F. Bournel

resonances in electron transmission (ETS) and x-ray absorption (XAS) spectroscopies of dimethyl(poly)sulphides (, 2, 3)

shape resonances involving S - C and S - S antibonding levels have been observed in low-energy electron transmission spectroscopy (ETS) and sulphur 1s excitation spectra (XAS) of dimethylsulphide (DMS), dimethyldisulphide (DMDS) and dimethyltrisulphide (DMTS). A correlation diagram is established for ionization energies (IEs) of valence occupied molecular orbitals, term values (TVs) of sulphur K-shell excited states and electron attachment energies (AEs) for temporary negative ion resonance states of these molecules showing a strong decrease of the HOMO - LUMO energy gap with the sulphur atom chain length.

Adsorption of acetonitrile and acrylonitrile on Si(0 0 1)-2×1 at room temperature studied by synchrotron radiation photoemission and NEXAFS spectroscopies

Abstract The present work is a comparative study of the adsorption modes of acetonitrile and of the conjugated molecule acrylonitrile on Si(0xa00xa01)-2×1 at room temperature, using synchrotron radiation photoemission spectroscopy (PES) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Both molecules chemisorb on the surface. Besides dissociated species revealed by PES, NEXAFS spectroscopy shows that a large fraction of acetonitrile molecules are di-σ bonded to the surface, e.g. after a [2+2]-like cycloaddition of the CN group with a silicon dimer. In the case of acrylonitrile, PES indicates that most of the molecules chemisorb non-dissociatively. Nevertheless multiple bonding geometries must be envisaged to account for the NEXAFS spectra: the major reaction products has a flat lying geometry, the two outer atoms of the molecule skeleton being bonded to two silicon atoms. Other geometries, which correspond to the reaction of the Cue605C bond with a silicon dimer or to the formation of a dative bond through the nitrogen lone pair with one silicon atom have also to be envisaged.

Empty levels probed by XAS and ETS in cyclic polymethylene sulfides (CH2)nS, n=2, 3, 4, 5

Abstract The sulfur K-shell photoabsorption spectra (XAS) and the electron transmission spectra (ETS) have been obtained for a series of cyclic polymethylene sulfides (CH 2 ) n S with n =2,xa03,xa04,xa05. These spectra are dominated by similar broad resonances with trapping of the impinging (ETS) or K-shell excited (XAS) electron in σ*(S–C) and π*(CH 2 ) orbitals. Calculation of the electron affinity is performed with the DFT/B3LYP technique and its evolution through this cyclic series and the corresponding open chain series of molecules shows good agreement with experimental results, enlightening the role of molecular strain in lowering the σ*(S–C) level in the three- and four-membered ring thio compounds.

Resonant Auger spectroscopy of solid acrylonitrile at the N K-edge

Abstract This work is a resonant Auger spectroscopy study of solid acrylonitrile at the N K-edge. The three π* NEXAFS transitions, denoted 3a″, 13a′ and 4a″ in the Cs symmetry group of the molecule, are polarized in the molecular plane (a′ symmetry) or perpendicular to it (a″ symmetry), the highest energy transition, 4a″, being close to the ionization potential (the term value is about −1 eV). A strong selectivity with the symmetry of the probed unoccupied orbital is observed for both participator and spectator channels intensities. At the 3a″ and 13a′ NEXAFS resonances, intense participator channels and strong spectator shifts are observed, indicative of a localization of the promoted electron around the core-hole. Departures from a Raman behavior are also seen and discussed in terms of possible vibronic effects. At the third NEXAFS resonance (4a″), two spectator branches are observed with two different spectator shifts. We propose that the electron promoted to this orbital remains localized around the core hole, however it has a non-zero probability of being transferred into a more ‘diffuse’ level.

Resonant Auger spectroscopy of poly(4-hydroxystyrene)

Abstract The electronic structure of poly(4-hydroxystyrene) (PHS), which presents strong similarities with that of phenol, has been studied via resonant Auger spectroscopy. Spectator shifts and relative intensities of participator channels are extracted from our data. Symmetry considerations on the occupied and unoccupied molecular orbitals (MO) are helpful in the assignment of the resonating valence band structures of PHS. However they are clearly not sufficient to explain the MO intensities when close-lying intermediate electronic states are involved, as interference effects may play an important role.

Adsorption of acetonitrile (CH{sub 3}CN) on Si(111)-7x7 at room temperature studied by synchrotron radiation core-level spectroscopies and excited-state density functional theory calculations

Neutron inelastic scattering has been used to examine the structural phase transition in deuterated benzil C{sub 14}D{sub 10}O{sub 2}. The transition in benzil, in which the unit cell goes from a trigonal P3{sub 1}21 unit cell above T{sub C} to a cell doubled P2{sub 1} unit cell below T{sub C}, leads to the emergence of a Bragg peak at the M-point of the high temperature Brillouin zone. It has previously been suggested that the softening of a transverse optic phonon at the {gamma}-point leads to the triggering of an instability at the M-point causing the transition to occur. This suggestion has been investigated by measuring the phonon spectrum at the M-point for a range of temperatures above T{sub C} and the phonon dispersion relation along the {gamma}-M direction just above T{sub C}. It is found that the transverse acoustic phonon at the M-point is of lower energy than the {gamma}-point optic mode and has a softening with temperature as T approaches T{sub C} from above that is much faster than that of the {gamma}-point optic mode. This behavior is inconsistent with the view that the {gamma}-point mode is responsible for triggering the phase transition. Rather the structural phase transition inmorexa0» benzil appears to be driven by a conventional soft TA mode at the M-point.«xa0lessThe double perovskites Sr{sub 2}FeMO{sub 6} (M=Re,Mo) belong to the important class of half-metallic magnetic materials. In this study we explore the effect of replacing the electronic 5d buffer element Re with variable valency by the main group element Sb with fixed valency. X-ray diffraction reveals Sr{sub 2}FeRe{sub 1-x}Sb{sub x}O{sub 6} (0<x<0.9) to crystallize without antisite disorder in the tetragonally distorted perovskite structure (space group I4/mmm). The ferrimagnetic behavior of the parent compound Sr{sub 2}FeReO{sub 6} changes to antiferromagnetic upon Sb substitution as was determined by magnetic susceptibility measurements. Samples up to a doping level of 0.3 are ferrimagnetic, while Sb contents higher than 0.6 result in an overall antiferromagnetic behavior. {sup 57}Fe and {sup 121}Sb Moessbauer spectroscopy specifies the valence state of Sb to be +5 within the whole range of substitution whereas the Fe valence state changes from +2.7 for the parent compound to +2.9 for Sr{sub 2}FeRe{sub 0.1}Sb{sub 0.9}O{sub 6}. Accordingly, Fe adopts the role of an electronic buffer element from Re upon heavy Sb doping. Additionally, {sup 57}Fe Moessbauer results show a coexistence of ferri- and antiferromagnetic clusters within the same perovskite-type crystal structure in the Sb substitution range 0.3<x<0.8, whereas Sr{sub 2}FeReO{sub 6} and Sr{submorexa0» 2}FeRe{sub 0.9}Sb{sub 0.1}O{sub 6} are purely ferrimagnetic and Sr{sub 2}FeRe{sub 0.1}Sb{sub 0.9}O{sub 6} contains antiferromagnetically ordered Fe sites only. Consequently, a replacement of the Re atoms by a nonmagnetic main group element such as Sb blocks the superexchange pathways -Fe-O-Re(Sb)-O-Fe- along the crystallographic axis of the perovskite unit cell and destroys the itinerant magnetism of the parent compound.«xa0lessWe have recently argued that manganites do not possess stripes of charge order, implying that the electron-lattice coupling is weak [Loudon et al., Phys. Rev. Lett. 94, 097202 (2005)]. Here we independently argue the same conclusion based on transmission electron microscopy measurements of a nanopatterned epitaxial film of La{sub 0.5}Ca{sub 0.5}MnO{sub 3}. In strain relaxed regions, the superlattice period is modified by 2% to 3% with respect to the parent lattice, suggesting that the two are not strongly tied.Minimalist theories of complex systems are broadly of two kinds: mean field and axiomatic. So far, all theories of complex properties absent from simple systems and intrinsic to glasses are axiomatic. Stretched Exponential Relaxation (SER) is the prototypical complex temporal property of glasses, discovered by Kohlrausch 150 years ago, and now observed almost universally in microscopically homogeneous, complex nonequilibrium materials, including luminescent electronic Coulomb glasses. A critical comparison of alternative axiomatic theories with both numerical simulations and experiments strongly favors channeled dynamical trap models over static percolative or energy landscape models. The topics discussed cover those reported since the authors review article in 1996, with an emphasis on parallels between channel bifurcation in electronic and molecular relaxation.The local atomic structure of the Ag induced Si(111)-({radical}(3)x{radical}(3)) surface has been investigated using photoelectron diffraction (PED) at 10 and 300 K. Two surface components, whose intensities varied by changing the photon energy as a consequence of diffraction effects, were observed in the Si 2p core-level spectra at both temperatures. The good agreement between the experimental PED patterns of the Si 2p surface components and the simulated PED patterns indicates that the atomic structure of this surface follows the inequivalent triangle model. Further, since the PED patterns obtained at 10 and 300 K resemble each other closely, we conclude that the local atomic structure of the Ag/Si(111)-({radical}(3)x{radical}(3)) surface is the same at the two temperatures, and thus that the origin of the transition reported in the literature is an order-disorder transition.Neutron diffraction was used to determine the crystal structure and magnetic ordering pattern of a La{sub 2}CuO{sub 4} single crystal, with and without applied magnetic field. A previously unreported, subtle monoclinic distortion of the crystal structure away from the orthorhombic space group Bmab was detected. The distortion is also present in lightly Sr-doped crystals. A refinement of the crystal structure shows that the deviation from orthorhombic symmetry is predominantly determined to drive a continuous reorientation of the copper spins from the orthorhombic b axis to the c axis, directly confirming predictions based on prior magnetoresistance and Raman scattering experiments. A spin-flop transition induced by a c-axis oriented field previously reported for nonstoichiometric La{sub 2}CuO{sub 4} is also observed, but the transition field (11.5 T) is significantly larger than that in the previous work.Positron annihilation spectroscopy was applied to study relaxed P-doped n-type and undoped Si{sub 1-x}Ge{sub x} layers with x up to 0.30. The as-grown SiGe layers were found to be defect free and annihilation parameters in a random SiGe alloy could be represented as superpositions of annihilations in bulk Si and Ge. A 2 MeV proton irradiation with a 1.6x10{sup 15} cm{sup -2} fluence was used to produce saturated positron trapping in monovacancy related defects in the n-type layers. The defects were identified as V-P pairs, the E center. The distribution of Si and Ge atoms surrounding the E center was the same as in the host lattice. The process leading to the formation of V-P pairs therefore does not seem to have a significant preference for either Si or Ge atoms. In undoped Si{sub 1-x}Ge{sub x} we find that a similar irradiation produces a low concentration of divacancies or larger vacancy defects and found no evidence of monovacancies surrounded by several Ge atoms.Structural properties of the spin chain and ladder compound Sr{sub 14}Cu{sub 24}O{sub 41} have been studied using high energy x-ray diffraction. Strong incommensurate modulation reflections are observed due to the lattice mismatch of the chain and ladder structure, respectively. While modulation reflections of low orders display only a weak temperature dependence, higher orders dramatically increase in intensity when cooling the sample to 10 K. All observed modulation reflections are indexed within a super space group symmetry and no structural phase transition could be identified between 10 K and room temperature. We argue that these modulation reflections are not caused by a fivefold periodicity of the chain lattice, as claimed by Fukuda et al., Phys. Rev. B 66, 012104 (2002), but that holes localize in the potential given by the lattice modulation, which in turn gives rise to a further deformation of the lattice.We report neutron diffraction experiments on the light-induced metastable state SI in single crystals of Na{sub 2}[Fe(CN){sub 5}NO]{center_dot}2D{sub 2}O. It is shown that the metastable state SI corresponds to a linkage isomer of the NO group, the so-called isonitrosyl configuration where the NO ligand is oxygen bound to the central iron atom.The impact of group-III vacancy diffusion, generated during dielectric cap induced intermixing, on the energy state transition and the inhomogeneity reduction in the InGaAs/GaAs quantum-dot structure is investigated. We use a three-dimensional quantum-dot diffusion model and photoluminescence data to determine the thermal and the interdiffusion properties of the quantum dot. The band gap energy variation related to the dot uniformity is found to be dominantly affected by the height fluctuation. A group-III vacancies migration energy H{sub m} for InGaAs quantum dots of 1.7 eV was deduced. This result is similar to the value obtained from the bulk and GaAs/AlGaAs quantum-well materials confirming the role of SiO{sub 2} capping enhanced group-III vacancy induced interdiffusion in the InGaAs quantum dots.We report vibrating wire viscometer experiments in the concentrated and dilute phase of saturated {sup 3}He-{sup 4}He mixtures showing that the slip length may become orders of magnitude larger than the mean free path due to specular scattering of the {sup 3}He quasiparticles with a {sup 4}He coating adsorbed at the surface of the wire. Since the liquid does not almost stick to the surface, the boundary conditions for fluid flow are unusual and not accounted for by the current theory for slip [H. Hoejgaard Jensen et al., J. Low Temp. Phys. 41, 473 (1980)]. The experimental results are in excellent agreement with a recent theory for slip [R. Bowley and J. Owers-Bradley, J. Low Temp. Phys. 136, 15 (2004)] which accounts for the effect of the cylindrical geometry and for velocity slip in directions normal as well as tangential to the surface of the wire. We find that our viscosity measurements in the dilute phase resulting from the data analysis based on the recent slip theory are in better agreement with the Fermi liquid theory than previous experimental results.Magnetization measurements prove that the magnetic properties of large-angle ({theta}>30 deg. ) bismuth bicrystals with a crystallite interface (CI) of twisting types essentially differ from well-known results on single-crystalline specimens. Two superconducting phases with T{sub c}{approx}8.4 K and {approx}4.3 K were observed at the CI of bicrystals while ordinary rhombohedral Bi is not a superconductor. We conclude that these phases have to do with the central part and the adjacent layers of the CI of bicrystals.A temperature-dependent x-ray absorption spectroscopy (XAS) study was performed to investigate the changes in electronic and atomic structure of La-deficient La{sub 0.7}Sr{sub 0.2}FeO{sub 3-{delta}} (L7S2FO3) and stoichiometric La{sub 0.8}Sr{sub 0.2}FeO{sub 3-{delta}} (L8S2FO3). La{sub 0.8}Sr{sub 0.2}FeO{sub 3-{delta}} is a promising cathode material for intermediate operating temperature (700-800 deg. C) solid oxide fuel cells. Performance improvements have been shown by increasing the La- or A-site deficiency in this material but a clear understanding of the mechanisms responsible for this improvement are still needed. Here we report an x-ray absorption spectroscopy (XAS) study as a function of temperature to investigate electronic and atomic structure changes of La-deficient La{sub 0.7}Sr{sub 0.2}FeO{sub 3-{delta}} (L7S2FO3) and stoichiometric La{sub 0.8}Sr{sub 0.2}FeO{sub 3-{delta}} (L8S2FO3). In particular we have measured the temperature-dependent changes in oxidation state, bond distance, Fe coordination number, and oxygen vacancies for both compounds. L7S2FO3 contains 10% A-site vacancies compared to stoichiometric L8S2FO3, which has a fully occupied A site and thus some form of charge compensation is necessary in the former to maintain charge neutrality. X-ray absorption near edge spectroscopy shows the presence of Fe{sup 3+} and Fe{sup 4+} in both L7S2FO3 and L8S2FO3 (mixed valence) as established by comparison with model compounds. Studies frommorexa0» room temperature to 850 deg. C show that Fe{sup 3+} dominates over Fe{sup 4+} in both materials with increasing dominance as the temperature is increased. Furthermore, the temperature-dependent study revealed the La-deficiency in L7S2FO3 leads to a higher concentration of both electron holes (i.e., more Fe{sup 4+} created) and oxygen vacancies, compared to the stoichiometric L8S2FO3. Analysis of the extended x-ray absorption fine structure shows that the Fe-O bond increases with the increase in temperature for both the systems.«xa0lessThe local structure around Ag ions in silver borate glasses g-Ag{sub 2}O{center_dot}nB{sub 2}O{sub 3} (n=2,4) was studied by x-ray absorption spectroscopy at the Ag K edge for temperatures from 77 to 450 K. Extended x-ray absorption fine structure (EXAFS) analysis based on cumulant expansion or multishell Gaussian model fails for these systems. Therefore, the radial distribution functions (RDFs) around Ag ions were reconstructed using a method based on the direct inversion of the EXAFS expression. The RDFs consist of about eight atoms (oxygens and borons), exhibit a relatively weak temperature dependence, and indicate the presence of strong static disorder. Two main components can be identified in RDFs, located at about 2.3-2.4 A and 2.5-3.4 A, respectively. The chemical types of atoms contributing to the RDF were determined via a simulation of configurationally averaged x-ray absorption near-edge structure (XANES) and EXAFS signals. The immediate neighborhood of Ag contains mostly oxygens while borons dominate at larger distances. The combination of EXAFS and XANES techniques allowed us to determine a more complete structural model than would be possible by relying solely on either EXAFS or XANES alone.Hall effects of the La{sub 0.7}Ce{sub 0.3}MnO{sub 3+{delta}} film, which is believed an electron-doped manganite, have been experimentally studied, and a positive normal Hall coefficient is observed below the Curie temperature when the oxygen content of the film varies in a wide range. These observations may be attributed to the presence of excessive oxygen and composition distribution in the film, which may occur companying tetravalent ion doping. Removing excessive oxygen drives the system into the electron-doping state, however, the resistivity increases monotonically with oxygen loss, and the metal-to-semiconductor transition typical for a hole-doped manganite disappears. These results suggest the determinative role of hole doping for the resistive and magnetic behaviors in La{sub 0.7}Ce{sub 0.3}MnO{sub 3+{delta}}.We studied the influence of the disorder introduced in polycrystalline MgB{sub 2} samples by neutron irradiation. To circumvent self-shielding effects due to the strong interaction between thermal neutrons and {sup 10}B we employed isotopically enriched {sup 11}B which contains 40 times less {sup 10}B than natural B. The comparison of electrical and structural properties of different series of samples irradiated in different neutron sources, also using Cd shields, allowed us to conclude that, despite the low {sup 10}B content, the main damage mechanisms are caused by thermal neutrons, whereas fast neutrons play a minor role. Irradiation leads to an improvement in both upper critical field and critical current density for an exposure level in the range 1-2x10{sup 18} cm{sup -2}. With increasing fluence the superconducting properties are depressed. An in-depth analysis of the critical field and current density behavior has been carried out to identify what scattering and pinning mechanisms come into play. Finally, the correlation between some characteristic lengths and the transition widths is analyzed.The structure of Na{sub 0.5}CoO{sub 2}, the low-temperature insulator that separates the antiferromagnetic and normal metals in the Na{sub x}CoO{sub 2} phase diagram, is studied by high-resolution powder neutron diffraction at temperatures between 10 and 300 K. Profile analysis confirms that it has an orthorhombic symmetry structure, space group Pnmm, consisting of layers of edge-sharing CoO{sub 6} octahedra in a triangular lattice, with Na ions occupying ordered positions in the interleaving planes. The oxygen content is found to be stoichiometric within 1%, indicating that the Na concentration accurately determines the electronic doping. The Na ordering creates two distinct Co sites, in parallel chains running along one crystallographic direction. The differences in their Co-O bond distances and the derived bond valence sums, reflections of the degree of charge ordering in this phase, are very small.The temperature dependence of the local structure of V{sub 2}O{sub 3} in the vicinity of the metal-to-insulator transition (MIT) has been investigated using hard x-ray absorption spectroscopy. It is shown that the vanadium pair distance along the hexagonal c axis changes abruptly at the MIT as expected. However, a continuous increase of the tilt of these pairs sets in already at higher temperatures and reaches its maximum value at the onset of the electronic and magnetic transition. These findings confirm recent theoretical results which claim that electron-lattice coupling is important for the MIT in V{sub 2}O{sub 3}. Our results suggest that the distortion of the symmetry of the basal plane plays a decisive role for the MIT and orbital degrees of freedom drive the MIT via changes in hybridization.We present here ab initio determinations of the nuclear-quadrupole moment Q of hyperfine-probe-nuclear states of three different In isotopes: the 5{sup +} 192 keV excited state of {sup 114}In (probe for nuclear quadrupole alignment spectroscopy), the 9/2{sup +} ground state of {sup 115}In (nuclear magnetic and nuclear quadrupole resonance probe), and the 3/2{sup +} 659 keV excited state of {sup 117}In (perturbed angular correlations probe). These nuclear-quadrupole moments were determined by comparing experimental nuclear-quadrupole frequencies to the electric field gradient tensor calculated with high accuracy at In sites in metallic indium within the density functional theory. These ab initio calculations were performed with the full-potential linearized augmented plane wave method. The results obtained for the quadrupole moments of {sup 114}In [Q({sup 114}In)=-0.14(1) b] are in clear discrepancy with those reported in the literature [Q({sup 114}In)=+0.16(6) b and +0.739(12) b]. For {sup 115}In and {sup 117}In our results are in excellent agreement with the literature and in the last case Q({sup 117}In) is determined with more precision. In the case of Q({sup 117}In), its sign cannot be determined because standard {gamma}-{gamma} perturbed angular correlations experiments are not sensitive to the sign of the nuclear-quadrupole frequency.An original epitaxial system consisting of two ferrimagnetic insulator layers (CoFe{sub 2}O{sub 4} and Fe{sub 3}O{sub 4}) separated by a nonmagnetic metallic layer (Au) has been grown. The transport properties in the current in plane geometry indicate that the conduction of the CoFe{sub 2}O{sub 4}/Au/Fe{sub 3}O{sub 4} trilayer takes place within the thin metallic layer. The giant magnetoresistance (GMR) observed (2.6% at 10 K) is associated to the switching from a parallel to an antiparallel configuration of the magnetization of the two ferrite layers and corresponds to the spin dependence of electron reflection at the interfaces with a large contribution of specular reflections. The increase of the GMR (5% at 10 K) in the symmetrical interface CoFe{sub 2}O{sub 4}/Fe{sub 3}O{sub 4}/Au/Fe{sub 3}O{sub 4} system and the effect of the interface roughness on the GMR confirm the presence of this spin-dependent specular reflection.X-ray scattering measurements on optimally doped single crystal samples of the high-temperature superconductor Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+{delta}} reveal the presence of three distinct incommensurate charge modulations, each involving a roughly fivefold increase in the unit cell dimension along the b direction. The strongest scattering comes from the well known (H, K{+-}0.21, L) modulation and its harmonics. However, we also observe broad diffraction which peak up at the L values complementary to those which characterize the known modulated structure. These diffraction features correspond to correlation lengths of roughly a unit cell dimension, {xi}{sub c}{approx}20 A in the c direction, and of {xi}{sub b}{approx}185 A parallel to the incommensurate wave vector. We interpret these features as arising from three-dimensional incommensurate domains and the interfaces between them, respectively. In addition we investigate the recently discovered incommensurate modulations which peak up at (1/2, K{+-}0.21, L) and related wave vectors. Here we explicitly study the L dependence of this scattering and see that these charge modulations are two dimensional in nature with weak correlations on the scale of a bilayer thickness, and that they correspond to short-range, isotropic correlation lengths within the basal plane. We relate these new incommensurate modulations to the electronic nanostructuremorexa0» observed in Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+{delta}} using STM topography.«xa0lessThe effect of externally applied pressure on the magnetic behavior of Cu{sub 2}Te{sub 2}O{sub 5}(Br{sub x}Cl{sub 1-x}){sub 2} with x=0, 0.73, and 1, is investigated by a combination of magnetic susceptibility, neutron diffraction, and neutron inelastic scattering measurements. The magnetic transition temperatures of the x=0 and 0.73 compositions are observed to increase linearly with increasing pressure at a rate of 0.23(2) and 0.04(1) K/kbar, respectively. However, the bromide shows contrasting behavior with a large suppression of the transition temperature under pressure, at a rate of -0.95(9) K/kbar. In neutron inelastic scattering measurements of Cu{sub 2}Te{sub 2}O{sub 5}Br{sub 2} under pressure only a small change to the ambient pressure magnetic excitations were observed. A peak in the density of states was seen to shift from {approx}5 meV in ambient pressure to {approx}6 meV under an applied pressure of 11.3 kbar, which was associated with an increase in the overall magnetic coupling strength.A KH{sub 2}PO{sub 4} (KDP) crystal, irradiated by a 1 MeV hydrogen ion beam to a dose of 10{sup 15} ions/cm{sup 2}, was studied by means of x-ray diffraction (XRD), {sup 1}H nuclear magnetic resonance (NMR), and dielectric constant measurements. The XRD pattern for the a-cut KDP crystal revealed a decrease in the lattice constant along the a axis after the proton irradiation. According to the {sup 1}H NMR spin-lattice relaxation rate measurements, the proton irradiation gave rise to reduction in the activation energy in the paraelectric phase, from 0.42 to 0.28 eV, in agreement with the temperature dependent second moment measurements indicating the proton motion is more activated after the proton irradiation. Besides, analysis of the temperature-dependent dielectric constants using a mean-field approximation revealed a change in the hydrogen bond induced by the proton irradiation.We study the quantum phase transition between the insulating and the globally coherent superfluid phases in the Bose-Hubbard model with T{sub 3} structure, the dice lattice. Even in the absence of any frustration the superfluid phase is characterized by modulation of the order parameter on the different sublattices of the T{sub 3} structure. The zero-temperature critical point as a function of magnetic field shows the characteristic butterfly form. At full frustration the superfluid region is strongly suppressed. In addition, due to the existence of the Aharonov-Bohm cages at f=1/2, we find some evidence for the existence of an intermediate insulating phase characterized by a zero superfluid stiffness but finite compressibility. In this intermediate phase bosons are localized due to the external frustration and the topology of the T{sub 3} lattice. We name this new phase the Aharonov-Bohm insulator. In the presence of charge frustration the phase diagram acquires the typical lobe structure. The form and hierarchy of the Mott insulating states with fractional fillings are dictated by the particular topology of the T{sub 3} lattice. The results presented were obtained by a variety of analytical methods: mean-field and variational techniques to approach the phase boundary from the superconducting side andmorexa0» a strongly coupled expansion appropriate for the Mott insulating region. In addition we performed quantum Monte Carlo simulations of the corresponding (2+1)-dimensional XY model to corroborate the analytical calculations with a more accurate quantitative analysis. We finally discuss experimental realization of the T{sub 3} lattice both with optical lattices and with Josephson junction arrays.«xa0less

Tungsten 3p X-ray absorption spectrum of WF6

Abstract The 3p (M3,xa0M2) X-ray absorption spectrum of tungsten (2200–2600 eV) in gaseous WF6 has been obtained with synchrotron radiation using a total ion yield technique. Both the 3p3/2 and 3p1/2 spectra are dominated by the 3p→5d unresolved ligand-field split (t2g*+eg*) lines. The difference between the deconvoluted M3 and M2 doublet lines is related to multiplet effects due to the coupling between the 3p core and the 5d valence levels inducing differential intensity transfer between the t2g* and eg* components at the two edges.

Adsorbate-driven reactive interfacial Pt-NiO1−x nanostructure formation on the Pt3Ni(111) alloy surface

Formation of catalytically reactive metal oxide interfaces on the Pt3Ni(111) surface is revealed using operando surface analysis. The origin of the synergistic catalytic effect between metal catalysts and reducible oxides has been debated for decades. Clarification of this effect, namely, the strong metal-support interaction (SMSI), requires an understanding of the geometric and electronic structures of metal-metal oxide interfaces under operando conditions. We show that the inherent lattice mismatch of bimetallic materials selectively creates surface segregation of subsurface metal atoms. Interfacial metal-metal oxide nanostructures are then formed under chemical reaction environments at ambient pressure, which thus increases the catalytic activity for the CO oxidation reaction. Our in situ surface characterizations using ambient-pressure scanning tunneling microscopy and ambient-pressure x-ray photoelectron spectroscopy exhibit (i) a Pt-skin layer on the Pt-Ni alloyed surface under ultrahigh vacuum, (ii) selective Ni segregation followed by the formation of NiO1−x clusters under oxygen gas, and (iii) the coexistence of NiO1−x clusters on the Pt-skin during the CO oxidation reaction. The formation of interfacial Pt-NiO1−x nanostructures is responsible for a highly efficient step in the CO oxidation reaction. Density functional theory calculations of the Pt3Ni(111) surface demonstrate that a CO molecule adsorbed on an exposed Pt atom with an interfacial oxygen from a segregated NiO1−x cluster has a low surface energy barrier of 0.37 eV, compared with 0.86 eV for the Pt(111) surface.