Parametrizing Nonbonded Interactions from Wetting Experiments via the Work of Adhesion: Example of Water on Graphene Surfaces

The question of the parametrization of interfacial nonbonded interactions for heterogeneous solid liquid systems is addressed through the example of water on graphene surfaces. We suggest that a reference value of the solid liquid work of adhesion W-SL rather than the corresponding wetting contact angle should be the quantity to reproduce through molecular simulations when deriving and testing interaction parameters. A relationship between W-SL and the adsorption energy of water On graphene is established almost independently of the water model. It is shown that this relationship also holds for water on graphite. The ability of different Lennard-Jones interaction potential parameters to reproduce the experimental value of W-SL a of water on graphite is evaluated. Furthermore, it is shown that the relationship mentioned above is able to predict quantitatively the value of W-SL for a classical model of water on hexagonal boron nitride and is in good agreement with the value of W-SL for a classical model of water on gold. We use this relationship to establish a direct connection between values of W-SL that can be obtained from macroscopic measurements of wetting contact angles and the adsorption energy of single water molecules obtained by quantum mechanical calculations.