Unambiguous characterization of in-plane dielectric response in nanoconfined liquids: water as a case study

Abstract

The in-plane dielectric constant of nanoconfined water has attracted growing interest over the last years. Nevertheless, this magnitude is not well-defined at the nanoscale due to its dependence on the arbitrary choice of water width. We propose the in-plane 2D polarizability, $\alpha_{\parallel}$, as an unambiguous characterization of the in-plane dielectric response under 2D confinement, in analogy to what has been recently done for the perpendicular response. Using classical molecular dynamics simulations, we compute $\alpha_{\parallel}$ via two independent and consistent methods: based on fluctuation--dissipation theory, and from the induced dipole moment when water is placed in a capacitor. Our results provide the framework to quantify the in-plane dielectric response of polar liquids across simulations and experiments.