Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R&D work at the beamline focuses on various aspects of nuclear waste disposal within INE's mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 × 10+6 times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between ∼2.1 keV (P K-edge) and ∼25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M- and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.

We applied relativistic multiconfigurational all-electron ab initio calculations including the spin–orbit interaction to calculate the 3d4f resonant inelastic X-ray scattering (RIXS) map (3d_3/2 → 5f_5/2 U M₄ absorption edge and 4f_5/2 → 3d_3/2 U M_β emission) of uranyl (UO₂²⁺). The calculated data are in excellent agreement with experimental results and allow a detailed understanding of the observed features and an unambiguous assignment of all involved intermediate and final states. The energies corresponding to the maxima of the resonant emission and the non-resonant (normal) emission were determined with high accuracy, and the corresponding X-ray absorption near edge structure spectra extracted at these two positions were simulated and agree well with the measured data. With the high quality of our theoretical data, we show that the cause of the splitting of the three main peaks in emission is due to the fine structure splitting of the 4f orbitals induced through the trans di-oxo bonds in uranyl and that we are able to obtain direct information about the energy differences between the 5f and 4f orbitals: Δ5f δ/ϕ – 4f δ/ϕ, Δ5f π* – 4f π, and Δ5f σ* – 4f σ from the 3d4f RIXS map. RIXS maps contain a wealth of information, and ab initio calculations facilitate an understanding of their complex structure in a clear and transparent way. With these calculations, we show that the multiconfigurational protocol, which is nowadays applied as a standard tool to study the X-ray spectra of transition metal complexes, can be extended to the calculation of RIXS maps of systems containing actinides.

Complexation between hexavalent neptunium and nitrate was studied in aqueous nitric acid solution using optical absorption, vibrational and X-ray absorption spectroscopies. Distributions of aqueous [NpO₂]²⁺, [NpO₂(NO₃)]⁺ and [NpO₂(NO₃)₂] species were obtained as a function of nitric acid concentration between 0 and 14 M. The crystal structure of [NpO₂(NO₃)₂(H₂O)₂]·H₂O was determined.