Measurement of UO2 surface oxidation using grazing-incidence x-ray diffraction: Implications for nuclear forensics
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nuclear (including radiation effects), materials a↗
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Radiation damage study of POCO ZXF-5Q graphite for neutrino production targets using 4.5 MeV helium ions
To address the challenges of increased beam power and target survivability associated with next-generation particle production beam lines, high dose, high-energy proton beam conditions are simulated using irradiation from low-energy ion beams. A low-energy ion irradiation study of POCO ZXF-5Q graphite under conditions similar to those of the NuMI NT-02 neutrino production target at the Fermi National Accelerator Laboratory is reported. Helium ion irradiation was performed at 100 ∘ C to a maximum damage level of 0.9 displacements per atom (DPA). Irradiation induced hardening, swelling of the irradiated region, inter-plane lattice expansion, and intraplane lattice contraction with increasing ion fluence was observed using micromechanical (nanoindentation, atomic force microscopy) and electron microscopy (high-resolution imaging, selected area diffraction) characterization. Similar changes were also observed in post irradiation examination of the NT-02 target indicating that ion irradiation can be a valuable tool for estimating radiation damage in proton beam targets. Caution must be exercised though, because the hardening, lattice alteration, and swelling occur to different magnitudes for a given damage level. The observed hardening and embrittlement were greater for ion irradiated graphite. For He ion irradiated samples the lattice spacing changes were smaller at low damage levels (78% less expansion and 71% less contraction at 0.1 DPA) and larger at high damage levels (38% more expansion and 5% more contraction at 0.9 DPA) relative to that observed in the NT-02 target. The magnitude of swelling was 8.5× greater under ion irradiation which is influenced by the differing damage gradients and inclusion of implanted He ions in the region of interest.
43 PARTICLE ACCELERATORS↗
Ultra-flexible framework breathing in response to dehydration in liskeardite, [(Al,Fe){sub 16}(AsO{sub 4}){sub 9}(OH){sub 21}(H{sub 2}O){sub 11}]·26H{sub 2}O, a natural open-framework compound
Dehydration of the natural open-framework compound, liskeardite, [(Al,Fe){sub 16}(AsO{sub 4}){sub 9}(OH){sub 21}(H{sub 2}O){sub 11}]·26H{sub 2}O, is accompanied by a change in the sign of the thermal expansion from positive to negative above room temperature, and at ~100 °C the structure undergoes a dramatic 2D contraction by co-operative rotation of heteropolyhedral columns that constitute the framework walls. Monoclinic liskeardite, I112 with a≈b≈24.7 Å, c ≈7.8 Å and β≈90° is transformed to a tetragonal phase, I-4 with a≈20.6 Å, c ≈7.7 Å. The associated 30% decrease in volume is unprecedented in inorganic microporous compounds. The flexibility of the contraction is related to the double-hinged nature of the column rotations about [001]. Octahedra in adjacent columns are interconnected by corner-sharing with the two pairs of anions forming opposing edges of AsO{sub 4} tetrahedra, so a double-hinged rotation mechanism operates. Thermal analysis and mass spectroscopic results for liskeardite show that the phase transition at ~100 °C is related to removal of the channel water. The tetragonal phase shows exceptionally large NTE behaviour. Over the temperature range 148–178 the NTE along a and b is close to linear with a magnitude of the order of −900×10{sup −6} °C{sup −1}. The contraction along the channel direction is smaller but still appreciable at −200×10{sup −6} °C{sup −1}. - Graphical abstract: Structure of the collapsed liskeardite framework, formed on dehydration above 100 °C. - Highlights: • The thermal expansion of the mineral liskeardite changes + to − above ambient. • Dehydration at 100 °C results in a record reversible 30% volume reduction. • In situ synchrotron XRD has led to a structural model for the dehydrated phase. • Framework breathing flexibility is attributed to a double-hinge rotation mechanism. • The dehydrated phase shows unprecedented -ve expansion for inorganic materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
On the marginal value of electricity storage
We investigate the problem of characterizing the economic value of energy storage capacity to a wind power producer (WPP) that sells its energy in a conventional two-settlement electricity market. The WPP can offer a forward contract to supply power in the day-ahead market, subject to financial penalties for imbalances between the contracted power and the power that is delivered in real-time. We consider the setting in which the WPP has access to a co-located energy storage system, and can thus reshape its wind power production subject to its storage capacity constraints. Modeling wind power as a random process, we show that the problem of determining optimal forward contract offerings—given recourse with storage—is convex. We further establish that the maximum expected profit is concave and non-decreasing in the energy storage capacity, which reveals that the greatest marginal benefit from energy storage is derived from initial investment in small storage capacity. We provide a characterization of the marginal value of small energy storage capacity to the WPP. The formulae we derive shed light on the relationship between the value of storage and certain statistical measures of variability in the underlying wind power process.
25 ENERGY STORAGE↗
Structural Distortions and Uniaxial Negative Thermal Expansion in the Polar Dion–Jacobson Oxide RbNdTa 2 O 7
We provide deeper insight into the crystal structures, sequential structural phase transitions (I2cm → Cmce → I4/mcm → P4/mmm), thermal expansion, and electronic properties of the n = 2 Dion–Jacobson polar oxide RbNdTa 2 O 7 , through X-ray powder diffraction, neutron powder diffraction, Raman studies, and density functional theory calculations. We observed a uniaxial negative thermal expansion (NTE) across the first-order transition, I2cm → Cmce, where the unit cell contracts along the c-axis, which is driven by a contraction of the NdTa 2 O 6 layer. Here, this NTE occurs within the temperature range of the first-order phase transition and contrasts with the corkscrew mechanism typically observed in Ruddlesden–Popper phases. In RbNdTa 2 O 7 , the I2cm (hybrid improper ferroelectric) → Cmce (antipolar) transition involves crucial changes in the bond lengths of Nd and Ta polyhedra, coupled with polar to antipolar displacement of the Nd ions, leading to a net contraction in the NdTa 2 O 6 layer along the c-axis, while preserving the overall octahedral tilting magnitude. This transition highlights the intricate interplay between the Nd and Ta coordination and the associated TaO 6 distortions. Temperature-dependent Raman spectra analysis further confirms the first-order structural transition and associated NTE, providing evidence for increased bond stiffness across this transition. Additionally, using neutron powder diffraction, we have determined that the transition I4/mcm → P4/mmm occurs at approximately 1150 K. Finally, we have calculated from DFT + U, the partial density of states, the energy bandgaps, and effective masses of the charge carriers of the polar ground structure.
Chemical structure↗
Tracking Co(I) Intermediate in operando in Photocatalytic Hydrogen Evolution by X-ray transient Absorption Spectroscopy and DFT Calculation
X-ray transient absorption spectroscopy (XTA) and optical transient spectroscopy (OTA) were used to probe the Co(I) intermediate generated in situ from an aqueous photocatalytic hydrogen evolution system, with [RuII(bpy)3]Cl2·6H2O as the photosensitizer, ascorbic acid/ascorbate as the electron donor, and the Co-polypyridyl complex ([CoII(DPABpy) Cl]Cl) as the pre-catalyst. Upon exposure to light, the XTA measured at Co K-edge visualizes the grow and decay of the Co(I) intermediate, and reveals its Co-N bond contraction of 0.09 ± 0.03 Å. Density functional theory (DFT) calculations support the bond contraction and illustrate that the metal-to-ligand π back-bonding greatly stabilizes the penta-coordinated Co(I) intermediate, which provides easy photon access. To the best of our knowledge, this is the first example of capturing the penta-coordinated Co(I) intermediate in operando with bond contraction by XTA, thereby providing new insights for fundamental understanding of structure– function relationship of cobalt-based molecular catalysts.
Li, Zhi-Jun↗
Ultrafast Carrier–Lattice Interactions and Interlayer Modulations of Bi 2 Se 3 by X-ray Free-Electron Laser Diffraction
We report as a 3D topological insulator, bismuth selenide (Bi 2 Se 3 ) has potential applications for electrically and optically controllable magnetic and optoelectronic devices. Understanding the coupling with its topological phase requires studying the interactions of carriers with the lattice on time scales down to the sub-picosecond regime. Here we investigate the ultrafast carrier-induced lattice contractions and interlayer modulations in Bi 2 Se 3 thin films by time-resolved diffraction using an X-ray free-electron laser. The lattice contraction depends on the carrier concentration and is followed by an interlayer expansion accompanied by oscillations. Using density functional theory (DFT) and the Lifshitz model, the initial contraction can be explained by van der Waals force modulation of the confined free carrier layers. Our theory suggests that band inversion, related to a topological phase transition, is modulated by the expansion of the interlayer distance. These results provide insights into the topological phase control by light-induced structural change on ultrafast timescales.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Single-Step Conversion of Ethanol to n-Butene over Ag-ZrO2/SiO2 Catalysts
Ethanol is a promising platform molecule for production of a variety of fuels and chemicals. Of particular interest is producing middle distillate fuels (i.e., jet and diesel blendstock) from renewable ethanol feedstock. State-of-the-art alcohol-to-jet technology requires multiple process steps based on catalytic dehydration of ethanol to form ethylene, followed by sometimes a multi-step oligomerization, and then hydrotreatment and distillation. Here we report on a new catalytic route in which ethanol is directly converted to n-butene (1- and 2-butene mixtures) over Ag-ZrO2/SBA-16, thus offering the potential for a reduction in the number of required processing steps versus conventional alcohol-to-jet technology. This catalyst system provides the balanced metal and Lewis acid sites required to selectively facilitate a cascading sequence of reactions that includes dehydrogenation, aldol condensation, Meerwein–Ponndorf–Verley reduction, dehydration, and hydrogenation. High conversion and selectivity toward either n-butene or 1,3-butadiene is achieved by tuning the hydrogen feed partial pressure and other process/catalyst parameters. With sufficient hydrogen partial pressure 1,3-butadiene is completely and selectively hydrogenated to form n-butene. The reaction mechanism was elucidated through operando-nuclear magnetic resonance investigations coupled with reactivity measurements. Combined experimental-computational investigation reveals how changes in silver and zirconium composition and the silver oxidation state affects reactivity under controlled hydrogen partial pressures and after prolonged run times. Finally, catalyst effectiveness also was demonstrated when using wet ethanol feed, thus highlighting process flexibility in terms of feedstock purity requirements. This work was financially supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy, Bioenergy Technologies Office, and was performed at the Pacific Northwest National Laboratory (PNNL) under Contract No. DE-AC05-76RL01830 and the National Renewable Energy Laboratory under Contract No. DE-AC36- 08GO28308. Part of the work conducted by S. A. Akhade was performed under the auspices of the U.S. DOE at Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344. This work was partly supported through the PNNL-WSU Distinguished Graduate Research Program for ADW. NMR and XPS experiments were performed using EMSL (grid.436923.9), a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research
Dagle, Vanessa↗
Ultradynamic Isoreticularly Expanded Porous Organic Crystals
Porous organic materials showcasing large framework dynamics present new paths for adsorption and separation with enhanced capacity and selectivity beyond the size-sieving limits, which is attributed to their guest-responsive sorption behaviors. Porous hydrogen-bonded crosslinked organic frameworks (H C OFs) are attractive for their remarkable ability to undergo guest-triggered expansion and contraction facilitated by their flexible covalent crosslinkages. However, the voids of H C OFs remain limited, which restrains the extent of the framework dynamics. Here in this work, we synthesized a series of H C OFs characterized by unprecedented size expansion capabilities induced by solvents. These H C OFs were constructed by isoreticularly co-crystallizing two complementary sets of hydrogen bonding building blocks to generate porous molecular crystals, which were crosslinked through thiol–ene/yne single-crystal-to-single-crystal transformations. The generated H C OFs exhibit enhanced chemical durability, high crystallinity, and extraordinary framework dynamics. For instance, H C OF-104 crystals featuring a pore diameter of 13.6 Å expanded in DMF to 300 ± 10% of their original lengths within just 1 min. This expansion allows the HCOFs to adsorb guest molecules that are significantly larger than the pore sizes of their crystalline states. Through methanol-induced contraction, these large guests were encapsulated in the fast-contracted H C OFs. These advancements in porous framework dynamics pave the way for new methods of encapsulating guests for targeted delivery.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure–activity relationship of Au/ZrO 2 catalyst on formation of hydroxyl groups and its influence on CO oxidation
We studied the effect of changes in morphology and surface hydroxyl species upon thermal treatment of zirconia on the oxidation activity of Au/ZrO 2 catalyst. We observed using transmission Fourier transform infrared (FTIR) spectroscopy progressive changes in the presence of monodentate (type I), bidentate (type II) and hydrogen bridged species (type III) for each of the thermally treated (85 to 500 °C) supports consisting of bare zirconia and Au/ZrO 2 catalysts. Furthermore, structural changes in zirconia were accompanied by an increase in crystal size (7 to 58 nm) and contraction of the supports porosity (SSA 532 to 7 m 2 g -1 ) with increasing thermal treatment. Deposition of gold nanoparticles under similar preparation conditions on different thermally treated zirconia resulted in changes in the mean gold cluster size, ranging from 3.7 to 5.6 nm. Changes in the surface hydroxyl species, support structure and size of the gold centers are important parameters responsible for the observed decrease (>90%) in CO conversion activity for the Au/ZrO 2 catalysts. Density functional theory calculations provide evidence of increased CO binding to Au nanoclusters in the presence of surface hydroxyls on zirconia, which increases charge transfer at the perimeter of the gold nanocluster on zirconia support. This further helps in reducing a model CO-oxidation reaction barrier in the presence of surface hydroxyls. Lastly, this work demonstrates the need to understand the structure–activity relationship of both the support and active particles for the design of catalytic materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structural hysteresis in dragline spider silks induced by supercontraction: an X-ray fiber micro-diffraction study
Interaction with water causes shrinkage and significant changes in the structure of spider dragline silks, which has been referred to as supercontraction in the literature. Preferred orientation or alignment of protein chains with respect to the fiber axis is extensively changed during this supercontraction process. Synchrotron X-ray micro-fiber diffraction experiments have been performed on Nephila clavipes and Argiope aurantia major and minor ampullate dragline spider fibers in the native dry, contracted (by immersion in water) and restretched (from contracted) states. Changes in the orientation of β-sheet nanocrystallites and the oriented component of the amorphous network have been determined from wide-angle X-ray diffraction patterns. While both the crystalline and amorphous components lose preferred orientation on wetting with water, the nano-crystallites regain their orientation on wet-restretching, whereas the oriented amorphous components only partially regain their orientation. Dragline major ampullate silks in both the species contract more than their minor ampullate silks.
36 MATERIALS SCIENCE↗
Ultrafast branching in intersystem crossing dynamics revealed by coherent vibrational wavepacket motions in a bimetallic Pt($\mathrm{II}$) complex
Ultrafast excited-state processes of transition metal complexes (TMCs) are governed by complicated interplays between electronic and nuclear dynamics, which demand a detailed understanding to achieve optimal functionalities of photoactive TMC-based materials for many applications. Here, in this work, we investigated a cyclometalated platinum(II) dimer known to undergo a Pt-Pt bond contraction in metal-metal-to-ligand-charge-transfer (MMLCT) excited state using femtosecond broadband transient absorption (fs-BBTA) spectroscopy in combination with geometry optimization and normal mode calculations. Using sub-20 fs pump and broadband probe pulses in fs-BBTA spectroscopy, we are able to correlate coherent vibrational wavepacket (CVWP) evolution with stimulated emission (SE) dynamics of the 1 MMLCT state. The results demonstrated that the 145 cm -1 CVWP motions with the damping times of ~ 0.9 ps and ~ 2 ps originate from coherent Pt-Pt stretching vibrations in the singlet and triplet MMLCT states, respectively. On the basis of excited-state potential energy surface calculations in our previous work, we rationalized that the CVWP transfer from Franck-Condon (FC) state to the 3 MMLCT state was mediated by a triplet ligand-centered ( 3 LC) intermediate state through two step intersystem crossing (ISC) on a time scale shorter than a period of the Pt-Pt stretching wavepacket motions. Moreover, it was found that the CVWP motion with 110 cm-1 frequency decays with the damping time of ~ 0.2 ps, well matching the time constant of 0.253 ps corresponding to a redshift in the SE feature at early time. This observation indicates that the Pt-Pt bond contraction changes the stretching frequency from 110 to 145 cm -1 and stabilize the 1 MMLCT state relative to the 3 LC state with the ~ 0.2 ps time scale. Thus, the ultrafast ISC from the 1 MMLCT to the 3 LC states occurs before the Pt-Pt bond shortening. The findings herein provide insight into understanding the impact of Pt-Pt bond contraction on ultrafast branching of the 1 MMLCT population into the direct ( 1 MMLCT → 3 MMLCT) and indirect ISC pathways ( 1 MMLCT → 3 LC → 3 MMLCT) in the Pt(II) dimer. These results revealed intricate excited state electronic and nuclear motions that could steer the reaction pathways with levels of details that have not achieved before
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Deformation of Granular Material under Continuous Rotation of Stress Principal Axes
The mechanical response of granular material to the rotation of stress principal axes is an issue of both practical and theoretical importance in soil mechanics. This study used a two-dimensional (2D) discrete-element method (DEM) simulation to investigate the deformation of granular material under the continuous rotation of stress principal axes while maintaining fixed principal stress values. The results show that under such rotation, the deformation can exceed that caused by fixed principal stress axes cyclic biaxial compression with a maximum deviatoric stress ratio that equals the fixed stress ratio during rotation. The volumetric strain was found to be contractive overall while oscillating within each load cycle for specimens with significant fabric anisotropy. Here, the initial fabric-anisotropy orientation was found to have little influence on the overall evolution of volumetric strain, although it was found to affect the development of shear strain. During the cycles of rotation of initial stress principal axes, the dilatancy of granular material, in the contractive direction, was found to be dominated by the evolving orientation of the major principal stress axis in reference to the initial major principal stress axis during anisotropic consolidation, and the influence of the initial fabric-anisotropy orientation was found to be trivial. As stress rotation continued, the influence of the relative orientation between stress and fabric became prominent, causing the material to dilate when the major principal stress axis rotated from the normal of the bedding plane to being perpendicular to it and causing contraction during the other half of the cycle.
58 GEOSCIENCES↗
Daubechies wavelets for linear scaling density functional theory
We demonstrate that Daubechies wavelets can be used to construct a minimal set of optimized localized adaptively contracted basis functions in which the Kohn-Sham orbitals can be represented with an arbitrarily high, controllable precision. Ground state energies and the forces acting on the ions can be calculated in this basis with the same accuracy as if they were calculated directly in a Daubechies wavelets basis, provided that the amplitude of these adaptively contracted basis functions is sufficiently small on the surface of the localization region, which is guaranteed by the optimization procedure described in this work. This approach reduces the computational costs of density functional theory calculations, and can be combined with sparse matrix algebra to obtain linear scaling with respect to the number of electrons in the system. Calculations on systems of 10 000 atoms or more thus become feasible in a systematic basis set with moderate computational resources. Further computational savings can be achieved by exploiting the similarity of the adaptively contracted basis functions for closely related environments, e.g., in geometry optimizations or combined calculations of neutral and charged systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Compact noncontraction semigroups of affine operators
We analyze compact multiplicative semigroups of affine operators acting in a finite-dimensional space. The main result states that every such semigroup is either contracting, that is, contains elements of arbitrarily small operator norm, or all its operators share a common invariant affine subspace on which this semigroup is contracting. The proof uses functional difference equations with contraction of the argument. We look at applications to self-affine partitions of convex sets, the investigation of finite affine semigroups and the proof of a criterion of primitivity for nonnegative matrix families. Bibliography: 32 titles.
97 MATHEMATICS AND COMPUTING↗
Commonly used FRET fluorophores promote collapse of an otherwise disordered protein
The dimensions that unfolded proteins, including intrinsically disordered proteins (IDPs), adopt in the absence of denaturant remain controversial. We developed an analysis procedure for small-angle X-ray scattering (SAXS) profiles and used it to demonstrate that even relatively hydrophobic IDPs remain nearly as expanded in water as they are in high denaturant concentrations. In contrast, as demonstrated here, most fluorescence resonance energy transfer (FRET) measurements have indicated that relatively hydrophobic IDPs contract significantly in the absence of denaturant. Here, we use two independent approaches to further explore this controversy. First, using SAXS we show that fluorophores employed in FRET can contribute to the observed discrepancy. Specifically, we find that addition of Alexa-488 to a normally expanded IDP causes contraction by an additional 15%, a value in reasonable accord with the contraction reported in FRET-based studies. Second, using our simulations and analysis procedure to accurately extract both the radius of gyration (R g ) and end-to-end distance (R ee ) from SAXS profiles, we tested the recent suggestion that FRET and SAXS results can be reconciled if the R g and R ee are “uncoupled” (i.e., no longer simply proportional), in contrast to the case for random walk homopolymers. We find, however, that even for unfolded proteins, these two measures of unfolded state dimensions remain proportional. Together, these results suggest that improved analysis procedures and a correction for significant, fluorophore-driven interactions are sufficient to reconcile prior SAXS and FRET studies, thus providing a unified picture of the nature of unfolded polypeptide chains in the absence of denaturant.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The distinctive mechanical and structural signatures of residual force enhancement in myofibers
In muscle, titin proteins connect myofilaments together and are thought to be critical for contraction, especially during residual force enhancement (RFE) when steady-state force is elevated after an active stretch. We investigated titin’s function during contraction using small-angle X-ray diffraction to track structural changes before and after 50% titin cleavage and in the RFE-deficient,mdmtitin mutant. We report that the RFE state is structurally distinct from pure isometric contractions, with increased thick filament strain and decreased lattice spacing, most likely caused by elevated titin-based forces. Furthermore, no RFE structural state was detected inmdmmuscle. We posit that decreased lattice spacing, increased thick filament stiffness, and increased non-cross-bridge forces are the major contributors to RFE. We conclude that titin directly contributes to RFE.
Science & Technology - Other Topics↗
THE EFFECTS OF PLASMA BETA AND ANISOTROPY INSTABILITIES ON THE DYNAMICS OF RECONNECTING MAGNETIC FIELDS IN THE HELIOSHEATH
The plasma {beta} (the ratio of the plasma pressure to the magnetic pressure) of a system can have a large effect on its dynamics as high {beta} enhances the effects of pressure anisotropies. We investigate the effects of {beta} in a system of stacked current sheets that break up into magnetic islands due to magnetic reconnection, which is analogous to the compressed heliospheric current sheet in the heliosheath. We find significant differences between systems with low and high initial values of {beta}. At low {beta}, growing magnetic islands are modestly elongated and become round as contraction releases magnetic stress and reduces magnetic energy. At high {beta}, the increase of the parallel pressure in contracting islands causes saturation of modestly elongated islands as island cores approach the marginal firehose condition. Only highly elongated islands reach finite size. The anisotropy within these islands prevents full contraction, leading to a final state of highly elongated islands in which further reconnection is suppressed. The elongation of islands at finite {beta} is further enhanced by reducing the electron-to-ion mass ratio to more realistic values. The results are directly relevant to reconnection in the sectored region of the heliosheath where there is evidence that elongated islands are present, and possibly to other high-{beta} systems such as astrophysical accretion flows and the magnetosphere of Saturn.
79 ASTRONOMY AND ASTROPHYSICS↗