RESUMO
We use molecular dynamics simulations to ascertain the effects of geometrical restriction on glass-forming tetrahedral liquids. Striving for a broad approach, we study families of waterlike and silicalike liquids, for which we systematically scale the partial charges and, hence, the relevance of the tetrahedral networks. The confined liquids and the confining matrices consist of the same type of particles to avoid disruptive interactions and distorted structures at the interfaces. Spatially resolved analyses show that these neutral confinements still impose static mobility gradients and density correlations on the liquids. We quantify the increasing degree and range of the altered properties upon cooling. For both families of models, common relations describe the confinement effects of all systems with tetrahedral order, while deviations occur for systems with lower polarities and different structures. The observations are rationalized by considering the fact that a pinned wall imprints a static energy landscape to a neighboring liquid. We explore the properties of this landscape based on changes in vibrational motion and structural relaxation and find that typical barrier heights amount to two to three times the activation energy of bulk dynamics. Combining the present and previous results, we predict the evolution of confinement effects down to the glass transition temperature for liquids without fragile-to-strong crossover. In addition, it is found for silicalike liquids that the temperature dependence of dynamic and static correlation lengths from confinement studies is not affected when cooling through fragile-to-strong transitions of the bulk materials, casting doubt on the relevance of these length scales for the glassy slowdown.
