Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach

Nanoscale investigation of light-matter interactions mediated by magnetic and electric coupling

In nano-optics, light is controlled at length scales smaller than the wavelength. Consequently, investigations of photonic nanostructures require a resolution beyond the diffraction limit. Near-field microscopy has been one of the pillars of nano-optics since 1980s, as it can provide the necessary subwavelength resolution. This thesis provides a careful study of the electro-magnetic response of the coated probe which forms the heart of a near-field microscope. With the resulting insights we succeed in performing a new type of nanoscale investigation which involves both magnetic and electric fields at the nanoscale. \ud Firstly, we show that an aperture probe can simultaneously map the two in-plane electric field components of light in a photonic nanostructure. By performing phase-sensitive near-field measurements of both components, we reconstruct the highly structured in-plane polarization state of light in a photonic crystal waveguide, leading to the observation of polarization singularities at the nanoscale.\ud Secondly, we found that a coated probe is sensitive to the out-of-plane component of a magnetic field at optical frequency. Although this magnetic coupling does not lead to a direct detection of the magnetic field, it gives rise to new a type of interaction between probe and sample. By controlling the probe position near a maximum of a rapidly varying magnetic field component of light trapped in a photonic crystal nanocavity, we induce a novel blue-shift of the resonance frequency. In addition, we are able to increase the photon lifetime of the cavity through magnetic interaction. \ud Thirdly, by engineering the geometry of an aperture probe at the nanoscale, we succeed in unambiguously mapping the magnetic field of propagating light in a photonic structure. By using metamaterials concepts, we simultaneously visualize the electric and magnetic component of light with subwavelength resolution and phase sensitivity

Diffraction line profiles of spherical hollow nanocrystals

An analytical expression of diffraction line profiles of spherical hollow nanocrystals (NCs) is derived. The particular features of the profile lines, enhanced peak tail intensity, are analyzed and..

Weak localization of light in superdiffusive random systems

L\'evy flights constitute a broad class of random walks that occur in many fields of research, from animal foraging in biology, to economy to geophysics. The recent advent of L\'evy glasses allows to study L\'evy flights in controlled way using light waves. This raises several questions about the influence of superdiffusion on optical interference effects like weak and strong localization. Super diffusive structures have the extraordinary property that all points are connected via direct jumps, meaning that finite-size effects become an essential part of the physical problem. Here we report on the experimental observation of weak localization in L\'evy glasses and compare results with recently developed optical transport theory in the superdiffusive regime. Experimental results are in good agreement with theory and allow to unveil how light propagates inside a finite-size superdiffusive system

Sintering and mechanical properties of β‐SiC powder obtained from waste tires

Plasma synthesized SiC powder obtained from quartz and carbonaceous residue of waste tires was successfully sintered at 1925 ℃ by pressureless liquid-phase method using yttria and alumina as sintering aids (T-SiC). Comparison with sintered SiC obtained from commercial powder (C-SiC) put in evidence of similar sintered density (98%T.D.), but much finer microstructure of T-SiC than that of C-SiC. T-SiC also showed higher flexural strength than C-SiC both at room temperature (508 vs. 458 MPa) and at 1500 ℃ (280 vs. 171 MPa). Difference in liquid phase was responsible for the differences in hardness and fracture toughness. The high value of the Young's modulus of T-SiC (427 MPa) confirmed the high degree of sinterability of this powder and that it can be a promising candidate for structural applications with high added value. © 2016, The Author(s)

New fluorescent polymeric nanocomposites synthesized by antimony dodecyl-mercaptide thermolysis in polymer

In this work, the formation of semiconductive Sb2S3 nanoparticles inside amorphous polystyrene has been achieved by thermal degradation of the corresponding antimony dodecyl-mercaptide, Sb(SC12H25)3. The thermolysis of the dodecyl-mercaptide precursor was studied as both pure phase and mercaptide solution in polystyrene. The thermal decom- position of the antimony mercaptide precursor at 350°C, under vacuum, showed the formation of a mixture of antimony trisulfide (stibnite, Sb2S3) and zero-valent antimony (Sb) phase. X-ray Powder Diffraction (XRD) and Rietveld analysis carried out on the obtained nanostructured powder confirmed the presence of Sb and Sb2S3 phases in 10.4 wt% and 89.6 wt% amount, respectively. The same pyrolysis reaction was carried out in the polymer and the resulting nanocompos- ite material was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-VIS spec- troscopy, and fluorescence spectroscopy. The nanocomposite structural characterization indicated the presence of well-dispersed nanoclusters of antimony and stibnite (15-30 nm in size) inside the amorphous polymeric phase. Optical measurements on the obtained nanocomposite films showed a strong emission at 432 nm upon excitation at 371 nm, prob- ably related to the presence of Sb2S3 nanoclusters

Hydrogeochemistry of Magra Valley (Italy) Aquifers: Geochemical Background of an Area Investigated for Seismic Precursors

AbstractWe present the results of a hydrogeochemical survey of 111 springs and wells from Magra Valley, a seismic area located in northern Tuscany, Italy. This survey was aimed at defining the geochemical background and the underground fluid circulation scheme of an area currently investigated for earthquake precursory phenomena, with the final goal of identifying a suitable location for installation of a continuous automatic monitoring station for the remote control of hydrogeochemical parameters. Six springs of the project were identified suitable for the purpose, and the Equi Na-Cl-type spring emerged as the best candidate for the installation of a monitoring station