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.
