Photophysics of C<Subscript>60</Subscript> and C<Subscript><Emphasis Type="Bold">60</Emphasis></Subscript><Superscript><Emphasis Type="Bold">-</Emphasis></Superscript> in faujasite zeolites

While the intercalation of C₆₀ and the formation of C ₆₀ ^- in the supercages of NaX and NaY are confirmed by using ¹²⁹Xe NMR and ESR, the photophysical properties of C₆₀ and C ₆₀ ^- are characterized by monitoring transient reflectance spectra and kinetics, fluorescence kinetics, and diffuse reflectance spectra. C ₆₀ ^- is considerably more abundant in NaY than in NaX. This difference is explained in terms of polarity difference between two zeolites. Both C₆₀ and C ₆₀ ^- have remarkably elongated excited-state lifetimes due to their collision-free environment in zeolitic nanocavities although C ₆₀ ^- has much shorter lifetimes than C₆₀. C ₆₀ ^- , in particular, shows intense absorption and emission due to its reduced symmetry in zeolites. Received 13 July 2001 and Received in final form 8 October 2001     

X-ray scattering study of the phase transitions in crystalline fullerene-biphenyl C 60 [(C 6 H 5 ) 2 ]

The phase diagram of the newly synthesized mixed crystal C₆₀-biphenyl is investigated as a function of temperature by single-crystal X-ray scattering. Diffuse scattering investigations evidencing complex disorder and local order effects are presented. Two phase transitions leading to two different doublings of the high temperature unit cell are observed, at 212 K and 147 K. The first transition is attributed to the ordering of twisted biphenyls, which couples to the orientational ordering of the C₆₀ molecules as the temperature decreases. Full ordering of the C₆₀ molecules is achieved below 100 K only, in the low temperature phase. The rich phase diagram of C₆₀-biphenyl is due to the interplay between fullerene and biphenyl ordering phenomena. Received 31 August 2001 and Received in final form 4 December 2001     

SiC bonding in ( C 60 ) n Si m clusters

This paper deals with a new type of SiC bonding where silicon atom seems to bridge C₆₀ molecules. We have studied films obtained by deposition of (C₆₀)_nSi_m clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight mass spectrometer. Mixed clusters (C₆₀)_nSi_m were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the (C₆₀)_nSi _n ⁺ , (C₆₀)_nSi _{n - 1} ⁺ and (C₆₀)_nSi _{n - 2} ⁺ species. This observation is in favor of the arrangement of these complexes as polymers where the C₆₀ cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering. The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected to be totally different from the sp³ lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C₆₀ molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments. Received 15 November 2000     

Radiative cooling of fullerene anions in a storage ring

Thermionic emission from hot fullerene anions, C_N ^-, has been measured in an electrostatic storage ring for even N values from 36 to 96. The decay is quenched by radiative cooling and hence the observations give information on the intensity of thermal radiation from fullerenes. The experiments are analysed by comparison with a simulation which includes the quantisation of photon energy and the statistics of emission. Experiments with heating of the molecules with a laser beam confirm the interpretation of the observations in terms of radiative cooling and give an independent estimate of the cooling rate for C₆₀ ^-. The measured cooling rates agree in general within a factor of two with the prediction from a classical dielectric model of a thermal radiation intensity of ∼ 300 eV/s for C₆₀ at 1 400 K, scaling approximately with the 6th power of the temperature and with the number of atoms in the molecule. Received 12 March 2001 and Received in final form 12 June 2001     

Evidence of local structural transition during oxidation process of RBCO epitaxial films using time resolved reflexafs measurements

We report results of a time resolved X-ray Absorption Spectroscopy (XAS) experiment on the oxidation process of epitaxial Y₁(Nd_0.05Ba_1.95)Cu₃O_x superconducting thin films. For the first time Cu K-edge XAS technique has been used to explore local structural changes around the Cu ions during the oxidation process of a high critical temperature superconducting film. The results show that during the oxygenation of a tetragonal Y₁(Nd_0.05Ba_1.95)Cu₃O_x additional local transitions appear in the orthorhombic I phase, which are not linked to long range order transformations as shown by in situ X-ray diffraction experiment. New questions concerning the dynamic microscopic process leading to the oxygenation and eventually to superconductivity of the complex R_1+xBa_2-xCu₃O_x (R = Y or rare earth) compounds arose from these results. Received 21 December 2001 Published online 25 June 2002     

Electronic structure and metal-insulator transition in SrTi 1 - x Ru xO 3

We studied the changes in the electronic structure of SrTi_1-xRu_xO₃ across the metal-insulator transition. The parent compound, SrTiO₃, is a well known diamagnetic insulator; whereas the doped compound, SrTi_1-xRu_xO₃, becomes a ferromagnetic metal above x _C = 0.35. The techniques used in the study were photoemission (PES) and O 1 s X-ray absorption (XAS) spectroscopy. The experimental spectra were analyzed in terms of band structure and Hubbard model calculations. The PES and XAS spectra of SrTi_1-xRu_xO₃ show the Ru 4 d bands growing in the band gap of SrTiO₃ . The analysis in terms of the Hubbard model indicates that the Ti 3 d and Ru 4 d bands are mostly decoupled. This suggests that the metal-insulator transition is a percolation transition like that of metals embedded in a rare gas matrix. Electron correlation effects are present in this system, but they do not seem to play a major role in the transition. Received 10 September 2001     

The electronic structure of the doped one-dimensional transition metal oxide Y 2 - x Ca x BaNiO 5 studied using X-ray absorption

A strong anisotropic distribution of the holes in Ni 3 d and O 2 p orbitals is observed in the polarization dependent O 1 s and Ni 2 p _3/2 X-ray absorption spectroscopy of the linear-chain nickelate Y_2-xCa_xBaNiO₅ (x = 0, 0.05, 0.1, 0.2), which demonstrates the one-dimensional nature of the electronic state in these compounds. The holes introduced by Ca-doping occupy both O 2 p and Ni 3 d orbitals along the NiO₅ chains. By comparing the experimental Ni 2 p _3/2 absorption spectra of Y_2-xCa_xBaNiO₅ to those from charge transfer multiplet calculations we can derive the orbital character of the additional holes to be of ∼60% O2 p and ∼40% Ni 3 d. Received 7 January 2002     

Photoexcitation of rare-gas neon and argon clusters doped with <Emphasis Type="Bold">H</Emphasis><Subscript><Emphasis Type="Bold">2</Emphasis></Subscript><Emphasis Type="Bold">O</Emphasis>

We have studied the fluorescence of electronically excited OH^*, H^* and H₂O^+* dissociation fragments after VUV excitation ( h ν≥11.6 eV) of rare-gas clusters (Rg = Ne, Ar) doped with H₂O molecules. In contrast to a free molecule, where Balmer H-series dominate the UV-visible spectra, only the OH ^* ( A ² Σ ⁺ ↦ X ² Π) emission band is observed in neon clusters. No emission of excited water ions has been observed. We find that while higher excitation energies (Ne vs. Ar) induce higher vibrational excitation of the OH^* ( A ) fragment, the rotational temperature is lower. This effect is attributed to the difference in the geometric position of the H₂O molecule on the surface or inside the Rg-cluster. The rotational relaxation in neon clusters is rapid while the vibrational relaxation is slow because of the coupling with the low energy matrix phonons. Received 7 March 2002 / Received in final form 27 May 2002 Published online 19 July 2002     

Investigation of S-H bonds in biologically important compounds by sulfur K-edge X-ray absorption spectroscopy

X-ray Absorption Near Edge Structure (XANES) spectroscopy, often provides a direct correlation between observed resonances in the spectrum and molecular bonds in the sample. This can be used as a fingerprint for the presence of a given molecular environment of the absorber atom in a sample. As the white line is found at similar energy positions for S-C and S-H bonds, this approach is impossible when both types of bond are present simultaneously, as often in biological systems. To develop a criterium for the presence of S-H bonds in such samples, reduced glutathione, reduced coenzyme A, cysteine and their corresponding oxidized forms were investigated using sulfur K-edge XANES, revealing a unique feature at 2 475.8 eV in the respective difference spectra. To correlate this structure to S-H bonds, H₂S and H₂S₂ were measured, whose difference spectrum also shows a structure at this energy position, whereas it is not present throughout a variety of C-S-C/C-S-S-C environments. Theoretical investigations suggest its correlation to a Rydberg transition occurring in the case of a S-H bond. Using this criterium, the presence of S-H bonds is in the purple sulfur bacterium Allochromatium vinosum during oxidation of intracellular accumulated sulfur, is proved, as expected from biological considerations. Received 1st February 2002 / Received in final form 10 June 2002 Published online 13 September 2002     

Molecular beam deflection experiments on mixed clusters

Gas phase Ti-C₆₀ clusters are studied by molecular beam electric deflection. The permanent dipole moment of the TiC₆₀ molecule is determined. It is equal to 8.1±1.5 D. This dipole is due to a transfer of electron from the transition metal atom to the C₆₀ cage. No dipole is observed for Ti(C₆₀)₂ molecules. This is in agreement with the symmetrical dumbbell-like structure that has been previously proposed. Received 22 November 2000     

Emission of intermediate-mass fragments in the interaction of 16O with 59Co, 93Nb and 197Au

In this paper we study the emission of ⁸Be_gs, B and N fragments in the interaction of ¹⁶O ions with ⁵⁹Co, ⁹³Nb and ¹⁹⁷Au at incident energies varying from 6 to 25 MeV/nucleon. The spectra of these fragments, as well as those of C fragments studied in a previous paper, are dominated at forward angles by a component originating from break-up of ¹⁶O. At the higher incident energies break-up occurs after quite a sizeable projectile energy loss. Another mechanism which dominates at large emission angles, favours the emission of low-energy fragments and is attributed to the coalescence of nucleons during the cascade of nucleon-nucleon interactions by means of which the excited nuclei produced in the primary two-ion interaction thermalize. Received: 21 January 2003 / Accepted: 27 March 2003 / Published online: 5 June 2003     

Molecular picture of excited states and fragmentation paths of the Na 5 F 4 cluster

The stability against fragmentation and possible relaxation of the lowest excited states of the Na₅F₄ cluster (representative of cubic non stoechiometric clusters with an excess sodium atom, also called sodium-tail) is investigated by means of one-electron pseudopotential calculations with particular reference to photoabsorption processes from the ground state. Whereas the equilibrium configuration of the ground state has C_3v symmetry, the doubly degenerate 1²E excited state is affected by a conical intersection and a Jahn-Teller effect associated with the rotation of the sodium tail around the C₃-axis. This yields a “Mexican hat" topology for the lowest sheet with three equivalent C_s minima. Alternatively the 2²A₁ state has a minimum retaining the C_3v symmetry. The dissociation paths of the cluster along the C₃-axis into respectively Na₄F_{4 +} Na and Na₄F_{3 +} NaF are also investigated. Among the former paths, the excited states are found adiabatically stable with respect to the products. However in the A₁ symmetry, fragmentation into NaF exhibits an interesting avoided crossing between configurations correlated respectively with Na₄F₃ ^{+ +} NaF^- and Na₄F_{3 +} NaF. Such interaction, similar to the well-known charge exchange processes in elementary molecules might induce non adiabatic predissociation of the 2²A₁ state. This mechanism is invoked to explain the differences between R2PI and depletion spectra, correlated with the dissociation or relaxation of the excited states. Received 24 March 2000 and Received in final form 11 July 2000     

Thermal dileptons from quark and hadron phases of an expanding fireball

A fireball model with time evolution based on transport calculations is used to examine the dilepton emission rate of an ultra-relativistic heavy-ion collision. A transition from hadronic matter to a quark-gluon plasma at a critical temperature T _C between 130-170 MeV is assumed. We also consider a possible mixed phase scenario. We include thermal corrections to the hadronic spectra below T _C and use perturbation theory above T _C. The sensitivity of the spectra with respect to the freeze-out temperature, the initial fireball temperature and the critical temperature is investigated. Received: 4 August 2000 / Accepted: 14 November 2000     

Vanadium valency and hybridization in V-doped hafnia investigated by electron energy loss spectroscopy

The valency of vanadium, and thus indirectly the oxygen stoichiometry, of V-doped hafnia synthesized under different atmospheres have been investigated on a nanometer scale by means of electron energy loss spectroscopy (EELS). The EELS V L_2,3 spectra are compared with the results of crystal field multiplet calculations and experiments on reference vanadium oxides. The EELS spectra indicate that V-doped hafnia prepared under reducing (H₂) and neutral (Ar) atmosphere are unambiguously substituted with trivalent vanadium atoms leading to the creation of oxygen vacancies in the structure. On the contrary, stoichiometric (Hf, V)O₂ compound (i.e. V⁴⁺) is more likely to be stabilized under oxidative (air) atmospheres. We also show that the amount of hybridization alters for the different compounds studied but may in part be analyzed by high spatially resolved EELS. The crystal field multiplet calculations particularly indicate that a simple reduction of the Slater integrals gives a good account of the spectral modification induced by hybridization for the case of tetravalent vanadium atoms. Received 17 November 2000 and Received in final form 17 April 2001     

Oxygen K-edge in vanadium oxides: simulations and experiments

Band-structure (BS) calculations of the density of states (DOS) using the full potential augmented plane waves code WIEN97 were performed on the four single-valence vanadium oxides VO, V₂O₃, VO₂ and V₂O₅. The DOS are discussed with respect to the distortions of the VO₆ octahedra, the oxidation states of vanadium and the orbital hybridisations of oxygen atoms. The simulated oxygen K-edge fine structures (ELNES) calculated with the TELNES program were compared with experimental results obtained by electron energy-loss spectrometry (EELS), showing good agreement. We show that changes in the fine structures of the investigated vanadium oxides mainly result from changes in the O-p DOS and not from the shift of the DOS according to a rigid band model. Received 17 December 2001 / Received in final form 19 June 2002 Published online 13 August 2002     

Isomorphous phase transition and orientational freezing in hexagonal mixed crystal C 70(1 - x) C60x. A pseudospin model

A four-state pseudospin model is constructed for the isomorphous phase transition hcp-2↦hcp-1 in pure C₇₀ and in C₇₀-rich mixed crystal C _{70(1 - x)} C_60x. With the specific anisotropic pseudospin interactions adapted to the C₇₀ crystal the model is equivalent to a two-state Ising model in a temperature-dependent field. Replica symmetric state of the model is shown to approach the critical point when the width of distribution of random fields and/or of random bonds increases. The temperature of the phase transition and the phase equilibrium temperature then are practically constant, whereas the experiment shows their strong decrease with x. The main effect of dilution resides in an x-dependence of the model parameters. Dilatometric data on the hexagonal C _{70(1 - x)} C_60x are used to fit these parameters. A metastable disordered phase subsisting below the phase transition is discovered in a range of the model parameters and is shown to be responsible for the macroscopic behaviour of the system. A good agreement with experimental data is obtained for the spontaneous strain and for the x-dependence of the hysteresis. Received 20 April 2001 and Received in final form 26 September 2001     

Growth of pentacene on Ag(1 1 1) surface: A NEXAFS study

Thin films of pentacene (C₂₂H₁₄) have become widely used in the field of organic electronics. Here films of C₂₂H₁₄ of thickness ranging from submonolayer to multilayer were thermally deposited on Ag(1 1 1) surface. The determination of molecular geometry in pentacene films on Ag(1 1 1) studied by X-ray absorption at different stages of growth up to one monolayer is presented.XAS spectra at the C K-edge were collected as a function of the direction of the electric field at the surface. The different features of the spectra were assigned to resonances related to the various molecular unoccupied states by the comparison with the absorption coefficient of the pentacene gas phase. The transitions involving antibonding π states show a pronounced angular dependence for all the measured coverages, from submonolayer to multilayer. The spectra analysis indicates a nearly planar chemisorption of the first pentacene layer with a tilt angle of 10°.     

Investigation of thin TiO2 films cosputtered with Si species

Titanium dioxide (TiO₂) films were fabricated by cosputtering titanium (Ti) target and SiO₂ or Si slice with ion-beam-sputtering deposition (IBSD) technique and were postannealed at 450 °C for 6 h. The variations of oxygen bonding, which included high-binding-energy oxygen (HBO), bridging oxygen (BO), low-binding-energy oxygen (LBO), and three chemical states of titanium (Ti⁴⁺, Ti³⁺ and Ti²⁺) were analyzed by X-ray photoelectron spectroscopy (XPS). The enhancement of HBO and reduction of BO in O 1s spectra as functions of SiO₂ or Si amount in cosputtered film imply the formation of Si-O-Ti linkage. Corresponding increase of Ti³⁺ in Ti 2p spectra further confirmed the property modification of the cosputtered film resulting from the variation of the chemical bonding. An observed correlation between the chemical structure and optical properties, refractive index and extinction coefficient, of the SiO₂ or Si cosputtered films demonstrated that the change of chemical bonding in the film results in the modification of optical properties. Furthermore, it was found that the optical properties of the cosputtered films were strongly depended on the cosputtering targets. In case of the Si cosputtered films both the refractive indices and extinction coefficients were reduced after postannealing, however, the opposite trend was observed in SiO₂ cosputtered films.     

Pure and Sb-doped SnO 2 nanoparticles studied by photoelectron spectroscopy

We describe photoemission results from pure and Sb-doped SnO₂ nanoparticles deposited on gold substrates. Photoelectron spectra with synchrotron radiation were recorded for Sn 3d, Sb 3d and O 1s core levels and valence bands in the 500-1200 eV energy range. For pure SnO₂ nanoparticles the surface is terminated by an oxygen rich layer with no obvious surface environment for Sn. When doped n-type with 9.1% or 16.7% Sb, dopant atoms are concentrated near the surface of the nanoparticles. The valence state of the dopant atoms is predominantly Sb^V. Plasmon satellite features are also observed in core level photoemission spectra and their intensity relative to the main peak increases with increasing photon energy. Received 30 November 2000     

Structures and energetics of carbon bridged C 60 clusters

The structures and energetics of carbon bridged C₆₀ clusters (C ₆₀ ) _n C_m have been studied by simulated annealing technique within the tight-binding molecular-dynamics. The “sp² addition” ball-and-chain dimers exhibit odd-even alternations over the number of chain atoms, with the dimers containing even chain atoms more stable against dissociation than their immediate neighbors containing odd chain atoms. In addition to the usual “sp² addition” dimers, a pentagon-linked C₁₂₁ isomer and a hexagon-linked C₁₂₂ isomer are also found to be stable. Based on our tight-binding calculations, trimers and larger clusters can be simply regarded as being made up of independent or weakly interacting dimers, if the C-C₆₀ joints on a single cage are not too close to each other. Large C₆₀ clusters connected by chains each containing only one or two carbon atoms have similar stability to that of constituent dimers, indicating the possibility to form stable C₆₀-carbon polymers. Received 17 January 2001 and Received in final form 26 February 2001