Diffusion dynamics of supercooled water modeled with the cage-jump motion and hydrogen-bond rearrangement

Abstract: The slow dynamics of glass-forming liquids is generally ascribed to the cage-jump motion. In the cage-jump picture, a molecule remains in a cage formed by neighboring molecules, and after a sufficiently long time, it jumps to escape from the original position by cage-breaking. The clarification of the cage-jump motion is therefore linked to unraveling the fundamental element of the slow dynamics. Here, we develop a cage-jump model for the dynamics of supercooled water. The caged and jumping states of a water molecule are introduced with respect to the hydrogen-bond (H-bond) rearrangement process, and describe the motion in supercooled states. It is then demonstrated from the molecular dynamics simulation of the TIP4P/2005 model that the characteristic length and time scales of cage-jump motions provide a good description of the self-diffusion constant that is determined in turn from the long-time behavior of the mean square displacement. Our cage-jump model thus enables to connect between H-bond dynamics and molecular diffusivity.