes in the tetrahedral order rather than in the local density are identified as the main cause for this change of the dynamical behavior in the center of smooth pores.

Ab initio H2O in realistic hydrophilic confinement.

A protocol for the ab initio construction of a realistic cylindrical pore in amorphous silica, serving as a geometric nanoscale confinement for liquids and solutions, is presented. Upon filling the pore with liquid water at different densities, the structure and dynamics of the liquid inside the confinement can be characterized. At high density, the pore introduces long-range oscillations into the water density profile, which makes the water structure unlike that of the bulk across the entire pore. The tetrahedral structure of water is also affected up to the second solvation shell of the pore wall. Furthermore, the effects of the confinement on hydrogen bonding and diffusion, resulting in a weakening and distortion of the water structure at the pore walls and a slowdown in diffusion, are characterized.