Erbium-induced blurring of the fractal surface of SnO<Subscript>2</Subscript> nanocrystals grown in silica

We show here what kind of modification of the interphase morphology of SnO₂ nanoparticles in silica (average nanocrystal radius, in undoped material; in erbium doped material) brings to the passivation of interfacial defects. Surface states, which may preclude the exploitation of UV excitonic emission, are reduced after doping by rare earth ions. We demonstrate, by means of transmission-electron-microscopy and small-angle-neutron-scattering data, that a smooth interphase with a non negligible thickness takes the place of the fractal and discontinuous boundary observed in undoped material.     

A diode-laser pump source with small focus diameter for end- pumped systems

A pump source with eight angular multiplexed laser diodes is built. The diode laser emission is collimated and focused using relatively inexpensive aspherical lenses. The maximum output power is 6.3W at 970nm. The overall transmittance of the beam shaping optics is T=85%. The electrical, temporal and spectral properties are studied. The variances of the spatial intensity distribution are r0x=99m and r0y=85m. The beam propagation factors are M2x=38 and M2y=112. The high intensity in the focus makes this system ideal for end pumping of solid state lasers.     

Sensitivity of Intrinsic Permeability to Electrokinetic Coupling in Shaly and Clayey Porous Media

Classical Darcy’s law assumes that the intrinsic permeability of porous media is only dependent on the micro-geometrical and structural properties of the inner geometry of the medium. There are, however, numerous experimental evidences that intrinsic permeability of shaly and clayey porous material is a function of the fluid phase used in the experiments. Several pore-scale processes have been proposed to explain the observed behavior. In this study, we conduct a detailed investigation of one such mechanism, namely the electrokinetic coupling. We have developed a numerical model to simulate this process at the pore-scale, incorporating a refined model of the electrical double layer. The model is used to conduct a detailed sensitivity analysis to elucidate the relative importance of several chemical–physical parameters on the intensity of the electrokinetic coupling. We found that permeability reduction due to this mechanism is likely to occur only if the effective pore-radius is smaller than 10⁻⁶ m. We also observed that electrokinetic coupling is strongly sensitive to electrophoretic mobility, which is normally reduced in clays compared to free-water conditions. Based on these findings, we set up a suite of stochastic pore-network simulations to quantify the extent of permeability reduction. We found that only if the effective pore-radius is ranging from 5 × 10⁻⁷ m to 5 × 10⁻⁸, electrokinetic coupling can be responsible for a 5–20% reduction of the intrinsic permeability, and, therefore, this mechanism has a minor impact on situations of practical environmental or mining interest.     

Intersystem crossing processes in nonplanar aromatic heterocyclic molecules

A comprehensive study of the photophysical properties of a series of monoaza[5]helicenes is presented on the basis of joint optical spectroscopy and quantum chemistry investigations. The molecules have been characterized by absorption and CW/time-resolved luminescence measurements. All quantities related to spin-orbit-coupling processes, such as intersystem crossing rates and radiative phosphorescence lifetimes, were found to depend strongly on the nitrogen position within the carbon backbone. Density functional theory and semiempirical quantum-chemical methods were used to evaluate the molecular geometries, the characteristics of the excited singlet and triplet states, and the spin-orbit coupling matrix elements. We demonstrate that the magnitude of spin-orbit coupling is directly correlated with the degree of deviation from planarity. The trends from the calculated photophysical quantities, namely, radiative fluorescence and phosphorescence decay rates and intersystem crossing rates, of the mono-aza-helicenes are fully consistent with experiment.     

Excited-state properties and emission spectra of nonplanar heterocyclic helicenes

We discuss the electron-vibration coupling in mono-aza-[5]helicenes on the basis of a Franck-Condon analysis and density functional theory (DFT) calculations of the fluorescence and phosphorescence spectra measured in ethanol. The geometries of the initial states were obtained from time-dependent DFT (S(1)) and unrestricted DFT (T(1)) excited-state optimizations. In general, the position of the nitrogen atom has only a minor impact on the vibronic fine-structure in both absorption and emission. The shapes of the emission spectra from the lowest singlet and triplet states are found to be determined by contributions from multiple normal modes. The results of the calculations demonstrate how the interplay among these normal modes results in qualitatively and quantitatively different spectra for fluorescence and phosphorescence.