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↗
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↗