Shear-stress function approach of hydration layer based on the Green-Kubo formula.

We present the analytic expression of the stress correlation (SC) function for the ubiquitous hydration water layer (HWL) using the Green-Kubo equation and the shear modulus of HWL. The SC function is then experimentally obtained by measuring the viscoelastic properties of HWL using shear-mode dynamic force spectroscopy. Interestingly, the SC changes sign from positive to negative as the HWL thickness increases, where the shear stresses acting on the HWLs bound to two nearby surfaces are out of phase. We also suggest that the repulsive hydration force originates from the SC of HWL. Our results provide the first demonstration of the microscopic understanding of the HWL viscoelasticity and may allow a deeper insight on the HWL dynamics as well as the complex liquids.