Interaction of Water Molecules with the α-Fe2O3(0001) Surface: A Combined Experimental and Computational Study

The interaction of water with the basal plane (0001) of α-Fe2O3 (hematite) is a fundamental and challenging topic in the fields of surface science and earth science. Despite intensive investigations, many issues remain unclear especially due to the lack of direct spectroscopic evidence. Here, water adsorption on the pristine Fe-terminated α-Fe2O3(0001) surface was investigated by polarization-dependent infrared reflection absorption spectroscopy and X-ray photoelectron spectroscopy in conjunction with calculations from density functional theory. The combined results provide solid evidence that the interaction of water with α-Fe2O3(0001) is dominated by the heterolytic dissociation yielding an OwD species coordinated in atop-configuration to surface Fe3+ and an OsD species resulting from the deuterium/hydrogen transfer to an adjacent substrate O2–. Both isolated hydroxyl groups do not feature any hydrogen bonding, while the intact water molecules were identified as minor species that are bound to surface Fe3+ ions and interact via a relatively strong H-bonding with substrate oxygen. Water adsorption on α-Fe2O3(0001) at 230 and 200 K leads to the formation of water thin films including bilayers and multilayers, which are characterized by different types of intermolecular H-bonds.