A systematic X-ray absorption study at actinide N6,7 (4f → 6d transitions) edges was performed for light-actinide oxides including data obtained for the first time for NpO2, PuO2, and UO3. The measurements were supported by ab initio calculations based on local-density-approximation with added 5f-5f Coulomb interaction (LDA+U). Improved energy resolution compared to common experiments at actinide L(2,3) (2p → 6d transitions) edges allowed us to resolve the major structures of the unoccupied 6d density of states (DOS) and estimate the crystal-field splittings in the 6d shell directly from the spectra of light-actinide dioxides. The measurements demonstrated an enhanced sensitivity of the N(6,7) spectral shape to changes in the compound crystal structure. For nonstoichiometric NpO(2-x), the filling of the entire band gap with Np 6d states was observed thus supporting a phase coexistence of Np metal and stoichiometric NpO2 which is in agreement with the tentative Np-O phase diagram.

A systematic X-ray absorption study at the U 3d, 4d, and 4f edges of UO2 was performed, and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescence-detection (HERFD) mode of X-ray absorption spectroscopy (XAS) at the U 3d(3/2) edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced core-hole lifetime broadening. This multiedge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree of the 5f localization in UO2. The results support the covalent character of UO2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications.

A systematic x-ray absorption study at the U 3d, 4d and 4f edges of UO2 was performed and the data were analyzed within framework of the Anderson impurity model. By applying the high-energy-resolution fluorescencedetection (HERFD) mode of x-ray absorption spectroscopy (XAS) at the U 3d3/2 edge and conducting the XAS measurements at the shallower U 4f levels, fine details of the XAS spectra were resolved resulting from reduced corehole lifetime broadening. This multi-edge study enabled a far more effective analysis of the electronic structure at the U sites and characterization of the chemical bonding and degree of the 5f localization in UO2. The results support the covalent character of UO2 and do not agree with the suggestions of rather ionic bonding in this compound as expressed in some publications. Introduction While it has been agreed that UO2 is a Mott-Hubbard system, where the energy gap has f − f character, the degree of localization/delocalization of the U 5f states in UO2 is still under debate. The conclusions about the character of chemical bonding in UO2 made by different research groups vary from ionic to highly covalent compound. The important characteristic in this respect is the U 5f occupancy (nf ) in the ground state of UO2 that is often estimated from the electronic structure calculations or x-ray spectroscopic measurements. For example, nf was deduced to be close to 2.0 electrons from the analysis of the resonant xray emission spectra at the U L3 edge of UO2 while the analysis of the x-ray photoemission spectroscopy (XPS) data suggested nf ' 2.3 electrons. The latter results indicate some degree of covalency in the chemical bonding of this dioxide. The employment of the advanced theoretical/computational formalisms, based on lo-

Soft x-ray emission and absorption spectroscopic data are reported for the O 1s region of a single crystal of UO2, a polycrystalline NpO2 sample, and a single crystal of PuO2. The experimental data are interpreted using first-principles correlated-electron calculations within the framework of the density functional theory with added Coulomb U interaction (DFT+U). A detailed analysis regarding the origin of different structures in the x-ray emission and x-ray absorption spectra is given and the effect of varying the intra-atomic Coulomb interaction-U for the 5f electrons is investigated. Our data indicate that O 1s x-ray absorption and emission spectroscopies can, in combination with DFT+U calculations, successfully be used to study 5f-shell Coulomb correlation effects in dioxides of light actinides. The values for the Coulomb U parameter in these dioxides are derived to be in the range of 4-5 eV.

The electrical resistivity of amorphous Fe100-xZrx metal alloy films and multilayers has been investigated in a wide temperature and composition range. The overall behavior of the resistivity is consistent with bulk measurements, exhibiting prominent semiconductor-like changes at low temperatures. The transition from positive (metallic) to negative temperature coefficient of resistivity behavior is accompanied by minute changes in magnetoresistance and we can therefore rule out magnetic phase changes as being the cause for the observed changes in the resistivity. Using x-ray absorption and emission spectroscopies we are able to probe the unoccupied and occupied electronic densities of states. The corresponding spectra are found to significantly overlap, as expected for a metallic-like electronic structure and the absence of a band gap. Besides a broadening of the x-ray emission lines expected from an amorphous material, remarkably small differences are observed in the electronic structures when changing the amount of Zr. The resistivity data were modeled and agreement with the Mott variable range hopping model was found, indicating localized electronic states due the disordered structure of the Fe100-xZrx alloys.

The electronic structure of single-crystal PuO${}_{2}$ is studied using O $1s$ x-ray absorption (XA) and x-ray emission. Interpretation of the experimental data is supported by extensive first-principles calculations on the basis of the $\mathrm{density}\mathrm{ }\mathrm{functional}\mathrm{ }\mathrm{theory}+U$ approach. The measured XA spectra show a significant difference in intensity for the first two peaks between different spots or areas on the single crystal. Our theoretical simulations show that the first peak, at $~$531 eV, can be attributed to O $2p$-Pu 5$f$ hybridization, while the second peak, at $~$533.4 eV, is due to hybridization of O 2$p$ with Pu $d$ states. The reasons for the observed differences in the O $1s$ XA spectra are explored by calculating a number of defect structures PuO${}_{2\ifmmode\pm\else\textpm\fi{}x}$ as well as by simulating the existence of Pu(V) sites. Our results indicate the presence of oxidation states higher than Pu(IV) in some areas of the single crystal. The findings also suggest that plutonium oxide with a Pu fraction in an oxidation state higher than Pu(IV) consists of inequivalent Pu sites with Pu${}^{(\mathrm{IV})}$O${}_{2}$ and Pu${}^{(\mathrm{V})}$O${}_{2}$ rather than representing a system where the Pu oxidation state is constantly fluctuating between Pu(IV) and Pu(V).

Temperature dependence of the electrical resistivity of highly amorphous Fe-Zr films and multilayers

We have used X-ray absorption (XA) and resonant inelastic X-ray scattering (RIXS) spectroscopies to study a series of copper compounds, namely Cu2O, CuO, Cu(OH)2, CuCl2, Cu2S, CuSO4, malachite (Cu2(CO3)2(OH)2) and atacamite (CuCl2·3Cu(OH)2). Cu 2p XA spectra provide information about oxidation states. Divalent copper gives a single narrow line due to excitations into the empty 3d state, whereas monovalent copper gives a broad band at higher energy due to transitions to 4s states. Chemical shifts of the main line in the Cu2+ XA spectra of different compounds are observed but in some cases they are too small to make a clear distinction between the species. It is shown that RIXS at the Cu 2p edge has a great potential to distinguish between the species due to large differences in spectral shapes for the same energy of the incident photon beam. First evidence for the possibility of detecting chemical composition of copper compounds is presented and discussed in details.

Resonant Inelastic X-ray Scattering as fingerprint for characterization of complex copper systems

An instrumental and experimental setup for soft x-ray spectroscopy meeting the requirements of a closed source for radioactivity is described. The system consists of a vacuum sealed cell containing the sample, mounted on a tubing system to ensure compatibility with most standard manipulators. The soft x rays penetrate a thin x-ray window separating the interior of the cell from the vacuum in the experimental chamber. Our first results for single crystal PuO2 confirm the feasibility of experiments using the setup. The results are consistent with results of first principles calculations and previously recorded spectra obtained using a standard open source setup. The results show that the closed source experimental system can be used to collect valuable experimental data from radioactive materials.

Soft x-ray emission spectroscopy was used to characterize the electronic structure of seven copper nitride films, one synthesized with atomic layer deposition (ALD) and six grown with chemical vapor deposition (CVD) at different preparation temperatures. Interpretation of the x-ray emission spectra was supported by calculations of the electronic structure for bulk pure Cu(3)N and Cu(3)N with: an excess of Cu atoms, oxygen or carbon impurities, and N vacancies. The calculations are shown to describe the experimental spectra quite well. Analysis of the x-ray spectra suggests that films grown in copper rich environments and above a cut-off temperature of approximately 360 °C have a growing fraction of copper enriched areas, while films prepared below this temperature do not have these areas with excess copper.

This study illustrates how the damage from copper corrosion can be reduced by modifying the chemistry of the copper surface environment. The surface modification of oxidized copper films induced by chemical reaction with Cl− and HCO3- in aqueous solutions was monitored by in situ X-ray absorption spectroscopy. The results show that corrosion of copper can be significantly reduced by adding even a small amount of sodium bicarbonate. The studied copper films corroded quickly in chloride solutions, whereas the same solution containing 1.1mM HCO3- prevented or slowed down the corrosion processes.

The possibilities for using x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS) to probe the Cu oxidation state and changes in the electronic structure during interaction between copper and ground-water solutions were examined. Surface modifications induced by chemical reactions of oxidized 100 Å Cu films with Cl−, SO42− and HCO3− ions in aqueous solutions with various concentrations were studied in situ using liquid cells. Copper corrosion processes in ground water were monitored for up to nine days. By comparing Cu 2p–3d, 4s transitions for a number of reference substances previously measured, changes in electronic structure of the Cu films were analysed. The XAS and RIXS spectral shape at the Cu edge, the chemical shift of the main line for Cu2+, and the energy positions of the observed satellites served as a tool for monitoring the changes during the reaction. It was found that the pH value and the Cl− concentration in solutions strongly affect the speed of the corrosion reaction.