Structure and dynamics of supercooled water in neutral confinements

We perform molecular dynamics simulations to study the structure and dynamics of liquid water in neutral nanopores, which are generated by pinning a suitable subset of water molecules in an equilibrium configuration of a bulk system. It is found that such neutral confinement does not disturb the structure of water, in particular, the local tetrahedral order, while it imposes a pronounced spatial inhomogeneity on the dynamics of water. Specifically, when the pore wall is approached, hopping motion sets in and water dynamics slows down. We show that the logarithm of the correlation time is an exponential function of the distance to the wall, indicating a tremendous gradient of water mobility across the confinement. Upon cooling, the length scale associated with this exponential distance dependence and, thus, the range of the wall effect increases, at least down to the critical temperature of mode coupling theory, T-c. Also, the temperature dependence of water dynamics varies across the pore, i.e., fragility is high in the pore center, while it is low near the pore wall. Due to all these effects, time-temperature superposition is violated. Our observations for a neutral confinement reveal that specific interactions at hydrophilic or hydrophobic walls are not the main cause of spatially inhomogeneous dynamics of confined water. In view of similarities with the behavior of Lennard-Jones liquids in neutral confinements, one may rather speculate that the effects observed for confined water are general and result from the existence of a static contribution to the energy landscape, which is imprinted by an immobile environment. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4798217]