H-bonding of an NH(3) gas molecule to H(2)O/Pt(111)--A barrier-free path.

Does an OH-flipping barrier hinder H-bond formation between a gas phase molecule and a water monolayer whose free OH ligands point toward a substrate? According to density functional theory calculations for water on Pt(111) the answer is yes, when the molecule is CO or N2, but no when it is NH3. The difference is the relatively strong attraction of the NH3 lone pair to free OH ligands.

Clusters, molecular layers, and 3D crystals of water on Ni(111).

We examined the growth and stability of ice layers on Ni(111) up to ∼7 molecular layers (ML) thick using scanning tunneling microscopy. At low coverage, films were comprised of ∼1 nm wide two-dimensional (2D) clusters. Only above ∼0.5 ML did patches of continuous 2D layers emerge, coexisting with the clusters until the first ML was complete. The structure of the continuous layer is clearly different from that of the 2D clusters. Subsequently, a second molecular layer grew on top of the first. 3D crystallites started to form only after this 2nd ML was complete. 2D clusters re-appeared when thicker films were partially evaporated, implying that these clusters represent the equilibrium configuration at low coverage. Binding energies and image simulations computed with density functional theory suggest that the 2D clusters are partially dissociated and surrounded by H adatoms. The complete 2D layer contains only intact water molecules because of the lack of favorable binding sites for H atoms. We propose molecular structures for the 2D layer that are composed of the same pentagon-heptagon binding motif and water density observed on Pt(111). The similarity of the water structures on Pt and Ni suggests a general prescription for generating low-energy configurations on close-packed metal substrates.

K+-hydration in a low-energy two-dimensional wetting layer on the basal surface of muscovite.

Density Functional Theory points to a key role of K(+) solvation in the low-energy two-dimensional arrangement of water molecules on the basal surface of muscovite. At a coverage of 9 water molecules per 2 surface potassium ions, there is room to accommodate the ions into wetting layers wherein half of them are hydrated by 3 and the other half by 4 water molecules, with no broken H-bonds, or wherein all are hydrated by 4. Relative to the "fully connected network of H-bonded water molecules" that Odelius et al. found to form "a cage around the potassium ions," the hydrating arrangements are several tens of meV/H2O better bound. Thus, low-temperature wetting on muscovite is not driven towards "ice-like" hexagonal coordination. Instead, solvation forces dominate.

Evidence for interlayer coupling and moiré periodic potentials in twisted bilayer graphene.

We report a study of the valence band dispersion of twisted bilayer graphene using angle-resolved photoemission spectroscopy and ab initio calculations. We observe two noninteracting cones near the Dirac crossing energy and the emergence of van Hove singularities where the cones overlap for large twist angles (>5°). Besides the expected interaction between the Dirac cones, minigaps appeared at the Brillouin zone boundaries of the moiré superlattice formed by the misorientation of the two graphene layers. We attribute the emergence of these minigaps to a periodic potential induced by the moiré. These anticrossing features point to coupling between the two graphene sheets, mediated by moiré periodic potentials.

A unique vibrational signature of rotated water monolayers on Pt(111): predicted and observed.

Six H-bonds in the periodic di-interstitial structure that accounts for scanning tunneling microscope images of "√37" and "√39" wetting layers on Pt(111) are some 0.2 Šshorter than H-bonds are in ice Ih. According to a broadly obeyed correlation, this density functional theory result implies a stringent test of the di-interstitial motif, namely the presence of an OH-stretch band red-shifted from that of ice Ih by more than 1000 cm(-1). Infrared absorption spectra satisfy the test, in showing a feature centered at about 1965 cm(-1), which grows in as deposited water orders.

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.

Partial dissociation of water on Ru(0001).

Initial water deposition on the moderately reactive precious metal surface Ru(0001) has been thought to produce an ice-like bilayer. However, calculations from first principles show that the wetting layer observed on Ru(0001) cannot be formed of undissociated water molecules. An energetically favorable alternative, consistent with the remarkable observation that the wetting layer's oxygen atoms are nearly coplanar, is a half-dissociated monolayer wherein water molecules and hydroxyl fragments are hydrogen-bonded in a hexagonal structure and hydrogen atoms bind directly to the metal.

Scanning Tunneling Microscopy Study of the Structure and Interaction between Carbon Monoxide and Hydrogen on the Ru(0001) Surface.

We use scanning tunneling microscopy (STM) to investigate the spatial arrangement of carbon monoxide (CO) and hydrogen (H) coadsorbed on a model catalyst surface, Ru(0001). We find that at cryogenic temperatures, CO forms small triangular islands of up to 21 molecules with hydrogen segregated outside of the islands. Furthermore, whereas for small island sizes (3-6 CO molecules) the molecules adsorb at hcp sites, a registry shift toward top sites occurs for larger islands (10-21 CO molecules). To characterize the CO structures better and to help interpret the data, we carried out density functional theory (DFT) calculations of the structure and simulations of the STM images, which reveal a delicate interplay between the repulsions of the different species.

CO-induced smoluchowski ripening of Pt cluster arrays on the graphene/Ir(111) moiré.

Regular Pt cluster arrays grown on the moiré template formed by graphene on Ir(111) were tested for their stability with respect to CO gas exposure. Cluster stability and adsorption-induced processes were analyzed as a function of cluster size, with in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. Small clusters containing fewer than 10 atoms were unstable upon CO adsorption. They sintered through Smoluchowski ripening-cluster diffusion and coalescence-rather than the frequently reported Ostwald ripening mediated by metal-adsorbate complexes. Larger clusters remained immobile upon CO adsorption but became more three-dimensional. Careful analysis of the experimental data complemented by ab initio density functional theory calculations provides insight into the origin of the CO-induced Pt cluster ripening and shape transformations.

Lattice match in density functional calculations: ice Ih vs. beta-AgI.

Density functional optimizations of the crystal parameters of ice Ih and beta-AgI imply lattice mismatches of 4.2 to 7.9%, in a survey of eight common, approximate (non-hybrid) functionals, too large to allow a meaningful contribution from Density Functional Theory to the discussion of the significance of lattice match in ice nucleation.

Lubrication theory of drag on a scanning probe in structured water, near a hydrophilic surface.

The drag is evaluated, in lubrication theory, on a parabolic-cylindrical tip moving parallel to a flat sample, in water, close enough that the presumed nanometer-thick, structured-water, "interphase" coatings of both it and the sample overlap. Assuming coatings of width, w, and of viscosity, eta, much larger than bulk water's, the friction force is predicted to equal -2pietacRphi(D/2w), where R is the tip's radius of curvature, c is its speed, D is the tip-sample separation, and Phi is a universal function whose value only differs noticeably from ln(2w/D) for D < w.

Two-dimensional Ir cluster lattice on a graphene moiré on Ir(111).

Lattices of Ir clusters have been grown by vapor phase deposition on graphene moirés on Ir(111). The clusters are highly ordered, and spatially and thermally stable below 500 K. Their narrow size distribution is tunable from 4 to about 130 atoms. A model for cluster binding to the graphene is presented based on scanning tunneling microscopy and density functional theory. The proposed binding mechanism suggests that similar cluster lattices might be grown of materials other than Ir.

Effect of high-viscosity interphases on drainage between hydrophilic surfaces.

Drainage of water from the region between an advancing probe tip and a flat sample is reconsidered under the assumption that the tip and sample surfaces are both coated by a thin water "interphase" (of width approximately a few nanometers) whose viscosity is much higher than that of the bulk liquid. A formula derived by solving the Navier-Stokes equations allows one to extract an interphase viscosity of approximately 59 kPa x s (or approximately 6.6 x 10(7) times the viscosity of bulk water at 25 degrees C) from interfacial force microscope measurements with both tip and sample functionalized hydrophilic by OH-terminated tri(ethylene glycol) undecylthiol, self-assambled monolayers.

Reactive wetting: H2O/Rh(111).

First-principles calculations imply that neither H2O bilayers nor half-dissociated, H2O+OH+H monolayers are thermodynamically stable on clean Rh(111). Thus, the experimental observation that Rh(111) supports a periodic 2D water adlayer needs an explanation. Chemistry involving common surface impurities, notably C atoms, may be the answer. Calculations show they provide favorable binding sites for H atoms detached from H2O. The resulting OH fragments can anchor a 2D water layer to the surface.

Experimental evidence for a partially dissociated water bilayer on Ru[0001].

Core-level photoelectron spectra, in excellent agreement with ab initio calculations, confirm that the stable wetting layer of water on Ru[0001] contains O-H and H2O in roughly 3:5 proportion, for OHx coverages between 0.25 and 0.7 ML, and T<170 K. Proton disorder explains why the wetting structure looks to low energy electron diffraction (LEED) to be an ordered p(square root of 3 x square root of 3)R30 degrees adlayer, even though approximately 3/8 of its molecules are dissociated. Complete dissociation to atomic oxygen starts near 190 K. Low photon flux in the synchrotron experiments ensured that the diagnosis of the nature of the wetting structure quantified by LEED is free of beam-induced damage.

Novel water overlayer growth on Pd(111) characterized with scanning tunneling microscopy and density functional theory.

Scanning tunneling microscopy (STM) images of water submonolayers on Pd(111) reveal quasiperiodic and isolated adclusters with internal structure that would ordinarily be ascribed to icelike puckered hexagonal units. However, density functional theory and STM simulations contradict this conventional picture, showing instead that the water adlayers are composed mainly of flat-lying molecules arranged in planar water hexagons. A new rule for two dimensional (2D) water growth is offered that generates the structures observed experimentally from planar hexamer units.