The chelating gadolinium-complex is routinely used as magnetic resonance imaging (MRI) -contrast enhancer. However, several safety issues have recently been reported by FDA and PRAC. There is an urgent need for the next generation of safer MRI-contrast enhancers, with improved local contrast and targeting capabilities. Cerium oxide nanoparticles (CeNPs) are designed with fractions of up to 50% gadolinium to utilize the superior MRI-contrast properties of gadolinium. CeNPs are well-tolerated in vivo and have redox properties making them suitable for biomedical applications, for example scavenging purposes on the tissue- and cellular level and during tumor treatment to reduce in vivo inflammatory processes. Our near edge X-ray absorption fine structure (NEXAFS) studies show that implementation of gadolinium changes the initial co-existence of oxidation states Ce3+ and Ce4+ of cerium, thereby affecting the scavenging properties of the nanoparticles. Based on ab initio electronic structure calculations, we describe the most prominent spectral features for the respective oxidation states. The as-prepared gadolinium-implemented CeNPs are 3–5 nm in size, have r1-relaxivities between 7–13 mM−1 s−1 and show clear antioxidative properties, all of which means they are promising theranostic agents for use in future biomedical applications.

First-principles calculations of the core-level binding energy shifts (CLS) for 3d inner-core electrons of Ag and Pd in fcc Ag-Pd alloy were carried out within the complete screening picture, which includes both initial and final state effects. These alloys show remarkable CLS that have the same sign for both alloy components, in contradiction to what would be expected from the potential model for core electron energies. We show that the main contribution to the core-level shift is due to the intra-atomic charge redistribution, which is related to the hybridization between the valence electron states of the alloy components. There is also a large contribution to the CLS from the core-hole relaxation energy.

First-principles theoretical calculations of the core-level binding-energy shift ͑CLS͒ for eight binary facecentered-cubic ͑fcc͒ disordered alloys, CuPd, AgPd, CuNi, NiPd, CuAu, PdAu, CuPt, and NiPt, are carried out within density-functional theory ͑DFT͒ using the coherent potential approximation. The shifts of the Cu and Ni 2p 3/2 , Ag and Pd 3d 5/2 , and Pt and Au 4f 7/2 core levels are calculated according to the complete screening picture, which includes both initial-state ͑core-electron energy eigenvalue͒ and final-state ͑core-hole screening͒ effects in the same scheme. The results are compared with available experimental data, and the agreement is shown to be good. The CLSs are analyzed in terms of initial-and final-state effects. We also compare the complete screening picture with the CLS obtained by the transition-state method, and find very good agreement between these two alternative approaches for the calculations within the DFT. In addition the sensitivity of the CLS to relativistic and magnetic effects is studied.

X-ray absorption near-edge structure spectra are calculated by fully solving the electron/core-hole Bethe-Salpeter equation ͑BSE͒ in an all-electron framework. We study transitions from shallow core states, including the Mg L 2,3 edge in MgO, the Li K edge in the Li halides LiF, LiCl, LiBr, and LiI, as well as Li 2 O. We illustrate the advantage of the many-body approach over a core-hole supercell calculation. Both schemes lead to strongly bound excitons, but the nonlocal treatment of the electron-hole interaction in the BSE turns out to be crucial for an agreement with experiment.

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We show that core-level binding energy shifts (CLS) can be reliably calculated within density functional theory. The scheme includes both the initial (electron energy eigenvalue) as well as final state (relaxation due to core-hole screening) effects in the same framework. The results include CLS as a function of composition in substitutional random bulk and surface alloys. Sensitivity of the CLS to the local chemical environment in the bulk and at the surface is demonstrated. A possibility to use the CLS for structural determination is discussed. Finally, an extension of the model is made for Auger kinetic energy shift calculations.

We obtain x-ray absorption near-edge structures (XANES) by solving the equation of motion for the two-particle Green's function for the electron-hole pair, the Bethe-Salpeter equation (BSE), within the all-electron full-potential linearized augmented plane wave method (FPLAPW). The excited states are calculated for the Li K-edge in the insulating solids LiF, Li(2)O and Li(2)S, and absorption spectra are compared with independent particle results using the random phase approximation (RPA), as well as supercell calculations using the core-hole approximation within density functional theory (DFT). The binding energies of strongly bound excitations are determined in the materials, and core-exciton wavefunctions are demonstrated for LiF.