Reactive Simulations of Silica Functionalization with Aromatic Hydrocarbons

Reactive molecular dynamics simulations are used to model the covalent functionalization of amorphous silica with aromatic hydrocarbons. Simulations show that the surface density of silanol-terminated phenyl, naphthyl, and anthracenyl molecules is lower than the maximum value calculated based on molecule geometry, and the simulation densities decrease faster with the number of aromatic rings than the geometric densities. The trends are analyzed in terms of the surface–silanol bonding configurations, tilt angles, local conformational ordering, and aggregation of surface-bound molecules under steady-state conditions. Results show that the surface density is affected by both the size and symmetry of the aromatic hydrocarbons. The correlations among bonding, orientation, and surface density identified here may guide the selection or design of molecules for functionalized surfaces.