Relaxations and interfacial water ordering at the corundum (110) surface

In situ high resolution specular X-ray reflectivity measurements were used to examine relaxations and interfacial water ordering occurring at the corundum (110)-water interface. Sample preparation affected the resulting surface structure. Annealing in air at 1373 K produced a reconstructed surface formed through an apparently ordered aluminum vacancy. The effect of the reconstruction on in-plane periodicity was not determined. The remaining aluminum sites on the surface maintain full coordination by oxygen and the surface was coated with a layer of physically adsorbed water. Ordering of water further from the surface was not observed. Acid etching of this surface and preparing a surface through annealing at 723 K both produced an unreconstructed surface with identical relaxations and water ordering. Relaxations were confined primarily to the top ∼4 Å of the surface and were dominated by an increased distribution width of the fully occupied surface aluminum site and outward relaxation of the oxygen surface functional groups. A layer of adsorbed water fully coated the surface and occurred in two distinct sites. Water above this showed signs of layering and indicated that water ordering extended 7-10 Å from the surface. Relaxations and the arrangement of interfacial water were nearly identical on both the unreconstructed corundum and isostructural hematite (110) surfaces. Comparison to corundum and hematite (012) suggests that the arrangement of interfacial water is primarily controlled by mineral surface structure.