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Understanding the influence of Coulomb and dispersion interactions on the wetting behavior of ionic liquids.

We study the role of dispersion and electrostatic interactions in the wetting behavior of ionic liquids on non-ionic solid substrates. We consider a simple model of an ionic liquid consisting of spherical ions that interact via Lennard-Jones and Coulomb potentials. Bulk and interfacial properties are computed for five fluids distinguished by the strength of the electrostatic interaction relative to the dispersion interaction. We employ Monte Carlo simulations and an interface-potential-based approach to calculate the liquid-vapor and substrate-fluid interfacial properties. Surface tensions for each fluid are evaluated over a range of temperatures that spans from a reduced temperature of approximately 0.6 to the critical point. Contact angles are calculated at select temperatures over a range of substrate-fluid interaction strengths that spans from the near-drying regime to the wetting regime. We observe that an increase in the relative strength of Coulombic interactions between ions leads to increasing deviation from Guggenheim's corresponding states theory. We show how this deviation is related to lower values of liquid-vapor excess entropies observed for strongly ionic fluids. Our results show that the qualitative nature of wetting behavior is significantly influenced by the competition between dispersion and electrostatic interactions. We discuss the influence of electrostatic interactions on the nature of wetting and drying transitions and corresponding states like behavior observed for contact angles. For all of the fluids studied, we observe a relatively narrow range of substrate-fluid interaction strengths wherein the contact angle is nearly independent of temperature. The influence of the ionic nature of the fluid on the temperature dependence of contact angle is also discussed.