The Counterintuitive Relationship between Orbital Energy, Orbital Overlap, and Bond Covalency in CeF 6 2– and CeCl 6 2–
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Booth, Corwin H.
Publications and source records attributed to Booth, Corwin H..
4f-Orbital mixing increases the magnetic susceptibility of Cp′ 3 Eu
X-ray absorption spectroscopy and variable temperature magnetometry show evidence of 4f-orbital mixing in Cp′ 3 Eu, which increases its magnetic susceptibility.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Realization of Organocerium-Based Fullerene Molecular Materials Showing Mott Insulator-Type Behavior
Abstract Electron-rich organocerium complexes (C 5 Me 4 H) 3 Ce and [(C 5 Me 5 ) 2 Ce(ortho-oxa)], with redox potentials E 1/2 = –0.82 V and E 1/2 = –0.86 V versus Fc/Fc + respectively, were reacted with fullerene (C 60 ) in different stoichiometries to obtain molecular materials. Structurally characterized co-crystals: [(C 5 Me 4 H) 3 Ce] 2 •C 60 (1) and [(C 5 Me 5 ) 2 Ce(ortho-oxa)] 3 •C 60 (2) of C 60 with cerium-based rare earth molecular precursors are reported for the first time. The extent of charge transfer in 1 and 2 was evaluated using a series of physical measurements: FT-IR, Raman, solidstate UV-vis-NIR spectroscopy, X-ray absorption near edge structure (XANES) spectroscopy, and magnetic susceptibility measurements. The physical measurements indicate that 1 and 2 comprise the cerium(III) oxidation state with formally neutral C 60 as a co-crystal in both cases. Pressure-dependent periodic density functional theory calculations were performed to study the electronic structure of 1. Inclusion of a Hubbard-U parameter removes Ce f states from the Fermi level, opens up a band gap, and stabilizes FM/AFM magnetic solutions that are isoenergetic because of the large distances between the Ce(III) cations. Furthermore, the electronic structure of this strongly correlated Mott insulator-type system is reminiscent of the well-studied Ce 2 O 3 .
36 MATERIALS SCIENCE↗
Strengths of covalent bonds in LnO 2 determined from O K-edge XANES spectra using a Hubbard model
A Hubbard model allows the covalent contribution to bond strength to be determined spectroscopically from O K-edge X-ray absorption fine structure spectra.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modeling Heterogeneity in UO 2 Nanoparticles Using X‐ray Absorption Spectroscopy
Abstract EXAFS provides the capability to interrogate nanoparticle (NP) structure in atomistic detail without relying on long‐range crystallinity. There is a limitation in that EXAFS provides averaged structural information, making it difficult to separate a small amount of heterogeneous structure from bulk. In this work, models were developed to extract surface‐specific information from conventional EXAFS measurements collected on UO 2 NPs of varying size. Specifically, the surface terminating species of UO 2 NPs was determined from comparison of coordination numbers with geometric models while the origin of static disorder was interrogated from user‐defined simulations. Results show that the degree of oxygenation on the NP surface does not significantly deviate from bulk surface and that static disorder is highly enhanced in NP surface layers but cannot be attributed to surface relaxation effects alone. The approach described herein has the potential to be adapted to a range of inorganic NP systems to interrogate surface structure.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Evaluation of 134 Ce as a PET imaging surrogate for antibody drug conjugates incorporating 225 Ac
The in vivo generator 134 Ce/ 134 La has the potential to serve as a PET imaging surrogate for both alpha-emitting 225 Ac and 227 Th radionuclides due to the unique Ce III /Ce IV redox couple and the relatively long half-life of 134 Ce. Furthermore, the purpose of this study was to demonstrate the compatibility of 134 Ce with DOTA-based antibody drug conjugates, which would act as therapeutic agents when incorporating 225 Ac.
62 RADIOLOGY AND NUCLEAR MEDICINE↗
Electronic structure studies reveal 4f/5d mixing and its effect on bonding characteristics in Ce-imido and -oxo complexes
Ce( iv ) complexes with multiple bonds display similar f 0 fractions, but different f/d hybridization, 5d-orbital energies, and TIP levels.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Correction: Enhanced 5f-δ bonding in [U(C 7 H 7 ) 2 ] - : C K-edge XAS, magnetism, and ab initio calculations
The authors regret that two references to the multi-configurational pair-density functional theory methods used in the wavefunction calculations did not appear in the main article. The references were originally included in the Methods section of the Electronic Supplementary Information as ref. 17a and b, but should also have appeared in the second paragraph on page 9564. The references are listed below as ref. 1 and 2. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Plutonium Co-precipitation with Calcite
The mobility of plutonium (Pu) in the environment is affected by Pu–mineral interactions, such as adsorption–desorption and structural incorporation. Calcite (CaCO 3 ) is a common secondary phase in near surface environments and a major component of many rocks and soils and is expected to form as an alteration product of cement-based materials planned for use in geological repositories. The reactivity of the calcite surface and its ability to tolerate significant variations in its chemical composition through substitution of Ca for other cations make calcite a potentially important sink for environmental contaminants. Here, single crystals of calcite were synthesized from aqueous solutions in equilibrium with air containing Pu as either Pu(VI) or Pu(IV) and characterized using a combination of laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and X-ray absorption spectroscopy (XAS). These data are used to assess the amount, structure, and oxidation state of Pu co-precipitated into calcite, providing insight into the potential for Pu sequestration in calcite precipitates. Overall, the XAS and LA–ICP–MS data support the co-precipitation of plutonyl [Pu(VI/V)] in the bulk calcite, although the exact nature of the co-precipitated Pu complex is difficult to elucidate in the synthesized material. Co-precipitated plutonyl could be incorporated in either distorted Ca lattice sites or defect sites, and we provide evidence to suggest that Pu(VI) is reduced mainly to Pu(V) in the precipitated solid. LA–ICP–MS additionally shows that the co-precipitation of Pu(VI/V) is favored over the co-precipitation of Pu(IV). Altogether, our results suggest that Pu sequestration in calcite under environmental conditions could immobilize Pu and isolate it from groundwater interactions in contaminated environments.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Enhanced 5f-δ bonding in [U(C 7 H 7 ) 2 ] − : C K-edge XAS, magnetism, and ab initio calculations
5f covalency in [U(C 7 H 7 ) 2 ] − was probed with carbon K-edge X-ray absorption spectroscopy (XAS) and electronic structure theory. The results are compared with earlier studies which show that the extent of δ-orbital mixing in [U(C 7 H 7 ) 2 ] 1− is larger than reported previously for U(C 8 H 8 ) 2 .
Qiao, Yusen↗
Using image area to control CCD systematic errors in spaceborne photometric and astrometric time-series measurements
The effect of some systematic errors for high-precision time-series spaceborne photometry and astrometry has been investigated with a CCD as the detector. The 'pixelization' of the images causes systematic error in astrometric measurements. It is shown that this pixelization noise scales as image radius r exp -3/2. Subpixel response gradients, not correctable by the 'flat field', and in conjunction with telescope pointing jitter, introduce further photometric and astrometric errors. Subpixel gradients are modeled using observed properties of real flat fields. These errors can be controlled by having an image span enough pixels. Large images are also favored by CCD dynamic range considerations. However, magnified stellar images can overlap, thus introducing another source of systematic error. An optimum image size is therefore a compromise between these competing factors.
Buffington, Andrew↗
A laboratory measurement of CCD photometric and dimensional stability
The sun exhibits periodic and quasi-periodic variability in its total luminosity, which provides information about its internal structure and dynamics. Variability ranges from a few minutes to many-year time scales, with amplitudes as small as a few ppm in the milliHz band. Extension of this analysis to a large sample of outer stars would be interesting: a panoramic detector such as a CCD could record many stars at once. To meet this objective, a ppm time-series differential precision is required. Laboratory CCD photometric measurements presented here are promising for such an instrument. Normalizing the response from a portion of the CCD area removes most of the individual-frame variability. When a trend attributed to a thermal transient in the CCD dewar is removed, the individual-frame photometric precision is about 0.0001, limited by photoelectron counting statistics. The time-series power spectrum is flat within the desired frequency domain. Analysis of the dimensional stability of the CCD within the same data set indicates better than ppm performance, when first-order bulk motion and magnification changes are removed.
Buffington, Andrew↗