| 1. |
- Andersen, J. N., et al.
(author)
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Vibrational fine structure in the C 1s core level photoemission of chemisorbed molecules : Ethylene and ethylidyne on Rh(111)
- 1997
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In: Chemical Physics Letters. - 0009-2614. ; 269:3-4, s. 371-377
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Journal article (peer-reviewed)abstract
- 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.
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| 2. |
- Beutler, A., et al.
(author)
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Coverage- and temperature-dependent site occupancy of carbon monoxide on Rh(111) studied by high-resolution core-level photoemission
- 1998
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In: Surface Science. - 0039-6028. ; 396:1-3, s. 117-136
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Journal article (peer-reviewed)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.
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| 3. |
- Beutler, A., et al.
(author)
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On the adsorption sites for CO on the Rh(111) single crystal surface
- 1997
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In: Surface Science. - 0039-6028. ; 371:2-3, s. 381-389
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Journal article (peer-reviewed)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 x 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.
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| 4. |
- Jaworowski, A. J., et al.
(author)
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Adsorption sites in O and CO coadsorption phases on Rh(111) investigated by high-resolution core-level photoemission
- 1999
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In: Surface Science. - 0039-6028. ; 431:1, s. 33-41
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Journal article (peer-reviewed)abstract
- 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.
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| 5. |
- Strisland, F., et al.
(author)
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Adsorption sites in coadsorption systems determined by photoemission spectroscopy : K and CO coadsorbed on Rh(111)
- 1998
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In: Surface Science. - 0039-6028. ; 410:2-3, s. 330-343
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Journal article (peer-reviewed)abstract
- The adsorption sites of coadsorbed K and CO on the Rh(111) surface have been determined using high-resolution core-level spectroscopy, low-energy electron diffraction and site-resolved photoelectron diffraction. For both a (2 × 2)-2CO-1K and a (2√3 × 2√3)-6CO-1K structure, we find that the CO molecules occupy threefold hollow sites and the K atoms on-top sites, contrary to the adsorption sites of K (threefold hollow site) and CO (on-top site below 0.5 monolayers) if adsorbed alone on Rh(111). Deposition of K onto a CO precovered surface is found to induce large shifts towards lower binding energy of the C and O 1s core levels (∼0.7 eV for C 1s and ∼1.5 eV for O 1s). The major part of these shifts is shown to arise from the K-induced site change of the CO molecules. This finding may be of importance in the interpretation of XPS data of related co-adsorption systems. Finally, it is suggested that the C and O 1s binding energies provide useful fingerprints of the CO adsorption site also for co-adsorption systems.
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