By using advanced data analysis techniques, we characterize the shape of the voids surrounding model polymers of different sizes in water, observed in molecular dynamics simulations. We find that even when the model polymer is folded, the voids are extremely rough, with branches that can extend to over 1 nm away from the polymer. Water molecules in contact with the void retain close-to-bulk properties in terms of local structure. The branches disappear, and the voids start resembling the quasispherical shape predicted by dewetting theory only when they surround particles with a radius ∼1 nm, well above the size occupied by a folded hydrophobic polymer. Our results provide fresh insights into the microscopic origins of the vapor-like interfaces underlying dewetting and drying transitions.
