Surface polarity and nanoscale solvation

Linear solvation theories are well established to describe electrostatic hydration of small solutes when the hydration free energy is dominated by the electrostatic free energy of the solute multipole. In contrast, hydration of nanometer solutes is driven by surface hydration. We address the question of whether the linear-response thermodynamics established for small multipolar solutes applies to surface hydration. To this end, molecular dynamics simulations are carried out on a model C180 solute that carries no global multipole, but the surface of which is decorated with radially pointing dipoles. Linear response is dramatically violated in this case. Further, two crossovers in the solvation thermodynamics are discovered as the surface polarity is increased. Both transformations produce strongly nonlinear solvation response. The second, more collective, crossover leads to a dramatic slowing down of the interfacial dynamics, reaching the time-scales of nanoseconds. Our picture offers the possibility of flipping water domains at interfaces of nanoparticles and biomolecules.