The order-disorder transition of the (3x3)Sn/Ge(111) phase

Growing attention has been drawn in the past years to the \alpha-phase (1/3 monolayer) of Sn on Ge(111), which undergoes a transition from the low temperature (3x3) phase to the room temperature (\sqrt3 x \sqrt3)R30 one. On the basis of scanning tunnelling microscopy experiments, this transition was claimed to be the manifestation of a surface charge density wave (SCDW), i.e. a periodic redistribution of charge, possibly accompanied by a periodic lattice distortion, which determines a change of the surface symmetry. As further experiments with different techniques were being performed, increasing doubts were cast about the SCDW model. We have measured by He scattering the long range order of the 1/3 monolayer phase of Sn on the Ge(111) surface throughout the phase transition. The transition has been found of the order-disorder type with a critical temperature Tc=220 K. The expected 3-State Potts critical exponents are shown to be consistent with the observed power law dependence of the (3x3) order parameter and its correlation length close to Tc, thus excluding a charge density wave driven phase transition.Comment: 6 pages with 4 figures; updated reference

Quantum size effects in the low temperature layer-by-layer growth of Pb on Ge(001)

The electronic properties of thin metallic films deviate from the corresponding bulk ones when the film thickness is comparable with the wavelength of the electrons at the Fermi level due to quantum size effects (QSE). QSE are expected to affect the film morphology and structure leading to the low temperature (LT) ``electronic growth'' of metals on semiconductors. In particular, layer-by-layer growth of Pb(111) films has been reported for deposition on Ge(001) below 130 K. An extremely flat morphology is preserved throughout deposition from four up to a dozen of monolayers. These flat films are shown to be metastable and to reorganize into large clusters uncovering the first Pb layer, pseudomorphic to the substrate, already at room temperature. Indications of QSE induced structural variations of the growing films have been reported for Pb growth on Ge(001), where the apparent height of the Pb(111) monatomic step was shown to change in an oscillatory fashion by He atom scattering (HAS) during layer-by-layer growth. The extent of the structural QSE has been obtained by a comparison of the HAS data with X-ray diffraction (XRD) and reflectivity experiments. Whereas step height variations as large as 20 % have been measured by HAS reflectivity, the displacement of the atomic planes from their bulk position, as measured by XRD, has been found to mainly affect the topmost Pb layer, but with a lower extent, i.e. the QSE observed by HAS are mainly due to a perpendicular displacement of the topmost layer charge density. The effect of the variable surface relaxation on the surface vibration has been studied by inelastic HAS to measure the acoustic dispersion of the low energy phonons.Comment: 28 pages (laTex,elsart) and 13 figures (eps); updated reference

Tuning ultrafast electron injection dynamics at organic-graphene/metal interfaces

We compare the ultrafast charge transfer dynamics of molecules on epitaxial graphene and bilayer graphene grown on Ni(111) interfaces through first principles calculations and X-ray resonant photoemission spectroscopy. We use 4,4'-bipyridine as a prototypical molecule for these explorations as the energy level alignment of core-excited molecular orbitals allows ultrafast injection of electrons from a substrate to a molecule on a femtosecond timescale. We show that the ultrafast injection of electrons from the substrate to the molecule is 3c4 times slower on weakly coupled bilayer graphene than on epitaxial graphene. Through our experiments and calculations, we can attribute this to a difference in the density of states close to the Fermi level between graphene and bilayer graphene. We therefore show how graphene coupling with the substrate influences charge transfer dynamics between organic molecules and graphene interfaces

TiO2(110) charge donation to an extended π-Conjugated molecule

The surface reduction of rutile TiO2(110) generates a state in the band gap whose excess electrons are spread among multiple sites, making the surface conductive and reactive. The charge extraction, hence the surface catalytic properties, depends critically on the spatial extent of the charge redistribution, which has been hitherto probed by small molecules that recombine at oxygen vacancy (Ovac) sites. We demonstrate by valence band resonant photoemission (RESPES) a very general charge extraction mechanism from a reduced TiO2(110) surface to an extended electron-acceptor organic molecule. Perylene-tetra-carboxylic-diimide (PTCDI) is not trapped at Ovac sites and forms a closely packed, planar layer on TiO2(110). In this con\ufb01guration, the perylene core spills out the substrate excess electrons, \ufb01lling the lowest unoccupied molecular orbital (LUMO). The charge transfer from the reduced surface to an extended pi-conjugated system demonstrates the universality of the injection/extraction mechanism, opening new perspectives for the coupling of reducible oxides to organic semiconductors and supported catalysts

PH dependence of listeriolysin O aggregation and pore-forming ability

Listeriolysin O (LLO) is the major factor implicated in the escape of Listeria monocytogenes from the phagolysosome. It is the only representative of cholesterol-dependent cytolysins that exhibits pH-dependent activity. Despite intense studies of LLO pH-dependence, this feature of the toxin still remains incompletely explained. Here we used fluorescence and CD spectroscopy to show that the structure of LLO is not detectably affected by pH at room temperature. We observed slightly altered haemolytic and permeabilizing activities at different pH values, which we relate to reduced binding of LLO to the lipid membranes. However, alkaline pH and elevated temperatures caused rapid denaturation of LLO. Aggregates of the toxin were able to bind Congo red and Thioflavin T dyes and were visible under transmission electron microscopy as large, amorphous, micrometer-sized assemblies. The aggregates had the biophysical properties of amyloid. Analytical ultracentrifugation indicated dimerization of the protein in acidic conditions, which protects the protein against premature denaturation in the phagolysosome, where toxin activity takes place. We therefore suggest that LLO spontaneously aggregates at the neutral pH found in the host cell cytosol and that this is a major mechanism of LLO inactivation. © 2011 FEBS

Periodic arrays of Cu-phthalocyanine chains on Au(110)

The structure of ultrathin Cu-phthalocyanine (Cu-Pc) films on the (1 x 2)-Au(I 10) surface has been studied. The overlayer deposition has been monitored in real time by helium atom scattering (HAS) and low energy electron diffraction (LEED). Throughout the monolayer regime the Cu-Pc molecules are systematically observed to line-up edge-to-edge along the [110] direction of the Au substrate, yielding a commensurate 5-fold periodicity (14.4 angstrom). Cu-Pc chains deconstruct the 2-fold Au missing row order in the early stage of deposition. A set of higher order periodicities (5-, 7-, and 3-fold) are progressively observed along [001] with increasing CuPc deposition, the 3-fold phase appearing at the monolayer saturation coverage. The corresponding molecular orientation has been studied by variable polarization absorption spectroscopy (XAS), whereas the Au substrate structure has been determined by out-of-plane surface X-ray diffraction. The (5 x 5) phase is found to be rather corrugated, and it exhibits a high degree of long-range order yielding the most prominent diffraction pattern. In the (5 x 5) phase, the Cu-Pc chains are found to lift the underneath missing row reconstruction, being separated by residual Au rows. Similarly, in the more compressed 3-fold monolayer phase, the Cu-Pc molecules were formerly found to lie within a shallow (1 x 3) An reconstruction [Cossaro, A.; et al. J. Phys. Chem. B 2004, 108, 14671]. From comparison of the different deposition stages, as measured in real time by HAS, we can draw a comprehensive picture of the system evolution. In fact, the observed periodicities at different coverage are always formed by an array of Cu-Pc chains in shallow troughs that are equally spaced by a number of uncovered Au rows, as dictated by the Cu-Pc coverage. The growth of Cu-Pc arrays in the submonolayer range is thus driven by an interchain repulsion mechanism

Copper-phthalocyanine induced reconstruction of Au(110)

The structure of ultrathin Cu-phthalocyanine (Cu-Pc) film on Au(110) has been studied by means of several diffraction tecniques: helium atom scattering (HAS), low energy electron diffraction (LEED) and grazing incidence X-ray diffraction (GIXD). HAS has been used to measure the long range order of the organic overlayer, whereas LEED at 200 eV has been used to probe the corresponding substrate reconstruction. At the monolayer coverage, the Au(110) substrate displays a reconstruction with a 3-fold periodicity along the [001] direction, whose structure has been studied by out of plane GIXD and variable polarization X-ray absorption near edge spectroscopy (XANES). We found the structure of the substrate unit cell to be an asymmetric shallow (1 x 3) reconstruction with the Cu-Pc molecules tilted by an angle of similar to32degrees from the (110) surface plane

Copper-phthalocyanine induced reconstruction of Au(110)

The structure of ultrathin Cu-phthalocyanine (Cu-Pc) film on Au(110) has been studied by means of several diffraction tecniques: helium atom scattering (HAS), low energy electron diffraction (LEED) and grazing incidence X-ray diffraction (GIXD). HAS has been used to measure the long range order of the organic overlayer, whereas LEED at 200 eV has been used to probe the corresponding substrate reconstruction. At the monolayer coverage, the Au(110) substrate displays a reconstruction with a 3-fold periodicity along the [001] direction, whose structure has been studied by out of plane GIXD and variable polarization X-ray absorption near edge spectroscopy (XANES). We found the structure of the substrate unit cell to be an asymmetric shallow (1 x 3) reconstruction with the Cu-Pc molecules tilted by an angle of similar to32degrees from the (110) surface plane