The temperature-dependent solvation of hydrophobic solutes in water is
investigated by largescale 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 Å 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 higherorder curvature corrections and water-discreteness effects