Fluctuating hydration structure around nanometer-size hydrophobic solutes. I. Caging and drying around C60 and C60H60 spheres.

The hydration structure around nanometer-size hydrophobic solutes is studied with molecular dynamics simulation by taking aqueous solutions of C60 and C60H60 as examples. In the hydration shell around a single C60 or C60H60, dipoles of simulated water molecules tend to be aligned to form the vortexlike coherent pattern which lasts for 100 ps, while individual water molecules stay within the hydration shell for about 10 ps. This structural pattern organized by fluctuating and diffusively moving molecules should be called a "fluctuating cage". In the narrow region between a pair of C60 molecules or a pair of C60H60 molecules, water density strongly fluctuates and is correlated to the mean force between solutes. The fluctuating caging and drying between solutes affect the hydrophobic interaction and dynamical behaviors of solutes.