Universal Repulsive Contribution to the Solvent-Induced Interaction Between Sizable, Curved Hydrophobes

Abstract

In addition to the direct attraction, sizable hydrophobes in water experience an attractive force mediated by interfacial water. Using simple geometric arguments, we identify the conditions at which the water-induced interaction between curved hydrocarbon surfaces becomes repulsive. The repulsive contribution arises from the thermodynamic penalty due to the emergence of the liquid/vapor boundary created as water gets expelled between curved hydrophobes. By augmenting the mean field approach with atomistic simulations of pristine and alkyl-coated graphitic nanoparticles in three distinct geometries, spherical, cylindrical and planar, immersed in water, we show the macroscopic thermodynamics remarkably works down to the molecular scale. The new insights improve the prediction and control of wetting and dispersion properties for a broad class of nonpolar nanoparticles