Abstract

In this work we present a systematic study of the lateral (parallel to the wall) and normal (perpendicular to the wall) nanostructure of the electric double layer at a heterogeneous interface between two regions of different surface charges, often found in nanoscale electrochemical devices. Specifically, classical density functional theory (DFT) is used to probe a cation concentration range of 10 mM to 1 M, for valences of +1, + 2, and +3, and a diameter range of 0.15–0.9 nm over widely varying surface charges (between −0.15 and +0.15 C/m2). The DFT results predict significant lateral and normal nanostructure in the form of ion concentration oscillations. These results are directly compared with those from Poisson–Boltzmann theory, showing significant deviation between the two theories, not only in the concentration profiles, but also in the sign of the electrostatic potential.