Water Layer at Hydrophobic Surface: Electrically Dead but Dynamically Alive?

The origin of the anomalous low value of the static dielectric constant (SDC) of confined water has been addressed and unearthed. While the low value is partly due to the different dielectric boundaries, a significant role is played by the "electrically dead layer" (EDL). As the observed dielectric constant is the harmonic mean of the grid-wise SDCs, the first layer, having the smallest SDC, makes a disproportionately large contribution. This enhanced contribution, in turn, arises from the orientationally ordered surface water molecules. They exhibit reduced fluctuations in collective dipole moment, as the molecules remain partly caged due to water-surface interactions. This phenomenon is found to be universal. We study the structure and dynamics of the water molecules which characterize the EDL. We demonstrate that while the EDL remains alive at a molecular level, with a finite residence time, it displays time scales not substantially different compared to the distant water layers.