Hydrogen CARS thermometry in H2–N2 mixtures at high pressure and medium temperatures: influence of linewidths models

In order to improve the accuracy of H₂ CARS thermometry, H₂ Q-branch CARS spectra have been recorded for various H₂-N₂ mixtures in a high-pressure cell at different pressures and temperatures (up to 40 bar and 875 K). Due to the low spectral resolution of broadband CARS experiments, the relevant spectral lineshape factor is the linewidth ratio &(Q(3))/&(Q(1)), since Q(1) and Q(3) are the most intense lines of the Q-branch spectrum in this temperature range. For the first time, the speed-inhomogeneous effects are accounted for in the simulation of the CARS profiles. The evaluated temperatures are in good agreement with reference values obtained by thermocouples. The specific role on the accuracy of H₂ CARS thermometry of the speed inhomogeneity is carefully analyzed, in connection with the influence of the nitrogen concentration.     

Molecular understanding of alumina supported single-site catalysts by a combination of experiment and theory

The nature and structure of grafted organometallic complexes on gamma-alumina are studied from a combination of experimental data (mass balance analysis, IR, NMR) and density functional theory calculations. The chemisorptive interactions of two complexes are analyzed and compared. The reaction of [Zr(CH2tBu)4] with alumina dehydroxylated at 500 degrees C gives {[(AlsO)2Zr(CH2tBu)]+[(tBuCH2)(Als)]-}, a bisgrafted cationic complex as major surface species. The DFT calculations show that the reaction with surface hydroxyls is very exothermic and that alkyl transfer on Al atoms is favored. In contrast, [W(CtBu)(CH2tBu)3] reacts with an alumina treated under identical conditions to give selectively a monografted neutral surface complex, [(AlsO)W(CtBu)(CH2tBu)2]. This was inferred by the evolution of 1 equiv of tBuCH3 per grafted W and the presence of remaining hydroxyls. The calculations show that the reaction of [W(CtBu)(CH2tBu)3] with surface hydroxyls is in fact less exothermic and has a considerably higher activation barrier than the one of the Zr complex. Additionally, the transfer of an alkyl ligand onto an adjacent Al center is disfavored, and hence cationic species are not formed. Some ligands of this monoaluminoxy surface complex interact with remaining surface hydroxyls, which explains the complexity of the experimental NMR and IR data.     

Preparation and characterization of MgB2 superconductor

The MgB₂ superconductor, synthesized using solid-state and liquid-phase sintering methods, have been characterized for various properties. The upper critical field, irreversibility line and critical current density have been determined using magnetization data. The current-voltage characteristics recorded under an applied magnetic field revealed the existence of vortex glass transition. The surface analysis using X-ray photoelectron spectroscopy shows that MgB₂ is sensitive to atmospheric degradation.     

On the ferromagnetic perovskite with potential GMR properties: The manganite La1−x K x MnO3

We investigate structural features (cell distortions), magnetic and electric properties versus temperature for La_1-x K _x MnO₃ (0.05 < x < 0.2) perovskites. All the phases crystallize in a rhomboedral symmetry (R3c) and are ferromagnetic. Curie temperatures are strongly dependent of x, with a maximum around 308 K for La_0.8K_0.2MnO₃. A sharp decrease of the resistivity is observed just below the Curie temperature, accompanied by a very steep increase of the spontaneous magnetization, characteristic of a conventional Brillouin type curve. The average magnetic moment of Mn is about 88 e.m.u/g at 5 K for the composition La_0.8K_0.2MnO₃. The transition from ferromagnetic-metallic to paramagnetic-semiconducting states is explained from the suggested distribution of the cations (La³⁺ _1-x K⁺ _x )_A(Mn⁴⁺ _1-2x Mn⁴⁺ _2x )_BO₃ by the double exchange of Mn³⁺-Mn⁴⁺ pairs at the B-sublattice. Preliminary magnetoresistance measurements on bulk ceramic samples display an MR effect of the same amplitude as in the case of the alkaline earth substituted La manganites.     

Luminescence self-quenching in Tm3+: YLF crystals: II. The luminescence decay and macrorates of energy transfer

Microparameters of migration and self-quenching of luminescence from the (³ P ₀, ¹ I ₆) levels of Tm ³⁺ ions are calculated and the luminescence decay from the ³ H ₄, ¹ G ₄, and ¹ _{D 2} levels are analyzed in the concentration series of LiY_1?x Tm_xF₄(x=0.5–10 at. %) crystals upon weak selective excitation. It is shown that the luminescence decay of a thulium ion concentration higher than 0.5 at. % cannot be described by the energy transfer that takes into account only the dipole-dipole interaction. The comparison of experimental kinetic curves with theoretical curves calculated within the framework of the known energy transfer models showed that multipole-multipole interaction is responsible for the self-quenching of the thulium levels. Contributions of higher multipole interactions to the self-quenching are estimated. The decay of luminescence from the ³ H ₄, ¹ G ₄, and ¹ D ₂ levels of Tm³⁺:YLF crystals with different concentrations of thulium ions is described analytically.     

Spectroscopic study of double sodium-yttrium fluoride crystals doped with erbium Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript>:Er<Superscript>3+</Superscript>: I. Intensities of luminescence spectra and kinetics of luminescence

Na_0.4Y_0.6F_2.2:Er³⁺ (NYF:Er) crystals with an erbium concentration as high as 100 at. % (Na_0.4Er_0.6F_2.2) were grown by the Bridgman-Stockbarger method. The optical spectra were investigated at low (6 K) and room temperatures. It is shown that the absorption spectrum of NYF:Er crystals contains wide bands (790–801 and 965–980 nm) corresponding to the emission range of laser diodes. The peak absorption cross section σ_a for the band peaked at λ=970.4 nm is 0.15×10^?20 cm². On the basis of the analysis of the absorption and luminescence spectra at low (6 and 12 K) temperatures, the structure of the Stark splitting of erbium levels was determined as a structure of quasi-centers for which Stark components are inhomogeneously broadened. The oscillator strengths of the transitions from the ground state of erbium to excited multiplets were calculated from the absorption spectra measured at T=300 K, and the intensity parameters Ω_t were determined by the Judd-Ofelt method: Ω₂=1.65×10^?20 cm², Ω₄=0.56× 10^?20 cm², and Ω₆=1.01×10^?20 cm². These values of the intensity parameters were used to calculate the probabilities of radiative transitions and the branching ratios. The rates of multiphonon nonradiative transitions in NYF: Er were estimated. The luminescence decay kinetics for radiative levels of erbium ions upon their selective excitation by nanosecond laser pulses was studied. The intracenter lifetimes of radiative levels of erbium ions were determined from the luminescence kinetics upon selective ion excitation by low-intensity light in a sample with a low erbium concentration (0.5%). It is demonstrated that, with an increase in temperature from 6 to 300 K, luminescence from the ⁴ G _11/2, ² G(H)_9/2, and ⁴ F _9/2 levels is quenched as a result of multiphonon nonradiative transitions. Luminescence from the ⁴ I _9/2 level is quenched only insignificantly with increasing temperature, and no quenching of luminescence from the ⁴ I _11/2 and ⁴ I _13/2 levels is observed. The spectra of steady-state luminescence of NYF:Er(0.5–15%) crystals were investigated upon broadband excitation by UV and UV-visible lamp light and selective time-resolved laser excitation. It is shown that low-lying levels of erbium ions separated by an energy gap smaller than 2500 cm^?1 are populated via cascade mechanisms. On the basis of the results obtained, it is concluded that NYF:Er ³⁺ crystals are promising candidates for active media of tunable diode-pumped lasers.     

Synthesis,X-ray,magnetic and electrical studies of substituted (Pr,Sr)MnO3 perovskites

A systematic study of the structural, magnetic and electrical properties of the manganites Pr_1-x Sr _x MnO₃(0≤ x ≤ 0.5) has been carried out. X-ray diffraction investigation shows a structural change with composition, from orthorhombic (0 ≤ x ≤ 0.2) to rhombohedral (0.25 ≤ x ≤ 0.5). The magnetic properties of Pr_1-x Sr _x MnO₃ samples could be explained on the basis of a double exchange mechanism between pairs of Mn³⁺ and Mn⁴⁺ ions. These properties are strongly dependent on the ratio of Mn³⁺/Mn⁴⁺. The maximum of the ferromagnetic transition temperature T_c is reached at x ≈ 0.35 corresponding to a value 1.85 of this ratio. The investigation of the electrical properties shows a semiconductor to metal transition as a function of temperature (0.25≤x≤0.4) with a metallic-like behaviour above a critical temperature T_p . A semiconducting-like one is observed for all the range of temperature (50–300 K) for (0 ≤ x ≤ 0.2 and x = 0.5). The evolution of activated energies with the carrier concentration has been investigated.     

Ammonia on Ni(1 1 1) surface studied by first principles: Bonding, multilayers structure and comparison with experimental IR and XPS data

DFT calculations have been performed on the adsorption of NH₃ on Ni(1 1 1) to obtain information on the structure of the absorbed species, the nature of the chemical interactions between the adsorbate and the surface and the structure of multilayers formed at high coverage. A cluster model, using localized basis functions as well as an approach based on plane waves and periodic boundary conditions have been considered. The two approaches lead to similar results for the relative stabilities of investigated adsorption sites (atop > fcc > hcp) with an adsorption energy of about 15-24 kcal/mol (depending on the coverage). On the atop site, α-ammonia adsorbs molecularly with an equilibrium distance between the nitrogen atom and the surface of 2.03 ± 0.02 Å and a geometry close to the one of the molecule in the gas phase. The good agreement between the two DFT approaches clearly underlines the local nature of the adsorption reaction. The vibrational frequencies computed for NH₃ adsorbed in this site are in good agreement with experimental values. They show that the interaction with the surface leads to a weakening of the strength of the N-H bond while the angular stretching is stronger. Both orbital and topological analyses were used to investigate chemical interactions between the cluster and the molecule. The results strongly suggest an electrostatic (non-covalent) interaction between the substrate and the molecule. Calculations with NH₃ coverages above 0.25 confirm that saturation occurs at a coverage of 0.25. Above the saturation coverage, ammonia molecules in excess form multiple layers (β and γ ammonia) bonded to the first layer by intermolecular hydrogen bonds. N 1s core level shifts calculations performed for the several investigated coverages are also in good agreement with experimental XPS data. It is shown that the H-bond network more than the bond to the surface allows to understand the N 1s core level variations.