The spontaneous curvature of the water-hydrophobe interface

The temperature-dependent solvation of hydrophobic solutes in water is investigated by large-scale molecular dynamics simulations. A simultaneous fit of solvation free energies for spheres and cylinders with radii up to R = 2 nm yields a negative Tolman length on the order of 1 angstrom at room temperature, equivalent to a spontaneous curvature that favors water droplets over cavities. Pronounced crossover effects of the surface free energy are analyzed in terms of higher-order curvature corrections and water-discreteness effects. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4755753]