Ultrathin ordered titanium oxide films on Pt(111) surface are prepared by reactive evaporation of Ti in oxygen. By varying the Ti dose and the annealing conditions (i.e., temperature and oxygen pressure), six different long-range ordered phases are obtained. They are characterized by means of low-energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). By careful optimization of the preparative parameters, we find conditions where predominantly single phases of TiO(x), revealing distinct LEED pattern and STM images, are produced. XPS binding energy and photoelectron diffraction (XPD) data indicate that all the phases, except one (the stoichiometric rect-TiO2), are one monolayer thick and composed of a Ti-O bilayer with interfacial Ti. Atomically resolved STM images confirm that these TiO(x) phases wet the Pt surface, in contrast to rect-TiO2. This indicates their interface stabilization. At a low Ti dose (0.4 monolayer equivalents, MLE), an incommensurate kagomé-like low-density phase (k-TiO(x) phase) is observed where hexagons are sharing their vertexes. At a higher Ti dose (0.8 MLE), two denser phases are found, both characterized by a zigzag motif (z- and z'-TiO(x) phases), but with distinct rectangular unit cells. Among them, z'-TiO(x), which is obtained by annealing in ultrahigh vacuum (UHV), shows a larger unit cell. When the postannealing of the 0.8 MLE deposit is carried out at high temperatures and high oxygen partial pressures, the incommensurate nonwetting, fully oxidized rect-TiO2 is found The symmetry and lattice dimensions are almost identical with rect-VO2, observed in the system VO(x)/Pd(111). At a higher coverage (1.2 MLE), two commensurate hexagonal phases are formed, namely the w- [(square root(43) x square root(43)) R 7.6 degrees] and w'-TiO(x) phase [(7 x 7) R 21.8 degrees]. They show wagon-wheel-like structures and have slightly different lattice dimensions. Larger Ti deposits produce TiO2 nanoclusters on top of the different monolayer films, as supported both by XPS and STM data. Besides the formation of TiO(x) surfaces phases, wormlike features are found on the bare parts of the substrate by STM. We suggest that these structures, probably multilayer disordered TiO2, represent growth precursors of the ordered phases. Our results on the different nanostructures are compared with literature data on similar systems, e.g., VO(x)/Pd(111), VO(x)/Rh(111), TiO(x)/Pd(111), TiO(x)/Pt(111), and TiO(x)/Ru(0001). Similar and distinct features are observed in the TiO(x)/Pt(111) case, which may be related to the different chemical natures of the overlayer and of the substrate.

Extreme ultraviolet and X-ray free-electron lasers (FELs) produce short-wavelength pulses with high intensity, ultrashort duration, well-defined polarization and transverse coherence, and have been utilized for many experiments previously possible only at long wavelengths: multiphoton ionization, pumping an atomic laser and four-wave mixing spectroscopy. However one important optical technique, coherent control, has not yet been demonstrated, because self-amplified spontaneous emission FELs have limited longitudinal coherence. Single-colour pulses from the FERMI seeded FEL are longitudinally coherent, and two-colour emission is predicted to be coherent. Here, we demonstrate the phase correlation of two colours, and manipulate it to control an experiment. Light of wavelengths 63.0 and 31.5nm ionized neon, and we controlled the asymmetry of the photoelectron angular distribution by adjusting the phase, with a temporal resolution of 3as. This opens the door to new short-wavelength coherent control experiments with ultrahigh time resolution and chemical sensitivity

A significant fraction of superfluid helium nanodroplets produced in a free-jet expansion has been observed to gain high angular momentum resulting in large centrifugal deformation. We measured single-shot diffraction patterns of individual rotating helium nanodroplets up to large scattering angles using intense extreme ultraviolet light pulses from the FERMI free-electron laser. Distinct asymmetric features in the wide-angle diffraction patterns enable the unique and systematic identification of the three-dimensional droplet shapes. The analysis of a large data set allows us to follow the evolution from axisymmetric oblate to triaxial prolate and two-lobed droplets. We find that the shapes of spinning superfluid helium droplets exhibit the same stages as classical rotating droplets while the previously reported metastable, oblate shapes of quantum droplets are not observed. Our three-dimensional analysis represents a valuable landmark for clarifying the interrelation between morphology and superfluidity on the nanometer scale.

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International audienceThe two single-pass, externally seeded free-electron lasers (FELs) of the FERMI user facility are designed around Apple-II-type undulators that can operate at arbitrary polarization in the vacuum ultraviolet-to-soft x-ray spectral range. Furthermore, within each FEL tuning range, any output wavelength and polarization can be set in less than a minute of routine operations. We report the first demonstration of the full output polarization capabilities of FERMI FEL-1 in a campaign of experiments where the wavelength and nominal polarization are set to a series of representative values, and the polarization of the emitted intense pulses is thoroughly characterized by three independent instruments and methods, expressly developed for the task. The measured radiation polarization is consistently >90% and is not significantly spoiled by the transport optics; differing, relative transport losses for horizontal and vertical polarization become more prominent at longer wavelengths and lead to a non-negligible ellipticity for an originally circularly polarized state. The results from the different polarimeter setups validate each other, allow a cross-calibration of the instruments, and constitute a benchmark for user experiments

The effects of the high-temperature reduction of Rh/CeO, catalyst on t h e hydrogenation of CO, CO,, acetone and ethene, and on the hydrogenolysis of ethane, in transient and continuous conditions, have been investigated. The high-temperature reduction (HTR) at 773 K induced a transient Rh-CeO, interaction in t h e catalyst which enhances the rate of CO, CO, and acetone hydrogenation. Temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) show t h e reduction of Ce4+ to Ce3+ after HTR in t h e near surface layers. W e suggest that the oxygen vacancies on the support (i.e. presence of Ce3') can interact with t h e CO moiety promoting its activation.

The pulse duration, and, more generally, the temporal intensity profile of free-electron laser (FEL)\ud pulses, is of utmost importance for exploring the new perspectives offered by FELs; it is a nontrivial\ud experimental parameter that needs to be characterized. We measured the pulse shape of an extreme\ud ultraviolet externally seeded FEL operating in high-gain harmonic generation mode. Two different methods\ud based on the cross-correlation of the FEL pulses with an external optical laser were used. The two methods,\ud one capable of single-shot performance, may both be implemented as online diagnostics in FEL facilities.\ud The measurements were carried out at the seeded FEL facility FERMI. The FEL temporal pulse\ud characteristics were measured and studied in a range of FEL wavelengths and machine settings, and they\ud were compared to the predictions of a theoretical model. The measurements allowed a direct observation of\ud the pulse lengthening and splitting at saturation, in agreement with the proposed theory

Well-ordered ultrathin TiO x layers on Pt(111) surface, prepared by reactive evaporation of Ti in oxygen, were characterized by means of Ti 2p and O 1s core level and by valence band photoelectron spectroscopy. Depending on the details of the preparation procedures, a total of six well-ordered structures, each of them characterized by a well-defined low energy electron diffraction pattern, were obtained. The core level data show that this wide range of structures can be rationalized in two main groups, i.e., a group of three stoichiometric (labeled as k‘, rect, and rect‘) and a group of a three substoichiometric (labeled as z, z‘, and w) ordered films. The valence band data are rather consistent with this basic distinction. In fact, valence band spectra relative to stoichiometric or substoichiometric films share common features and are quite different from spectra relative to the other group. On the other hand, the valence band data appear to be more sensitive to the details of the film structure by also displaying electronic features that are particular to each individual film. The valence band data are discussed with the aid of theoretical and experimental results for bulk surfaces and compounds available in the literature. It turns out that mixing with Pt states plays a major role in determining the electronic structure of the reduced substoichiometric films, whose spectral data are also consistent with a stoichiometry close to TiO and with the presence of a Ti−Pt interface. This finding is in agreement with previously reported photoelectron diffraction data. The stoichiometric films show a valence band structure that is strongly reminiscent of the one measured on the stoichiometric bulk TiO2 surface. Deviations from the bulk band structure appear in the form of a narrowing of the band and in a shift toward lower binding energy. The band narrowing effect is attributed to the spatial confinement of the TiO2-like films, while the shift is attributed to mixing of film and Pt substrate derived states. Finally, the rect structure shows a (film thickness dependent) anomalous spectral shape that is tentatively attributed to its peculiar geometric structure.