Reaction of water with MgO(100) surfaces: Part III. X-ray standing wave studies

Clean MgO(100) surfaces cleaved in vacuum and exposed to water vapor or bulk water were studied using the X-ray standing wave (XSW) technique in back reflection mode and surface sensitive, element specific O KLL and Mg KLL Auger electron yield detection. The effects of surface charging were mitigated, but not entirely eliminated, by using a low-energy electron flood gun. Simulation of the XSW signal showed that the effect of surface charging on the XSW data could be minimized with careful experimental design. We demonstrate that the XSW method can be applied to studies of insulating surfaces, and our results for MgO(100) surfaces exposed to water vapor or bulk water indicate the following: (1) the vacuum-cleaved clean surface undergoes no surface reconstruction or significant relaxation perpendicular to the surface; (2) Mg–OH distances on surfaces exposed to water vapor or bulk water measured perpendicular to the (100) surface are the same as in bulk MgO; and (3) the z-position of the surface Mg atoms does not change within the estimated error [±2% of the (200) spacing] after the surface is fully hydroxylated. Our results for the clean, vacuum-cleaved surface disagree with results from impact collision ion-scattering spectroscopy and surface-extended electron-loss fine structure for MgO(100), which indicate 15 and 17% inward relaxation, respectively, and they support results from low-energy electron diffraction, reflection high-energy electron diffraction, and photoelectron diffraction that show little, if any, relaxation or rumpling of the surface.