Hydration structure of diamondoids from reactive force fields

Abstract: Diamondoids are promising materials for applications in catalysis and nanotechnology. Since many of their applications are in aqueous environments, to understand their function it is essential to know the structure and dynamics of the water molecules in their first hydration shells. In this study, we develop an improved reactive force field (ReaxFF) parameter set for atomistically resolved molecular dynamics simulations of hydrated diamondoids to characterize their interfacial water structure. We parameterize the force field and validate the water structure against geometry-optimized structures from density functional theory. We compare the results to water structures around diamondoids with all partial charges set to zero, and around charged smooth spheres, and find qualitatively similar water structuring in all cases. However, the response of the water molecules is most sensitive to the partial charges in the atomistically resolved diamondoids. From the systematic exclusion of atomistic detail we can draw generic conclusions about the nature of the hydrophobic effect at nanoparticle interfaces and link it to the interfacial water structure. The interactions between discrete partial charges on short length scales affect the hydration structures strongly but the hydrophobic effect seems to be stable against these short scale surface perturbations. Our methods and the workflow we present are transferable to other hydrocarbons and interfacial systems.