7 research outputs found
Characterization of bonding differences by advanced synchrotron based X-ray spectroscopy
The present PhD thesis demonstrates differences in relative electronic densities and mixing of metal with ligand valence orbitals between the n-Pr-BTP ligand, the [Ln(n-Pr-BTP)3](OTf)3 and [An(n-Pr-BTP)3](OTf)3 complexes using N K edge XANES spectroscopy, Ln/An L3 edge HR-XANES spectroscopy and quantum chemical calculations. A spectrometer for high-energy resolution X-ray emission spectroscopy and a liquid cell for non-resonant inelastic X-ray scattering were designed, built and commissioned
Opportunities and challenges of applying advanced X-ray spectroscopy to actinide and lanthanide N-donor ligand systems
N-donor ligands such as n-Pr-BTP [2,6-bisÂ(5,6-diÂpropyl-1,2,4-triazin-3-yl)Âpyridine] preferentially bind trivalent actinides (An) over trivalent lanthanides (Ln) in liquid–liquid separation. However, the chemical and physical processes responsible for this selectivity are not yet well understood. Here, an explorative comparative X-ray spectroscopy and computational (L3-edge) study for the An/Ln L-edge and the N K-edge of [An/Ln(n-Pr-BTP) ](NO), [Ln(n-Pr-BTP) ](CFSO) and [Ln(n-Pr-BTP) ](ClO) complexes is presented. High-resolution X-ray absorption near-edge structure (HR-XANES) L-edge data reveal additional features in the pre- and post-edge range of the spectra that are investigated using the quantum chemical codes FEFF and FDMNES. X-ray Raman spectroscopy studies demonstrate the applicability of this novel technique for investigations of liquid samples of partitioning systems at the N K-edge