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The effects of ion-ion and ion-wall correlations in nanochannels are explored, specifically how they influence voltage- and pressure-driven currents and pressure-to-voltage energy conversion. Cations of different diameters (0.15, 0.3, and 0.9 nm) and different valences (+1, +2, and +3) at concentrations ranging from 10(-6) M to 1 M are considered in 50-nm- and 100-nm-wide nanoslits with wall surface charges ranging from 0 C/m(2) to -0.3 C/m(2). These parameters are typical of nanofluidic devices. Ion correlations have significant effects on device properties over large parts of this parameter space. These effects are the result of ion layering (oscillatory concentration profiles) for large monovalent cations and charge inversion (more cations in the first layer near the wall than necessary to neutralize the surface charge) for the multivalent cations. The ions were modeled as charged, hard spheres using density functional theory of fluids, and current was computed with the Navier-Stokes equations with two different no-slip conditions.

Ion Correlations in Nanofluidic Channels: Effects of Ion Size, Valence, and Concentration on Voltage- and Pressure-Driven Currents