Anomalous dielectric response of nanoconfined water.

In order to develop a microscopic level understanding of the anomalous dielectric properties of nanoconfined water (NCW), we study and compare three different systems, namely, (i) NCW between parallel graphene sheets (NCW-GSs), (ii) NCW inside graphene covered nanosphere (NCW-Sph), and (iii) a collection of one- and two-dimensional constrained Ising spins with fixed orientations at the termini. We evaluate the dielectric constant and study the scaling of ε with size by using linear response theory and computer simulations. We find that the perpendicular component remains anomalously low at smaller inter-plate separations (d) over a relatively wide range of d. For NCW-Sph, we could evaluate the dielectric constant exactly and again find a low value and a slow convergence to the bulk. To obtain a measure of surface influence into the bulk, we introduce and calculate correlation lengths to find values of ∼9 nm for NCW-GS and ∼5 nm for NCW-Sph, which are surprisingly large, especially for water. We discover that the dipole moment autocorrelations exhibit an unexpected ultrafast decay. We observe the presence of a ubiquitous frequency of ∼1000 cm, associated only with the perpendicular component for NCW-GS. This (caging) frequency seems to play a pivotal role in controlling both static and dynamic dielectric responses in the perpendicular direction. It disappears with an increase in d in a manner that corroborates with the estimated correlation length. A similar observation is obtained for NCW-Sph. Interestingly, one- and two-dimensional Ising model systems that follow Glauber spin-flip dynamics reproduce the general characteristics.