Chiroptical activity of holmium pyrogermanate: tetragonal Ho2Ge2O7

Chiroptical luminescence and circular dichroism measurements are reported for single crystals of Ho₂Ge₂O₇. These crystals belong to the tetragonal space group P4,2,2 (or P4₃2₁2) with Z=4. Each Ho³⁺ ion in the crystal structure is coordinated to seven oxygens to form a distorted pentagonal bipyramid. The Ho³⁺ ions exhibit luminescence from several excited multiplet levels; chiroptical luminescence spectra are reported for ⁶I₈ → ⁶F₆, ⁶S₂, and ⁶F₃ at a sample temperature of 10 K. Room-temperature absorption and circular dichroism measurements are reported for the ⁶I₈ → ⁶F₆, ⁵S₂, ⁶F₄, and ⁶F₃ transition regions.     

Analysis of the fluorescence of the ion Eu in fluoroborate glasses containing silver particles

We have studied theoretically and experimentally the fluorescence enhancement in fluoroborate glasses, doped with the ion Eu³⁺, containing small silver particles. The model developed shows that the gain coefficient has quenching and enhancement regions. The absorption peak of the metallic particles occurs at 425 nm, which is not in resonance with the ⁵L₆ level of the ion Eu³⁺. For this reason it is not possible to make a complete comparison between theoretical and experimental results, but the structure of the absorption spectra allows us to check some crucial aspects of the problem, such as energy transfer, enhancement of the local field and the high absorption by the particle system. Results of electronic microscopy have revealed non-uniformity of the particle distribution with average radii of approximately 20 Å and 35 Å and a measured localized mean filling factor of 0.02.     

Absorption spectra of solid rare earth complexes obtained from the inner filter effect on luminescence

The inner filter effect is observed in luminescence whenever a second substance is present that has absorptions which overlap the luminescence. This results in a diminution of the luminescence at those wavelengths and is generally observed in solution. In the present communication we show that this effect can be observed when a solid rare earth complex is physically mixed with a solid luminescent organic matrix with which it does not interact. The resulting luminescence is reduced in emission intensity at those wavelengths corresponding to the absorptions of the rare earth ion. This is illustrated with a mixture of Na₃[Ho(ODA)₃] ·2NaClO₄·6H₂O and pyrene at 77 K, and it is shown that the absorption spectrum of the holmium complex can be extracted from the luminescence spectrum of pyrene. This absorption spectrum is in good agreement with that obtained by conventional spectroscopy with a single crystal.     

Catalytic behaviour and surface properties of supported lanthana

This paper deals with the role of dispersed lanthana as an active phase in several catalytic reactions: CO hydrogenation, CO oxidation, and oxidative dimerization of methane.

Characterization of the prepared catalysts indicates that lanthana can be effectively dispersed on silica and on ceria. While in the case of silica-supported catalysts lanthana appears at the surface, leading to an almost full coverage for loadings higher than 40%, in the case of ceria-based systems, lanthana forms a solid solution with the support.

In all the reactions studied, the presence of lanthana can be related to significant changes in the catalytic properties of the bare supports. Thus, the selectivity towards the total oxidation products observed on pure ceria is decreased, and the low activity shown by silica is enhanced. For the CO+H₂ reaction, the addition of lanthana also generates upgraded products.     

The electronic structure of organometallic complexes of the f elements XXVIII: Interpretation of the optical and magnetochemical data of a cyclohexylisocyanide adduct derived from Tris(η-cyclopentadienyl)samarium(III)

The absorption spectrum of Cp₃Sm·CNC₆H₁₁ has been measured at room temperature and at low temperatures in a hydrocarbon glass and in a KBr pellet. Electron paramagnetic resonance and magnetic susceptibility measurements are also reported in this paper. The observed optical bands were assigned on the basis of calculations which assumed that the crystal field parameters of the samarium complex were the same as for the previously analyzed Cp₃Pr·CNC₆H₁₃. The parameters of an empirical Hamiltonian were fitted to the energies of 39 levels to give an r.m.s. deviation of 21 cm⁻. On the basis of the wavefunctions of the crystal field ground state obtained from the fit, the ground state g values and the temperature-dependent magnetic susceptibility were calculated and compared with the experimental values.     

Uniaxial compression of Swiss-type cheese at different strain rates

Rheological behaviour of 48 Swiss-type cheese samples in lubricated uniaxial compression was evaluated at three initial strain rates ranging from 4·76 × 10⁻³ to 7·62 × 10⁻² s⁻¹. Modulus, apparent fracture stress and apparent fracture strain increased significantly with increasing strain rate, which is attributed to the viscoelastic nature of cheese. The influence of strain rate on apparent fracture strain strongly depended on the shape of the stress-strain curves. The relationship between the rheological parameters evaluated at different strain rates proved to be significant. The strain rate dependency of the apparent fracture strain is further explained by the contribution of elastic and viscous components, which was evaluated in relaxation experiments in the linear viscoelastic region.     

Quantitative x-ray photoelectron spectroscopy analysis of alkali ions / zirconia systems

Zirconia-supported alkali ions, containing Na, from 0.74 to 3.61 wt.%, and K, from 0.91 to 4.76 wt.%, have been studied by X-Ray Photoelectron Spectroscopy, X-ray diffraction and chemical analyses. The results show that the alkali ions remain dispersed on the zirconia surface. After treatment at 773 K in air, 5h, the Na containing samples maintain a good dispersion at low Na content, whereas for the more concentrated samples, agglomeration and incorporation in solid solution have been detected. The K based system shows neither agglomeration nor incorporation in solid solution of potassium ions. The XPS intensity ratios are compared with calculated values, according to different models, to account for the changes in surface morphology.     

Volume effects and associations in liquid alloys

The regular associated solution model for binary systems has been modified by incorporating the size of the complex as an explicit variable. The thermodynamic properties of the liquid alloy and the interactions between theA _μB type of complex and the unassociated atoms in anA-B binary have been evaluated as a function of relative size of the complex using the activity coefficients at infinite dilution and activity data at one other composition in the binary. The computational procedure adopted for determining the concentration of clusters and interaction energies in the associated liquid is similar to that proposed by Lele and Rao. The analysis has been applied to the thermodynamic mixing functions of liquid Al-Ca alloys believed to contain Al₂Ca associates. It is found that the size of the cluster significantly affects the interaction energies between the complex and the unassociated atoms, while the equilibrium constant and enthalpy change for the association reaction exhibit only minor variation, when the equations are fitted to experimental data. The interaction energy between unassociated free atoms remains virtually unaltered as the size of the complex is varied between extreme values. Accurate data on free energy, enthalpy, and volume of mixing at the same temperature on alloy systems with compound forming tendency would permit a rigorous test of the proposed model.