First-principles study on the adsorption structure of water molecules on a pyrite (100) surface

The hydration structure of water molecule adsorption at different coverages of a monolayer on a pyrite (100) surface were simulated using the density functional theory (DFT) method. The results demonstrate that the Fe-O interaction weakens and the adsorption energy per water molecule decreases with increasing water coverage, except at a monolayer coverage of 12/12 (i.e., full coverage). H-S and H-O hydrogen bonds were formed on the nearest surface layer. When large amounts of water molecules adsorb onto the surface, the adsorbed water molecules can be divided into three layers: the layer nearest to the surface, the second nearest to the surface, and the layer farthest from the surface. The thickness of the former two layers is approximately 5.5 Å. The three layers have water densities of 1.12 g/cm3, 1.08 g/cm3, and 0.95 g/cm3, respectively, suggesting that there is a strong interaction between the pyrite surface and water molecules and the influence of surface structure on water adsorption reaches a distance of more than 10 Å. Dynamics simulations suggest that the water molecules close to the mineral surfaces are in an orderly arrangement while those far from the surface are disordered.