Dielectric response of polar liquids in narrow slit pores

Based on molecular dynamics (MD) simulations and a simple (Stockmayer) model we investigate the static and dynamic dielectric response of polar liquids confined to narrow slit pores. The MD simulations are used to calculate the time-dependent polarization fluctuations along directions parallel and perpendicular to the walls, from which the components of the frequency-dependent dielectric tensor can be derived via linear response theory. Our numerical results reveal that the system's response is strongly anisotropic. The parallel dielectric function, epsilon(parallel to)(omega), has Debye-like character very similar to the corresponding isotropic bulk function, epsilon(bulk)(omega), at the same chemical potential. Indeed, the main confinement effect on epsilon(parallel to)(omega) consists in a shift toward smaller values relative to the bulk function. On the other hand, in the perpendicular direction we observe a characteristic peak in the absorption part of the dielectric function, epsilon(perpendicular to)(omega). This peak is absent in the bulk system and reflects strongly pronounced, damped oscillations in the polarization fluctuations normal to the walls. We discuss two possible origins of the oscillations (and the resulting absorption peak), that is collective oscillations of dipoles in clusters formed parallel to the walls, and the existence of a dipolaron mode previously observed in MD simulations of bulk polar fluids.