Screening and collective effects in randomly pinned fluids: a new theoretical framework

We propose a theoretical framework for the dynamics of bulk isotropic hard-sphere systems in the presence of randomly pinned particles and apply this theory to supercooled water to validate it. Structural relaxation is mainly governed by local and non-local activated process. As the pinned fraction grows, a local caging constraint becomes stronger and the long range collective aspect of relaxation is screened by immobile obstacles. Different responses of the local and cooperative motions results in subtle predictions for how the alpha relaxation time varies with pinning and density. Our theoretical analysis for the relaxation time of water with pinned molecules quantitatively well describe previous simulations. In addition, the thermal dependence of relaxation for unpinned bulk water is also consistent with prior computational and experimental data.

Automated summary

The study proposes a theoretical framework for the dynamics of bulk isotropic hard-sphere systems in the presence of randomly pinned particles and applies it to supercooled water. It reveals that as the fraction of pinned particles increases, the local caging constraint becomes stronger, and the long-range collective relaxation is screened by immobile obstacles, resulting in different responses of local and cooperative motions.