arXiv subjects
Publications and source records attributed to Philippe Sainctavit.
The tris pyrazolyl borate ligand imposes a rigid scaffold around Fe( ii ) ensuring a robust magnetic anisotropy when the molecules assembled as monolayers suffer from the dissymmetric environment of the substrate/vacuum interface.
The nanoscale distribution of magnetic anisotropies was measured in core@shell MnFe$_2$O$_4$@CoFe$_2$O$_4$ 7.0 nm particles using a combination of element selective magnetic spectroscopies with different probing depths. As this picture is not accessible by any other technique, emergent magnetic properties were revealed. The coercive field is not constant in a whole nanospinel. The very thin (0.5 nm) CoFe$_2$O$_4$ hard shell imposes a strong magnetic anisotropy to the otherwise very soft MnFe$_2$O$_4$ core: a large gradient in coercivity was measured inside the MnFe$_2$O$_4$ core with lower values close to the interface region, while the inner core presents a substantial coercive field (0.54 T) and a very high remnant magnetization (90% of the magnetization at saturation).
After a review of temperature-dependent experimental x-ray absorption near-edge structure (XANES) and related theoretical developments, we present the Al K-edge XANES spectra of corundum and beryl for temperature ranging from 300K to 930K. These experimental results provide a first evidence of the role of thermal fluctuation in XANES at the Al K-edge especially in the pre-edge region. The study is carried out by polarized XANES measurements of single crystals. For any orientation of the sample with respect to the x-ray beam, the pre-edge peak grows and shifts to lower energy with temperature. In addition temperature induces modifications in the position and intensities of the main XANES features. First-principles DFT calculations are performed for both compounds. They show that the pre-edge peak originates from forbidden 1s to 3s transitions induced by vibrations. Three existing theoretical models are used to take vibrations into account in the absorption cross section calculations: i) an average of the XANES spectra over the thermal displacements of the absorbing atom around its equilibrium position, ii) a method based on the crude Born-Oppenheimer approximation where only the initial state is averaged over thermal displacements, iii) a convolution of the spectra obtained for the atoms at the equilibrium positions with an approximate phonon spectral function. The theoretical spectra so obtained permit to qualitatively understand the origin of the spectral modifications induced by temperature. However the correct treatment of thermal fluctuation in XANES spectroscopy requires more sophisticated theoretical tools.
The influence of atomic vibrations on x-ray absorption near edge structure (XANES) is calculated by assuming that vibrational energies are small with respect to the instrumental resolution. The resulting expression shows that, at the K-edge, vibrations enable electric dipole transitions to 3s and 3d final states. The theory is applied to the K-edge of Al in Al2O3 corundum and of Ti in TiO2 rutile and compared with experiment. At the Al K-edge, sizeable transitions towards 3s final states are obtained, leading to a clear improvement of the agreement with experimental spectra. At the Ti K-edge, electric dipole transitions towards 3d final states explain the temperature dependence of the pre-edge features.
The angular dependence (x-ray linear dichroism) of the Cr K pre-edge in MgAl2O4:Cr3+ spinel is measured by means of x-ray absorption near edge structure spectroscopy (XANES) and compared to calculations based on density functional theory (DFT) and ligand field multiplet theory (LFM). We also present an efficient method, based on symmetry considerations, to compute the dichroism of the cubic crystal starting from the dichroism of a single substitutional site. DFT shows that the electric dipole transitions do not contribute to the features visible in the pre-edge and provides a clear vision of the assignment of the 1s-->3d transitions. However, DFT is unable to reproduce quantitatively the angular dependence of the pre-edge, which is, on the other side, well reproduced by LFM calculations. The most relevant factors determining the dichroism of Cr K pre-edge are identified as the site distortion and 3d-3d electronic repulsion. From this combined DFT, LFM approach is concluded that when the pre-edge features are more intense than 4 % of the edge jump, pure quadrupole transitions cannot explain alone the origin of the pre-edge. Finally, the shape of the dichroic signal is more sensitive than the isotropic spectrum to the trigonal distortion of the substitutional site. This suggests the possibility to obtain quantitative information on site distortion from the x-ray linear dichroism by performing angular dependent measurements on single crystals.
We determine the structural relaxations around paramagnetic impurities (Ti, Cr, Fe) in corundum (alpha-Al2O3), by combining x-ray absorption near edge structure (XANES) experiments and ab initio calculations. The structural relaxations are found to be very local. We then show that XANES is sensitive to small variations in interatomic distances within the coordination shell of the absorbing atom. The experiments were carried out on single crystals of ruby and sapphires. Linear dichroic signals are essential to characterize the geometry of the impurity site. The calculations were performed within a self-consistent ``non muffin-tin'' framework, that uses pseudopotentials, plane-wave basis set, and the continued fraction for the absorption cross section.