Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands.

Toward equatorial planarity about uranyl: synthesis and structure of tridentate nitrogen-donor {UO2}2+ complexes.

The reaction of UO2Cl2·3THF with the tridentate nitrogen donor ligand 2,6-bis(2-benzimidazolyl)pyridine (H2BBP) in pyridine leads to the formation of three different complexes: [(UO2)(H2BBP)Cl2] (1), [(UO)2(HBBP)(Py)Cl] (2), and [(UO2)(BBP)(Py)2] (3) after successive deprotonation of H2BBP with a strong base. Crystallographic determination of 1-3 reveals that increased charge through ligand deprotonation and displacement of chloride leads to equatorial planarity about uranyl as well as a more compact overall coordination geometry. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra of 1-3 at the U-4d edges have been recorded using a soft X-ray Scanning Transmission X-ray Microscope (STXM) and reveal the uranium 4d5/2 and 4d3/2 transitions at energies associated with uranium in the hexavalent oxidation state. First-principles Density Functional Theory (DFT) electronic structure calculations for the complexes have been performed to determine and validate the coordination characteristics, which correspond well to the experimental results.

Shallow impurity level calculations in semiconductors using ab initio methods.

An ab initio method is presented to calculate shallow impurity levels in bulk semiconductors. This method combines the GW calculation for the treatment of the central-cell potential with a potential patching method for large systems (with 64,000 atoms) to describe the impurity state wave functions. The calculated acceptor levels in Si, GaAs, and an isovalent bound state of GaP are in excellent agreement with experiments with a root-mean-square error of 8.4 meV.

Serial Uterine Artery Embolization for the Treatment of Placenta Percreta in the First Trimester: A Case Report.

Two patients with placenta percreta underwent uterine artery embolization (UAE) for abnormally invasive placenta (AIP) in the first trimester. Patient 1 had a 9-week cervical ectopic, while Patient 2 had a 9-week cesarean scar pregnancy. Elective termination of pregnancy was performed in both patients. UAE was performed with tris-acryl gelatin microspheres as well as gelfoam until stasis and was repeated in cases of revascularization. Both patients were followed with US/MRI/MRA scans and ß-hCG levels. Revascularization occurred in both patients following UAE, requiring multiple embolizations to achieve complete placental involution. Serial bland UAE may be an effective technique in the treatment of first-trimester AIP, with the distinct advantage of maintaining a patient's fertility. LEVEL OF EVIDENCE: Level IV.

Coordination Characteristics of Uranyl BBP Complexes: Insights from an Electronic Structure Analysis.

Organic ligand complexes of lanthanide/actinide ions have been studied extensively for applications in nuclear fuel storage and recycling. Several complexes of 2,6-bis(2-benzimidazyl)pyridine (H2BBP) featuring the uranyl moiety have been reported recently, and the present study investigates the coordination characteristics of these complexes using density functional theory-based electronic structure analysis. In particular, with the aid of several computational models, the nonplanar equatorial coordination about uranyl, observed in some of the compounds, is studied and its origin traced to steric effects.

Bright and ultra-fast scintillation from a semiconductor?

Semiconductor scintillators are worth studying because they include both the highest luminosities and shortest decay times of all known scintillators. Moreover, many semiconductors have the heaviest stable elements (Tl, Hg, Pb, Bi) as a major constituent and a high ion pair yield that is proportional to the energy deposited. We review the scintillation properties of semiconductors activated by native defects, isoelectronic impurities, donors and acceptors with special emphasis on those that have exceptionally high luminosities (e.g. ZnO:Zn, ZnS:Ag,Cl, CdS:Ag,Cl) and those that have ultra-fast decay times (e.g. ZnO:Ga; CdS:In). We discuss underlying mechanisms that are consistent with these properties and the possibilities for achieving (1) 200,000 photons/MeV and 1% fwhm energy resolution for 662 keV gamma rays, (2) ultra-fast (ns) decay times and coincident resolving times of 30 ps fwhm for time-of-flight positron emission tomography, and (3) both a high luminosity and an ultra-fast decay time from the same scintillator at cryogenic temperatures.