Confined Water's Dielectric Constant Reduction Is Due to the Surrounding Low Dielectric Media and Not to Interfacial Molecular Ordering

Liquid water confined within nanometer-sized channels exhibits a surprisingly low dielectric constant along the direction orthogonal to the channel walls. This is typically assumed to result from a pronounced heterogeneity across the sample: the dielectric constant would be bulk-like everywhere except at the interface, where it would be dramatically reduced by strong restrictions on interfacial molecules. Here we study the dielectric properties of water confined within graphene slit channels via classical molecular dynamics simulations. We show that the permittivity reduction is not due to any important alignment of interfacial water molecules, but instead to the long-ranged anisotropic dipole correlations combined with an excluded-volume effect of the low-dielectric confining material. The bulk permittivity is gradually recovered only over several nanometers due to the impact of long-range electrostatics, rather than structural features. This has important consequences for the control of, e.g., ion transport and chemical reactivity in nanoscopic channels and droplets.

Automated summary

The reduction in dielectric constant of water confined within nanometer-sized channels is primarily attributed to long-ranged anisotropic dipole correlations and the excluded-volume effect of low-dielectric confining material, rather than important alignment of interfacial water molecules. The gradual recovery of bulk permittivity is influenced by long-range electrostatics, not structural features.