Electronic structure of americium sesquioxide probed by resonant inelastic x-ray scattering

The Am $5d$-$5f$ resonant inelastic x-ray scattering (RIXS) data of americium sesquioxide were measured at incident photon energies throughout the Am $O_{4,5}$ edges. The experiment was supported by calculations using several model approaches. While the experimental Am $O_{4,5}$ x-ray absorption spectrum of Am$_2$O$_3$ is compared with the spectra calculated in the framework of atomic multiplet and crystal-field multiplet theories and Anderson impurity model (AIM) for the Am(III) system, the recorded Am $5d$-$5f$ RIXS data are essentially reproduced by the crystal-field multiplet calculations. A combination of the experimental scattering geometry and theoretical analysis of the character of the electronic states probed during the RIXS process confirms that the ground state of Am$_2$O$_3$ is singlet $\Gamma_1$. An appearance of the low-intense charge-transfer satellite in the Am $5d$-$5f$ RIXS spectra at an energy loss of $\sim$5.5 eV, suggests weak Am $5f$-O $2p$ hybridization which is in agreement with AIM estimations of the $5f$ occupancy from spectroscopic data in Am$_2$O$_3$ as being 6.05 electrons

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO2+ also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO2+ and UO2+, but not the next two, NpO2+ and PuO2+. The An-O bond dissociation energies (BDEs) decrease from PaO2+ to PuO2+, such that the observation of a parallel decrease in the An-O bond reactivity is intriguing. To elucidate oxo exchange, we here extend experimental studies to AmO2+, americyl(V), and CmO2+, curyl(V), which were produced in remarkable abundance by electrospray ionization of Am3+ and Cm3+ solutions. Like other AnO2+, americyl(V) and curyl(V) adsorb up to four H2O molecules to form tetrahydrates AnO2(H2O)4+ with the actinide hexacoordinated by oxygen atoms. It was found that AmO2+ does not oxo-exchange, whereas CmO2+ does, establishing a "turn" to increasing the reactivity from americyl to curyl, which validates computational predictions. Because oxo exchange occurs via conversion of an actinyl(V) hydrate, AnO2(H2O)+, to an actinide(V) hydroxide, AnO(OH)2+, it reflects the propensity for actinyl(V) hydrolysis: PaO2+ hydrolyzes and oxo-exchanges most easily, despite the fact that it has the highest BDE of all AnO2+. A reexamination of the computational results for actinyl(V) oxo exchange reveals distinctive properties and chemistry of curyl(V) species, particularly CmO(OH)2+

Selective nitrogen adsorption via backbonding in a metal-organic framework with exposed vanadium sites.

Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations1-4. Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N2, through backbonding interactions5-7, and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates8. Here, we report a metal-organic framework featuring exposed vanadium(II) centres capable of back-donating electron density to weak π acids to successfully target π acidity for separation applications. This adsorption mechanism, together with a high concentration of available adsorption sites, results in record N2 capacities and selectivities for the removal of N2 from mixtures with CH4, while further enabling olefin/paraffin separations at elevated temperatures. Ultimately, incorporating such π-basic metal centres into porous materials offers a handle for capturing and activating key molecular species within next-generation adsorbents

Understanding the Subsurface Reactive Transport of Transuranic Contaminants at DOE Sites

Our primary hypothesis is that actinides can interact with surfaces in fundamentally different ways than other metals, metalloids, and oxyanions and that this fundamental difference requires new approaches to studying and modeling transuranic sorption to minerals and geomedia. This project supports a key mission of the SBR program to develop sufficient scientific understanding such that DOE sites will be able to incorporate coupled physical, chemical, and biological processes into decision making for environmental management and long-term stewardship, while also supporting DOE’s commitment to education, training, and collaboration with DOE user facilities

Resonant Photoemission in f-Electron Systems: Pu and Gd

Resonant photoemission in the Pu 5f and Pu 6p states is compared to that in the Gd 4f and Gd 5p states. Spectral simulations, based upon an atomic model with angular momentum coupling, are compared to the Gd and Pu results. Additional spectroscopic measurements of Pu, including core level photoemission and x-ray absorption, are also presented

Research program to investigate the fundamental chemistry of technetium

The objective of this research is to increase the knowledge of the fundamental technetium chemistry necessary to address challenges to the safe, long-term disposal of high-level nuclear waste posed by this element. The primary issues examined during the course of this project were the behavior of technetium and its surrogate rhenium during waste vitrification and glass corrosion. Since the redox behavior of technetium can play a large role in determining its volatility, one goal of this research was to better understand the behavior of technetium in glass as a function of the redox potential of the glass melt. In addition, the behavior of rhenium was examined, since rhenium is commonly used as a surrogate for technetium in waste vitrification studies. A number of glasses similar to Hanford Low Activity Waste (LAW) glasses were prepared under controlled atmospheres. The redox state of the glass was determined from the Fe(II)/Fe(III) ratio in the cooled glass, and the speciation of technetium and rhenium was determined by x-ray absorption fine structure (XAFS) spectroscopy. The behavior of rhenium and technetium during glass alteration was also examined using the vapor hydration test (VHT)

An in-situ cell for characterization of solids by soft X-rayabsorption

An in-situ cell using ''lab-on-a-chip'' technologies has been designed and tested for characterization of catalysts and environmental materials using soft X-ray absorption spectroscopy and spectromicroscopy at photon energies above 250 eV. The sample compartment is 1.0 mm in diameter with a gas path length of 0.8 mm to minimize X-ray absorption in the gas phase. The sample compartment can be heated to 533 K by an Al resistive heater and gas flows up to 5.0 cm{sup 3} min{sup -1} can be supplied to the sample compartment through microchannels. The performance of the cell was tested by acquiring Cu L{sub 3}-edge XANES data during the reduction and oxidation of a silica-supported Cu catalyst using the beam line 11.0.2 Scanning Transmission X-ray Microscope (STXM) at the Advanced Light Source of LBNL. Two-dimensional images of individual catalyst particles were recorded at photon energies between 926 eV and 937 eV, the energy range in which the Cu(II) and Cu(I) L{sub 3} absorption edges are observed. Oxidation state specific images of the catalyst clearly show the disappearance of Cu(II) species during the exposure of the oxidized sample to 4% CO in He while increasing the temperature from 308 K to 473 K. Reoxidation restores the intensity of the image associated with Cu(II). L-edge XANES spectra obtained from stacks of STXM images show that with increasing temperature the Cu(II) peak intensity decreases as the Cu(I) peak intensity increases

Performance Characteristics of Beamline 6.3.1 from 200 eV to 2000 eV at the Advanced Light Source

Bend magnet beamline 6.3.1 at the Advanced Light Source operates from 200 eV to 2000 eV, primarily used for x-ray absorption fine structure investigations. The beamline optics consist of a compact, entrance-slitless, Hettrick-Underwood type variable-line-spacing plane-grating monochromator and refocusing mirrors to provide a 25 μm × 500 μm spot at the focal point in the reflectometer end station. Wavelength is scanned by the simple rotation of the grating and illuminates a fixed exit slit. The LabView based beamline control and data acquisition computer code has been implemented to provide a convenient interface to the user. The dedicated end station is a reflectometer that is isolated from the beamline by a differential ion pump. The reflectometer can position samples to within 4 μm with an angular position of 0.002°, has total electron and fluorescence yield detectors, and pumps down in about 30 minutes. External end stations can be mounted downstream of the reflectometer as well. The versatility and simplicity of beamline 6.3.1 have made it useful for a wide range of applications such as the characterization of optical components, reflective coatings, and the investigation of a diverse range of materials in both the solid state and in solution

Transuranic interfacial reaction studies on manganese oxidemineral surfaces

Several DOE sites have been contaminated by transuranicradionuclide (TRU) discharges including neptunium and plutonium. Theirinteraction with the surrounding geological media can affect thetransport and remediation of these radionuclides in the environment.Manganese based minerals, present as minor phases in the vadose zone, canpreferentially sequester TRU over other minerals present in largerquantities. The objective of this project is to understand theinteractions between plutonium and neptunium and manganese oxyhydroxideminerals to predict potential hazards they represent to the environment,as well as to provide important scientific information for the design ofeffective remediation strategies for contaminated DOE sites

Surprising Coordination Geometry Differences in Ce(IV)- and Pu(IV)-Maltol Complexes

As part of a study to characterize the detailed coordination behavior of Pu(IV), single crystal X-ray diffraction structures have been determined for Pu(IV) and Ce(IV) complexes with the naturally-occurring ligand maltol (3-hydroxy-2-methyl-pyran-4-one) and its derivative bromomaltol (5-bromo-3-hydroxy-2-methyl-pyran-4-one). Although Ce(IV) is generally accepted as a structural analog for Pu(IV), and the maltol complexes of these two metals are isostructural, the corresponding bromomaltol complexes are strikingly different with respect to ligand orientation about the metal ion: All complexes exhibit trigonal dodecahedral coordination geometry but the Ce(IV)-bromomaltol complex displays an uncommon ligand arrangement not mirrored in the Pu(IV) complex, although the two metal species are generally accepted to be structural analogs