Mark E. Gallagher

Order and disorder in the wetting layer on Ru(0001)

The growth of an intact water monolayer on Ru(0001) has been investigated by comparing the ordering of O and Ru, determined by low-energy electron diffraction (LEED), with that of the top layer of O and H, as probed by He atom scattering (HAS). Although LEED shows that water forms an extended commensurate (square root 3 x square root 3) R30 degrees structure as the coverage approaches 0.67 monolayer, the HAS distributions are insensitive to the exact water coverage and show a very low specular reflectivity, indicating a disordered water layer. The angular profile from a D2O monolayer shows a broad diffuse peak in the angular scattering distribution at a momentum exchange similar to the position of the second-order (1/3, 1/3) peaks, but the maxima show little variation with scattering azimuth. H2O shows a slightly higher He reflectivity and more clearly resolved angular structure, with broad, faint peaks appearing close to the first-order diffraction positions. The origin of this disorder is discussed based on density functional calculations for the monolayer which find that water forms chains of flat and H-down molecules within a hexagonal hydrogen-bonding network, rather than the ice bilayer usually assumed. This arrangement leads to long-range order in the O location, but disorder in the O height and the proton orientation. We discuss how this combination of lateral order in the adsorption site, but disorder in the water orientation, is reflected in the sharp square root 3 LEED pattern but diffuse, broad peaks in He scattering.

From ultra-high vacuum to the electrochemical interface: x-ray scattering studies of model electrocatalysts.

In-situ surface X-ray scattering (SXS) has become a powerful probe of the atomic structure at the metal-electrolyte interface. In this paper we describe an experiment in which a Pt(111) sample is prepared under ultra-high vacuum (UHV) conditions to have a p(2 x 2) oxygen layer adsorbed on the surface. The surface is then studied using SXS under UHV conditions before successive transfer to a bulk water environment and then to the electrochemical environment (0.1 M KOH solution) under an applied electrode potential. The Pt surface structure is examined in detail using crystal truncation rod (CTR) measurements under these different conditions. Finally, some suggestions for future experiments on alloy materials, using the same methodology, are proposed and discussed in relation to previous results.