The role of H-H interactions and impurities on the structure and energetics of H/Pd(111).

Understanding hydrogen incorporation into palladium requires detailed knowledge of surface and subsurface structure and atomic interactions as surface hydrogen is being embedded. Using density functional theory (DFT), we examine the energies of hydrogen layers of varying coverage adsorbed on Pd(111). We find that H-H and H-Pd interactions promote the formation of the well-known 3×3 phases but also favor an unreported (3 × 3) phase at high H coverages for which we present experimental evidence. We relate the stability of isolated H vacancies of the (3 × 3) phase to the need of H2 molecules to access bare Pd before they can dissociate. Following higher hydrogen dosage, we observe initial steps of hydride formation, starting with small clusters of subsurface hydrogen. The interaction between H and Pd is complicated by the persistent presence of carbon at the surface. X-ray photoelectron spectroscopy experiments show that trace amounts of carbon, emerging from the Pd bulk despite many surface cleaning cycles, become mobile enough to repopulate the C-depleted surface at temperatures above 200 K. When exposed to hydrogen, these surface carbon atoms react to form benzene, as evidenced by scanning tunneling microscopy observations interpreted with DFT.

Pentagons and heptagons in the first water layer on Pt(111).

Scanning tunneling topography of long-unexplained "square root of 37" and "square root of 39" periodic wetting arrangements of water molecules on Pt(111) reveals triangular depressions embedded in a hexagonal H2O-molecule lattice. Remarkably, the hexagons are rotated 30° relative to the "classic bilayer" model of water-metal adsorption. With support from density functional theory energetics and image simulation, we assign the depressions to clusters of flat-lying water molecules. 5- and 7-member rings of H2O molecules separate these clusters from surrounding "H-down" molecules.

Interpretation of high-resolution images of the best-bound wetting layers on Pt(111).

Two interpretations have been proposed of dark triangles observed in scanning tunneling microscopy (STM) images of the best bound, √37×√37-R25.3°, and √39×√39-R16.1° periodic water monolayers on Pt(111). In one, a "Y"-shaped tetramer of water molecules is removed, leaving a vacancy island behind; the other assumes the Y is replaced by a hexagon of H(2)O molecules, amounting to a di-interstitial. Consistent only with the di-interstitial model are thermal desorption and CO coadsorption data, STM line scans, and total energies obtained from density functional theory calculations.

Observation of surface self-diffusion on ice.

To determine the role of surface diffusion on the morphology of ice surfaces we track the evolution with STM of 2D ice-island arrays on the basal surface of ice films on Pt(111) between 115 and 135 K. In contrast with previous measurements at higher temperatures, we find that the evolution is dominated by surface diffusion. The extracted surface self-diffusion coefficient has an activation energy of 0.4+/-0.1 eV, much less than the value previously measured for bulk diffusion.

Labyrinthine island growth during Pd/Ru(0001) heteroepitaxy.

Using low energy electron microscopy we observe that Pd deposited on Ru only attaches to small sections of the atomic step edges surrounding Pd islands. This causes a novel epitaxial growth mode in which islands advance in a snakelike motion, giving rise to labyrinthine patterns. Based on density functional theory together with scanning tunneling microscopy and low energy electron microscopy we propose that this growth mode is caused by a surface alloy forming around growing islands. This alloy gradually reduces step attachment rates, resulting in an instability that favors adatom attachment at fast advancing step sections.

Self-assembly via adsorbate-driven dislocation reactions.

Deposition of S onto a monolayer of Ag/Ru(0001) transforms the herringbone pattern of the clean Ag film into a strikingly regular array of 2D-vacancy islands [Nature (London) 397, 238 (1999)]]. Time-resolved scanning tunneling microscopy reveals that this nanometer-scale restructuring occurs by a cooperative mechanism involving the sequential formation of triangular regions with fcc and hcp stacking. Using a 2D Frenkel-Kontorova model, we can simulate the creation of these triangular building blocks via basic dislocation motions and reactions.