Georg Held

Determination of adsorption sites of pure and coadsorbed CO on Ni(111) by high resolution X-ray photoelectron spectroscopy

O 1s and C 1s peak positions from high resolution X-ray photoelectron spectroscopy were used to determine adsorption sites of CO and CO coadsorbed with O and benzene, respectively, on Ni(111). Pure CO layers at 80 K were characterised by low energy electron diffraction and temperature programmed desorption and studied by X-ray photoelectron spectroscopy in a wide coverage range. For low coverages up to the well-known c(4 × 2) structure (ΘCO = 0.5 ML) the CO resides on threefold hollow sites. In the structure (ΘCO = 0.57 ML) the on-top and bridge sites are occupied; for the compressed rect structure (ΘCO = 0.62 ML) there is no clear preference for high symmetry adsorption sites. At room temperature the additional occupation of on-top and bridge sites is even observed at low coverages. In the (benzene + 2CO) structure the CO resides most likely on threefold hollow sites with benzene molecules occupying the same adsorption sites. After the adsorption onto a p(2 × 2) oxygen layer at about 100 K the CO occupies two sites: on-top and bridge or hollow sites. If this layer is annealed to 260 K only the on-top sites are left on the surface.

Kinetic parameters of CO adsorbed on Pt(111) studied by in situ high resolution x-ray photoelectron spectroscopy

The kinetics of the adsorption system CO/Pt(111) has been studied by time-resolved high-resolution x-ray photoelectron spectroscopy using third generation synchrotron radiation at BESSY II. CO is dosed by a supersonic molecular beam device which allows for a high sample pressure (here up to 10−6 mbar) and a fast switching of the pressure. The site-specific occupation of CO adsorbed on on-top and bridge sites is determined quantitatively from C 1s spectra, which can be taken with a minimum collection time of 1.5 s per spectrum. Based on the observation of thermal equilibrium between the two sites, we perform a phenomenological analysis of the data, assuming a constant binding energy difference ΔE. From the on-top/bridge occupation ratio as a function of coverage obtained by uptake measurements we extract a value of ΔE=41 meV. With the same ansatz, ΔE is calculated from temperature-dependent measurements at a constant coverage. Finally, determination of the coverage during isothermal desorption is used to o...

Realistic molecular distortions and strong substrate buckling induced by the chemisorption of benzene on Ni{111}

A detailed structural determination of the Ni{111}–(√7×√7)R19.1°–C6H6 overlayer has been performed using automated fully dynamical low energy electron diffraction I–V analysis. In the most likely geometry (RP = 0.26, total energy range: 1552 eV) benzene adsorbs with its center 1.91 A above an hcp site and with its C–C bonds oriented parallel to the close‐packed rows of the substrate. The molecular radius is found to be slightly expanded relative to the gas phase (1.48 A and 1.50 A vs 1.40 A) and no significant vertical buckling can be seen (< 0.04±0.05 A). The topmost Ni layer is strongly buckled (0.14 A) with the height of the Ni atoms decreasing with increasing lateral distance from the molecule (+0.08, 0.00, and –0.06 A with respect to the clean surface). A second similarly low RP factor minimum for adsorption on a bridge site was dismissed because of significantly higher R1 and R2 values and the extreme molecular distortions of this geometry. The resulting structure is fully consistent with recent UPS...

A low‐energy electron diffraction data acquisition system for very low electron doses based upon a slow scan charge coupled device camera

We have developed a video low‐energy electron diffraction (LEED) system on the basis of a slow scan charge coupled device (CCD) camera which is capable of collecting LEED IV data at very low electron doses quickly and therefore enables us to study extremely beam sensitive surface structures which have not been accessible to LEED IV analysis before. The slow scan CCD camera allows separating the relatively short data acquisition process from the more lengthy digitizing, storage, and data analysis processes. Typical total effective exposure times can therefore be reduced to about 200–300 s (1 s per energy point) at a primary beam current of 100 nA which corresponds to a total dose of about 12 e per adsorbate particle; further decrease is possible. The total measurement time for collecting a complete set of LEED images is of the order of 30–40 min which assures the exclusion of contamination effects, even for sensitive layers. The IV curves are then extracted from the digitally stored images off‐line which a...

Chemical composition and reactivity of water on hexagonal Pt-group metal surfaces.

The dissociation behaviour and valence-electronic structure of water adsorbed on clean and oxygen-covered Ru{0001}, Rh{111}, Pd{111}, Ir{111} and Pt{111} surfaces has been studied by high-resolution X-ray photoelectron spectroscopy with the aim of identifying similarities and trends within the Pt-group metals. On average, we find higher reactivity for the 4d metals (Ru, Rh, Pd) as compared to 5d (Ir, Pt), which is correlated with characteristic shifts in the 1b(1) and 3a(1) molecular orbitals of water. Small amounts of oxygen (< 0.2 ML) induce dissociation of water on all five surfaces, for higher coverages (> 0.25 ML) only intact water is observed. Under UHV conditions these higher coverages can only be reached on the 4d metals, the 5d metals are, therefore, not passivated.

Global and local expression of chirality in serine on the Cu{110} surface

Establishing a molecular-level understanding of enantioselectivity and chiral resolution at the organic-inorganic interfaces is a key challenge in the field of heterogeneous catalysis. As a model system, we investigate the adsorption geometry of serine on Cu{110} using a combination of low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The chirality of enantiopure chemisorbed layers, where serine is in its deprotonated (anionic) state, is expressed at three levels: (i) the molecules form dimers whose orientation with respect to the substrate depends on the molecular chirality, (ii) dimers of L- and D-enantiomers aggregate into superstructures with chiral (-1 ∓2; 4 0) lattices, respectively, which are mirror images of each other, and (iii) small islands have elongated shapes with the dominant direction depending on the chirality of the molecules. Dimer and superlattice formation can be explained in terms of intra- and interdimer bonds involving carboxylate, amino, and β-OH groups. The stability of the layers increases with the size of ordered islands. In racemic mixtures, we observe chiral resolution into small ordered enantiopure islands, which appears to be driven by the formation of homochiral dimer subunits and the directionality of interdimer hydrogen bonds. These islands show the same enantiospecific elongated shapes those as in low-coverage enantiopure layers.

The structure of the mixed OH+H2O overlayer on Pt{111}

The structure of the mixed p(3 x 3)-(3OH + 3H2O) phase on Pt[111] has been investigated by low-energy electron diffraction-IV structure analysis. The OH + H2O overlayer consists of hexagonal rings of coplanar oxygen atoms interlinked by hydrogen bonds. Lateral shifts of the O atoms away from atop sites result in different O-O separations and hexagons with only large separations (2.81 and 3.02 angstroms) linked by hexagons with alternating separations of 2.49 and 2.813.02 angstroms. This unusual pattern is consistent with a hydrogen-bonded network in which water is adsorbed in cyclic rings separated by OH in a p(3 x 3) structure. The top-most two layers of the Pt atoms relax inwards with respect to the clean surface and both show vertical buckling of up to 0.06 angstroms. In addition, significant shifts away from the lateral bulk positions have been found for the second layer of Pt atoms.

Hydrogen Bond-Induced Pair Formation of Glycine on the Chiral Cu{531} Surface

Enantio-specific interactions on intrinsically chiral or chirally modified surfaces can be identified experimentally via comparison of the adsorption geometries of similar nonchiral and chiral molecules. Information about the effects of substrate-related and intermolecular interactions on the adsorption geometry of glycine, the only natural nonchiral amino acid, is therefore important for identifying enantio-specific interactions of larger chiral amino acids. We have studied the long- and short-range adsorption geometry and bonding properties of glycine on the intrinsically chiral Cu{531} surface with low-energy electron diffraction, near-edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. For coverages between 0.15 and 0.33 ML (saturated chemisorbed layer) and temperatures between 300 and 430 K, glycine molecules adsorb in two different azimuthal orientations, which are associated with adsorption sites on the {110} and {311} microfacets of Cu{531}. Both types of adsorption sites allow a triangular footprint with surface bonds through the two oxygen atoms and the nitrogen atom. The occupation of the two adsorption sites is equal for all coverages, which can be explained by pair formation due to similar site-specific adsorption energies and the possibility of forming hydrogen bonds between molecules on adjacent {110} and {311} sites. This is not the case for alanine and points toward higher site specificity in the case of alanine, which is eventually responsible for the enantiomeric differences observed for the alanine system.

Alignment of a model amyloid peptide fragment in bulk and at a solid surface

The alignment of model amyloid peptide YYKLVFFC is investigated in bulk and at a solid surface using a range of spectroscopic methods employing polarized radiation. The peptide is based on a core sequence of the amyloid beta (Abeta) peptide, KLVFF. The attached tyrosine and cysteine units are exploited to yield information on alignment and possible formation of disulfide or dityrosine links. Polarized Raman spectroscopy on aligned stalks provides information on tyrosine orientation, which complements data from linear dichroism (LD) on aqueous solutions subjected to shear in a Couette cell. LD provides a detailed picture of alignment of peptide strands and aromatic residues and was also used to probe the kinetics of self-assembly. This suggests initial association of phenylalanine residues, followed by subsequent registry of strands and orientation of tyrosine residues. X-ray diffraction (XRD) data from aligned stalks is used to extract orientational order parameters from the 0.48 nm reflection in the cross-beta pattern, from which an orientational distribution function is obtained. X-ray diffraction on solutions subject to capillary flow confirmed orientation in situ at the level of the cross-beta pattern. The information on fibril and tyrosine orientation from polarized Raman spectroscopy is compared with results from NEXAFS experiments on samples prepared as films on silicon. This indicates fibrils are aligned parallel to the surface, with phenyl ring normals perpendicular to the surface. Possible disulfide bridging leading to peptide dimer formation was excluded by Raman spectroscopy, whereas dityrosine formation was probed by fluorescence experiments and was found not to occur except under alkaline conditions. Congo red binding was found not to influence the cross-beta XRD pattern.

The Importance of Attractive Three-Point Interaction in Enantioselective Surface Chemistry: Stereospecific Adsorption of Serine on the Intrinsically Chiral Cu{531} Surface

Both enantiomers of serine adsorb on the intrinsically chiral Cu{531} surface in two different adsorption geometries, depending on the coverage. At saturation, substrate bonds are formed through the two oxygen atoms of the carboxylate group and the amino group (μ3 coordination), whereas at lower coverage, an additional bond is formed through the deprotonated β-OH group (μ4 coordination). The latter adsorption geometry involves substrate bonds through three side groups of the chiral center, respectively, which leads to significantly larger enantiomeric differences in adsorption geometries and energies compared to the μ3 coordination, which involves only two side groups. This relatively simple model system demonstrates, in direct comparison, that attractive interactions of three side groups with the substrate are much more effective in inducing strong enantiomeric differences in heterogeneous chiral catalyst systems than hydrogen bonds or repulsive interactions.