Energy shifts in photoemission lines during the tetragonal- to cubic-phase transition in BaTiO3 single crystals and systems with CoFe2O4 and NiFe2O4 overlayers.

In BaTiO3 the phase transition from tetragonal to cubic is connected with the disappearance of the ferroelectric polarization. In photoelectron spectroscopy huge transient shifts in the binding energies of all core-level photoemission lines have been observed while heating and cooling through the Curie temperature. Excitation energies from 2 keV to 6 keV have been used to show this to be a bulk effect and not a surface effect alone. These observations are discussed in terms of charging, which results from the disappearance of the ferroelectric polarization. This mechanism has previously been proposed as the origin of electron emission in ferroelectric materials. Besides the jump-like shifts, additional permanent shifts in binding energies have been observed for the tetragonal and the cubic phase. These experimental shifts have been related to theoretical ones from ab initio calculations. In addition to BaTiO3 single crystals, systems with CoFe2O4 and NiFe2O4 overlayers on BaTiO3 have been investigated. The low conductivity of these layers sets them apart from metallic overlayers like Fe or Co, where the shifts are suppressed. This difference adds further support for charging as the origin of the effect.

XMCD studies of thin Co films on BaTiO3.

Different layer thicknesses of cobalt ranging from 2.6 Å (1.5 ML) up to 55 Å (30.5 ML) deposited on ferroelectric BaTiO3 have been studied regarding their magnetic behavior. The layers have been characterized using XMCD spectroscopy at remanent magnetization. After careful data analysis the magnetic moments of the cobalt could be determined using the sum rule formalism. There is a sudden and abrupt onset in magnetism starting at thicknesses of 9 Å (5 ML) of cobalt for measurements at 120 K and of 10 Å (5.5 ML) if measured at room temperature. Initial island growth and subsequent coalescence of Co on BaTiO3 is suggested to explain the sudden onset. In that context, no magnetically dead layers are observed.

Ethene adsorption and dehydrogenation on clean and oxygen precovered Ni(111) studied by high resolution x-ray photoelectron spectroscopy.

The adsorption and thermal evolution of ethene (ethylene) on clean and oxygen precovered Ni(111) was investigated with high resolution x-ray photoelectron spectroscopy using synchrotron radiation at BESSY II. The high resolution spectra allow to unequivocally identify the local environment of individual carbon atoms. Upon adsorption at 110 K, ethene adsorbs in a geometry, where the two carbon atoms within the intact ethene molecule occupy nonequivalent sites, most likely hollow and on top; this new result unambiguously solves an old puzzle concerning the adsorption geometry of ethene on Ni(111). On the oxygen precovered surface a different adsorption geometry is found with both carbon atoms occupying equivalent hollow sites. Upon heating ethene on the clean surface, we can confirm the dehydrogenation to ethine (acetylene), which adsorbs in a geometry, where both carbon atoms occupy equivalent sites. On the oxygen precovered surface dehydrogenation of ethene is completely suppressed. For the identification of the adsorbed species and the quantitative analysis the vibrational fine structure of the x-ray photoelectron spectra was analyzed in detail.

Interaction between silver nanowires and CO on a stepped platinum surface.

We studied the interplay between Ag decoration of a stepped Pt(355) surface and CO adsorption by in situ high-resolution x-ray photoelectron spectroscopy. Varying amounts of Ag deposited at 300 K initially lead to a row-by-row growth starting from the lower Pt step edges. Such decoration of the step sites results in a change in the CO adsorption behavior. An apparent blocking of step sites for low CO coverages is attributed to a change in the electronic structure, resulting in a C 1s binding energy of CO at step sites being equal to that for CO at terrace on-top sites in the presence of Ag. Higher CO coverages induce the formation of embedded Ag clusters within the upper terraces, thus freeing up a part of the original Pt step sites for CO adsorption, as was derived by a comparison to density functional theory calculations in the corresponding surface models.

Site blocking and CO/sulfur site exchange processes on stepped Pt surfaces.

The influence of preadsorbed sulfur on the adsorption of CO on Pt(355) and Pt(322) is investigated systematically for sulfur precoverages between 0.02 and 0.30 ML by in situ x-ray photoelectron spectroscopy of the C 1s and S 2p core levels. The two surfaces have the same nominal terrace width of 5 atomic rows, but different step orientation. For both, at low temperatures (130 and 150 K), S preferentially adsorbs at the steps and passivates them for CO adsorption. The required S precoverage is significantly smaller for Pt(322), because of the lower number of steps as a result of the S-induced double-step formation. Upon heating, population of step sites with CO occurs due to irreversible CO/S site exchange. At low S precoverages, the characteristic transition temperatures of 165 K for Pt(355) and 245 K for Pt(322) are significantly different, indicating a higher activation barrier for the CO/S site exchange process for Pt(322). For medium to high S precoverages the transition temperature stays unchanged for Pt(322) but increases for Pt(355). The observed behavior is attributed to a kinetic passivation of the steps by sulfur at low temperatures, which is lifted upon heating.

Adsorption and reaction of cyclohexene on a Ni(111) surface.

We studied the adsorption and reaction of cyclohexene (C6H10) on Ni(111) at different temperatures with high-resolution in-situ X-ray photoelectron spectroscopy (HR-XPS). For exposure at 125 K, we find intact cyclohexene with two distinct C 1s signals at 283.3 and 284.2 eV, due to the nonequivalent carbon atoms in the molecule. The energetic separation is significantly increased relative to the gas-phase value, due to the interaction with the substrate. Upon exposure at 210 K, complete dehydrogenation of cyclohexene to benzene (C6H6) and hydrogen is observed; coverage-dependent changes of the benzene adsorption site occur in a way similar to those for pure benzene layers, which indicates a phase separation in benzene and hydrogen islands. The thermal evolution of the adsorbed layers was studied by temperature-programmed (TP-) XPS and temperature-programmed desorption spectroscopy (TPD). Upon heating, the benzene + hydrogen layer formed at 210 K shows a coverage-dependent reorientation of the benzene molecules during partial desorption. The cyclohexene layer adsorbed at 125 K only shows partial conversion of cyclohexene to benzene and hydrogen upon heating to 185 or 210 K, with the remaining cyclohexene being stable up to approximately 300 K. We propose that upon heating these molecules are stabilized by coadsorbed benzene and hydrogen; furthermore, the mobility of benzene and hydrogen in this coadsorbed layer is reduced, so that no phase separation can occur.

A detailed analysis of vibrational excitations in x-ray photoelectron spectra of adsorbed small hydrocarbons.

The vibrational fine structure of x-ray photoelectron (XP) spectra of a number of different small hydrocarbon molecules and reaction intermediates adsorbed on Pt(111) and Ni(111) has been investigated in detail. The data for methyl, methylidyne, acetylene, and ethylene can consistently be analyzed within the linear coupling model. The S factor, i.e., the intensity ratio of the first vibrationally excited to the adiabatic transition, is obtained to be 0.17+/-0.02 per C-H bond; for the deuterated species a value of 0.23+/-0.02 is obtained. Therefore, the vibrational fine structure can be used for fingerprinting in the analysis of XP spectra and for identifying unknown reaction intermediates. From the data, Deltar, the change of the minimum in the potential energy curve upon core ionization, is calculated within the linear coupling model using a first order correction. For all adsorbates, including the deuterated ones, a value of Deltar=0.060+/-0.004 A is obtained. Furthermore, from the binding energy of the adiabatic peak and from the energy of the vibrational excitation in the ionic final state some information on the adsorbate/substrate bond and the adsorption site can be derived.

A site-selective in situ study of CO adsorption and desorption on Pt(355).

Using time-dependent high-resolution x-ray photoelectron spectroscopy at BESSY II, the adsorption and desorption processes of CO on stepped Pt(355) = Pt[5(111) x (111)] were investigated. From a quantitative analysis of C 1s data, the distribution of CO on the various adsorption sites can be determined continuously during adsorption and desorption. These unique data show that the terrace sites are only occupied when the step sites are almost saturated, even at temperatures as low as 130 K. The coverage-dependent occupation of on-top and bridge adsorption sites on the (111) terraces of Pt(355) is found to differ from that on Pt(111), which is attributed to the finite width of the terraces and changes in adsorbate-adsorbate interactions. In particular, no long-range order of the adsorbate layer could be observed by low-energy electron diffraction. Further details are derived from sticking coefficient measurements using the method devised by King and Wells [Proc. R. Soc. London, Ser. A 339, 245 (1974)] and temperature-programmed desorption. The CO saturation coverage is found to be slightly smaller on the stepped surface as compared to that on Pt(111). The initial sticking coefficient has the same high value of 0.91 for both surfaces.

Hydrogenation of single-walled carbon nanotubes.

Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls, and such C-H bonds can be completely broken by heating to 600 degrees C. We demonstrate approximately 65 +/- 15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes, which is equivalent to 5.1 +/- 1.2 wt % hydrogen capacity. We also show that the hydrogenation is a reversible process.

Kinetics of the CO oxidation reaction on Pt(111) studied by in situ high-resolution x-ray photoelectron spectroscopy.

High-resolution x-ray photoelectron spectroscopy has been used to study the kinetics of the CO oxidation reaction on a Pt(111) surface in situ. The study focuses on the interaction of a preadsorbed p(2x2) layer of atomic oxygen with CO dosed using a supersonic molecular beam. Measurements of O 1s and C 1s spectra at 120 K show that CO adsorbs on the oxygen precovered substrate, but no reaction occurs. A maximum CO coverage of 0.23 ML (monolayer) is observed, with CO exclusively bound on on-top sites. In accordance with the literature, bridge sites are blocked by the presence of atomic oxygen. The reaction of CO with preadsorbed O to CO(2) is studied isothermally in a temperature range between 275 and 305 K. The reaction rate initially increases with CO pressure, but saturates at 9x10(-7) mbar. The data indicate that a certain amount of disordered oxygen within the p(2x2) layer acts as a starting point of the reaction and for a given temperature reacts with a higher rate than O in the well-ordered oxygen p(2x2) phase. For the reaction of CO with this ordered phase, the results confirm the assumption of a reaction mechanism, which is restricted to the edges of compact oxygen islands. The activation energy of the reaction is determined to (0.53+/-0.04) eV, with a prefactor of 4.7x10(6+/-0.7) s(-1).

Multi-atom resonant photoemission: A method for determining near-neighbor atomic identities and bonding

Measurements and theoretical calculations are reported for an interatomic multi-atom resonant photoemission (MARPE) effect that permits direct determination of near-neighbor atomic identities (atomic numbers). MARPE occurs when the photon energy is tuned to a core-level absorption edge of an atom neighboring the emitting atom, with the emitting level having a lower binding energy than the resonant level. Large peak-intensity enhancements of 33 to 105 percent and energy-integrated effects of 11 to 29 percent were seen in three metal oxides. MARPE should also be sensitive to bond distance, bonding type, and magnetic order, and be observable via the secondary processes of x-ray fluorescence and Auger decay.

[Morphologic studies of reactive changes in the joint cartilage in experimental erysipelas arthritis]. / Morphologische Utersuchungen zu reaktiven Veränderungen des Gelenkknorpels bei experimenteller Rotlauf-Arthritis.

In experimentally Erysipelothrix rhusiopathiae-induced polyarthritis of pigs, important pathomechanisms of bacterial invasion of the articular cartilage matrix were studied. Furthermore, observations were made concerning inflammatory cartilage changes in the transitional zone of the distal femur condyle. The morphological changes were a loss of proteoglycans, proliferation and transformation of cartilage cells, compensatory formation of collagenous fibers progressing to cartilage fibrosis and pannus formation. As histology only represents a static picture, different methods are necessary to finally verify the dynamics of this process. It appears likely, that cartilage and pannus combined, and synergistically after fibroblastic transformation, produce a reparative scar in the area of cartilage alteration.

Articular cartilage canals--a new pathogenetic mechanism in infectious arthritis.

In experimentally-induced erysipelas polyarthritis, preexisting cartilage canals in articular cartilage play a crucial role during the very onset of the disease. This observation might have some implications for the pathogenesis of other infectious arthritides in young animals or even rheumatoid arthritis in man.

The role of cartilage canals in the pathogenesis of experimentally induced polyarthritis.

Porcine articular cartilage from cases of experimentally induced Erysipelas polyarthritis, a comparative model of rheumatoid arthritis (RA) in man, was examined with different histological and immunohistochemical techniques. The preexisting canals in articular cartilage played a crucial role during the flooding and deposition of arthritogenic microorganisms deep into the cartilage matrix. Subsequently this vascularized tissue mediated the same inflammatory reactions in hyaline cartilage of young animals as seen in other connective tissues. However, these stereotypical responses to injury were modulated by the unique composition and structure of articular cartilage.