J. N. Andersen

Beamline I311 at MAX-LAB: A VUV/soft X-ray undulator beamline for high resolution electron spectroscopy

We describe a beamline based on a plane-grating monochromator and an end-station designed for high resolution photoemission and photoabsorption spectroscopy on surfaces and interfaces using undulator radiation in the energy range 30 1500 eV. The general design of the beamline is based on a horizontally focusing pre-mirror, an SX-700 type of plane-grating monochromator and re-focusing optics of Kirkpatrick-Baez design.

CO adsorption on Pd(1 1 1): a high-resolution core level photoemission and electron energy loss spectroscopy study

By combining high-resolution X-ray photoelectron and electron energy loss spectroscopies a comprehensive analysis of the adsorption of CO on Pd(1 1 1) at 300 K has been performed. The characteristic fingerprints for various CO‐ Pd(1 1 1) bonding configurations have been identified from the decomposition analysis of the adsorbate C 1s and the substrate Pd 3d5=2 core-level photoemission spectra obtained after CO adsorption at 120 K. The cO4 2U structure at 0.5 monolayer (ML) and theO2 2U-3CO structure at 0.75 ML formed at low temperature have been used for calibration purposes. The core-level results are consistent with CO adsorbing in a mixture of fcc and hcp threefold hollow sites in the cO4 2U structure and of hollow and on-top sites in theO2 2U structure, as reported in the literature. For CO adsorption at 300 K, a diAerent site occupation is evidenced by the presence of two components in the C 1s and Pd 3d5=2 core-level and C‐O stretching vibration lineshapes. At coverages up to 0.1 ML only fcc threefold hollow sites in a O AAA

On the adsorption sites for CO on the Rh(111) single crystal surface

Abstract High resolution photoemission applied to the C 1s and Rh 3d core levels has been used to investigate the adsorption sites at low temperature of CO on the Rh(111) single crystal surface as a function of CO coverage. Two different sites are found to be occupied by the CO molecules. At coverages up to 0.5 monolayers the majority of the molecules are found to adsorb in on-top sites whereas at higher coverages three-fold hollow sites become increasingly populated. The different C 1s binding energy of the CO molecules in these two sites makes it possible to measure diffraction induced intensity variations versus photon energy in a site specific manner. The saturation (2 × 2)-3CO structure formed at a coverage of 0.75 monolayers is argued to contain one on-top and two three-fold hollow molecules per unit cell.

Alkali metal adsorption on Al(111)

The submonolayer adsorption of Na, K, Rb, and Cs on the Al(111) surface at 100 K and at room temperature is investigated by high resolution core level spectroscopy and low energy electron diffraction. It is found that the first alkali atoms on the surface adsorb at surface defects. At higher coverages, up to approximately one third of the maximum submonolayer coverage, alkali atoms adsorbed at defects coexist with a dispersed phase. At higher coverages island formation is found to occur for the majority of the systems. It is argued that all of the ordered structures formed at room temperature involve a disruption of the Al(111) surface in contrast to the situation at 100 K where the alkali atoms adsorb as adatoms.

Vibrational fine structure in the C 1s core level photoemission of chemisorbed molecules : Ethylene and ethylidyne on Rh(111)

The origin of fine structure in the core-level photoemission spectra of the C2H4, C2D4, C2H3 and C2D3 molecules chemisorbed on Rh(111) is probed in a careful high-resolution study showing that this structure arises from internal molecular vibrations rather than from other chemically-shifted carbon atoms. It is shown by comparison of the adsorbate and gas-phase spectra that the underlying features are the same despite differences arising from adsorption. This new approach to the investigation of adsorbed molecules may prove to be useful in further studies of other systems and the possibility that such effects may exist could lead to the reinterpretation of other adsorbate systems.

Coverage- and temperature-dependent site occupancy of carbon monoxide on Rh(111) studied by high-resolution core-level photoemission

Abstract High-resolution core-level photoemission is used to study structural aspects for the molecular adsorption of CO on the Rh(111) single-crystal surface, and in particular to derive the adsorption sites. The site sensitivity of the core-level binding energy and the fact that the core level photoemission signal is proportional to the adsorbate coverage make it possible to study quantitatively how the occupation of different sites changes with temperature and/or CO coverage. For the CO Rh (111) adsorption system we find two sites (on-top and three-fold hollow) to be occupied by the CO molecules. At coverages up to 0.33 ML only on-top sites are occupied, whereas at higher coverages a mixture of three-fold hollow and on-top sites are found. The distribution between these two sites is found to depend strongly on temperature. Quantitative studies of these reversible, temperature-dependent site changes have been carried out for a number of CO coverages. For coverages between 0.33 and ∼0.54 ML, increasing the temperature results in part of the molecules moving from on-top to three-fold hollow sites. This change is strongest for a (4 × 4) structure formed at 0.5 ML where an order-disorder transition is observed at a temperature of 120 K. For coverages above ∼0.54 ML, increasing the temperature leads instead to a decrease of the relative occupation of the three-fold hollow sites. For coverages below 0.33 ML, the molecules occupy on-top sites at all temperatures.

Photoabsorption and the unoccupied partial density of states of chemisorbed molecules

The 1s to 2π* resonances have been studied for CO strongly chemisorbed on Ni(100) and weakly chemisorbed on Cu(100) using high resolution X-ray absorption spectroscopy. We show that the spectra can be consistently described in terms of the local density of unoccupied 2π* electron states with the Fermi level obtained from corresponding X-ray photoelectron spectra. The core hole is demonstrated to induce large shifts in the unoccupied 2π* density of states.

Vibrational fine structure in the C 1s photoemission spectrum of the methoxy species chemisorbed on Cu(100)

The C 1s photoemission spectrum of methoxy (CH3O) chemisorbed on Cu(100) is demonstrated to contain a resolvable fine structure due to excitation of the molecular C-H normal vibrational mode. The origin of the fine structure is ascertained by substituting hydrogen with deuterium in the methoxy overlayers and by comparison to gas-phase C 1s spectra for methanol (CH3OH). The vibrational fine structure is demonstrated to provide a fingerprint of the hydrocarbon group present on the surface.

The surface core-level shift of the Pd(100) single-crystal surface

The surface core-level shift of the Pd(100) single-crystal surface has been measured from high-resolution Pd 3d core-level spectra. The surface atoms are found to have 0.44+or-0.03 eV lower binding energy than the bulk atoms. The result is compared with theoretical estimates.

Adsorption sites in O and CO coadsorption phases on Rh(111) investigated by high-resolution core-level photoemission

High-resolution core-level spectroscopy is used in combination with low-energy electron diffraction (LEED) and photoelectron diffraction to identify the adsorption sites for three different coadsorbed phases consisting of ordered overlayers of oxygen coadsorbed with CO on the Rh(111) single-crystal surface. The three ordered overlayer structures, which may be denoted as 2O + CO/Rh(111), O + CO/Rh(111) and O+2CO/Rh(111), all show (2 × 2) LEED patterns. In the 2O + CO and O + CO phases the CO molecules are found to occupy only on-top sites while the O + 2CO phase shows CO molecules in both on-top and three-fold hollow sites. In all cases the oxygen atoms are found in three-fold hollow sites. For the O + CO and O + 2CO phases our results confirm previous determinations by LEED, while the 2O + CO phase has not been observed before on Rh(111). The core-level binding energies of the C 1s and O 1s core levels for both adsorbates are characteristics of the adsorption site and are very close to the binding energies found for the pure cases of only oxygen or CO adsorbed on Rh(111). In the coadsorption phases we find that the interaction between the adsorbates has only a minor influence on the core-level binding energies. For the O + 2CO/Rh(111) coadsorption phase we find that a full CO coverage is not obtained; less than 80% of the unit cells contain two CO molecules, in line with previous findings. (Less)