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DOE OSTI2021

Synthesis and Transport Properties of the Family of Zintl Phases Ca 3 RESb 3 (RE = La–Nd, Sm, Gd–Tm, Lu): Exploring the Roles of Crystallographic Disorder and Core 4f Electrons for Enhancing Thermoelectric Performance

Zintl phases with complex crystal structures have been studied as promising candidate-materials for thermoelectric (TE) applications. Here, we report the syntheses of the family of rare-earth metal Zintl phases with the general formula Ca 4–x RE x Sb 3 (x ≈ 1; RE = La–Nd, Sm, Gd–Tm, Lu). The structural elucidation is based on refinements of single-crystal X-ray diffraction data for 12 unique chemical compositions. The cubic structure is confirmed as belonging to the anti-Th 3 P 4 structure type (space group I4¯3d, no. 220, Z = 4), where the Ca and RE atoms share the same atomic site with ca. 75% and 25% occupancies, respectively. Such crystallographic disordering of divalent Ca and trivalent RE atoms in the structure provides a pathway to intricate bonding. The latter, together with the presence of heavy elements such as Sb and the lanthanides, are expected to enhance the scattering probability of phonons, thereby leading to as low thermal conductivity κ as that of the ordered RE 4 Sb 3 . The drive of the hypothetical parent compound Ca 4 Sb 3 to be stabilized by alloying with rare-earth metals can be understood following the Zintl-Klemm concept, as the resultant formula may be rationalized as (Ca 2+ ) 3 RE 3+ (Sb 3– ) 3 , indicating the realization of closed-shell electronic configurations for all elements. This notion is confirmed by electronic structure calculations, which reveal narrow bandgaps E g = 0.77 and 0.53 eV for Ca 3 LaSb 3 and Ca 3 LuSb 3 , respectively. Additionally, the incorporation of RE atoms into the structure drives the phase into a state of a degenerate semiconductor with dominant hole charge carriers.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Success of Commercial Building Re-tuning in Federal Buildings: Results and Case Studies

Re-tuning is a form of scaled-down retrocomissioning for commercial buildings that targets low- and no-cost control changes to building automation systems (BASs) to achieve immediate energy savings. A retrospective analysis of re-tuning for a set of 26 Federal office buildings and courthouses is presented, detailing the re-tuning process that was employed, the types of re-tuning measures that were commonly implemented, the most impactful of those measures, and an analysis of the energy and cost savings achieved as a result of the process. The portfolio of buildings that participated in these re-tuning efforts was benchmarked as having, on average, very efficient baselines. However, these buildings achieved, on average, 12.1% annual energy savings as a result of the re-tuning efforts, with an associated cost savings of $1.62/year per square meter of floor space ($0.151/year per square foot). Several key factors that are observed to promote successful re-tuning outcomes are discussed as well.

Fernandez, Nicholas↗

DOE OSTI2016

Excimer laser assisted re-oxidation of BaTiO{sub 3} thin films on Ni metal foils

Excimer laser assisted re-oxidation for reduced, crystallized BaTiO{sub 3} thin films on Ni-foils was investigated. It was found that the BaTiO{sub 3} can be re-oxidized at an oxygen partial pressure of ∼50 mTorr and substrate temperature of 350 °C without forming a NiO{sub x} interface layer between the film and base metal foil. The dielectric permittivity of re-oxidized films was >1000 with loss tangent values <2% at 100 Hz, 30 mV{sub rms} excitation signal. Electron Energy Loss Spectroscopy indicated that BaTiO{sub 3} thin films can be re-oxidized to an oxygen stoichiometry close to ∼3 (e.g., stoichiometric). High resolution cross sectional transmission electron microscopy showed no evidence of NiO{sub x} formation between the BaTiO{sub 3} and the Ni foil upon excimer laser re-oxidation. Spectroscopic ellipsometry studies on laser re-oxidized [001]{sub C} and [111]{sub C} BaTiO{sub 3} single crystals indicate that the re-oxidation of BaTiO{sub 3} single crystals is augmented by photo-excitation of the ozone, as well as laser pulse induced temperature and local stress gradients.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2023

Quasi-one-dimensional Pb 5 Re 3 O 15 : A 5 d realization of the Heisenberg antiferromagnetic spin-1/2 chain

Quasi-one-dimensional (1D) magnetic compounds connect the exact solutions of low-dimensional magnetic geometries, which promise quantum spin liquid behavior and exotic quasiparticles, with real-world materials, in which competing magnetic interactions affect their implementation in quantum information science. Here, the structural determination and quasi-1D magnetic behavior of a previously unreported compound, Pb 5 ⁢Re 3 ⁡O 15 , is presented. Like the anisotropic triangular A 3 ⁢ReO 5 ⁢Cl 2 (A = Ba, Sr, Ca) materials, Pb 5 ⁢Re 3 ⁡O 15 contains [ReO 5 ] square pyramids inserted into anion-centered quasi-two-dimensional layers and hosts spin-1/2 moments on the Re 6+ ions. Pb 5 ⁢Re 3 ⁡O 15 , however, has a more ideal quasi-1D geometry than the A 3 ⁢ReO 5 ⁢Cl 2 materials, with larger interchain distances and interlayer spacing. Quasi-1D magnetic behavior in Pb 5 ⁢Re 3 ⁡O 15 is confirmed by fitting the temperature-dependent magnetic susceptibility with the Bonner-Fisher model for a spin-1/2 antiferromagnetically coupled chain, yielding an intrachain coupling constant of |J|/k B =54.5K. Pb 5 ⁢Re 3 ⁡O 15 is highly insulating at room temperature, and heat capacity data below 10 K reveal a linear-T contribution that suggests the presence of low-temperature spinon excitations. Finally, with a lack of three-dimensional ordering down to at least 0.6 K, Pb 5 ⁢Re 3 ⁡O 15 is proposed as a model system for studying the quantum magnetism of quasi-1D Heisenberg chains in a real-world 5d 1 antiferromagnetic material.

36 MATERIALS SCIENCE↗

DOE OSTI2014

SU-E-J-52: Dosimetric Benefit of Adaptive Re-Planning in Lung Cancer Stereotactic Body Radiotherapy (SBRT)

Purpose: To investigate the dosimetric benefit of adaptive re-planning for lung stereotactic body radiotherapy(SBRT). Methods: Five lung cancer patients with SBRT treatment were retrospectively investigated. Our in-house supercomputing online re-planning environment (SCORE) was used to realize the re-planning process. First a deformable image registration was carried out to transfer contours from treatment planning CT to each treatment CBCT. Then an automatic re-planning using original plan DVH guided fluence-map optimization is performed to get a new plan for the up-to-date patient geometry. We compared the re-optimized plan to the original plan projected on the up-to-date patient geometry in critical dosimetric parameters, such as PTV coverage, spinal cord maximum and volumetric constraint dose, esophagus maximum and volumetric constraint dose. Results: The average volume of PTV covered by prescription dose for all patients was improved by 7.56% after the adaptive re-planning. The volume of the spinal cord receiving 14.5Gy and 23Gy (V14.5, V23) decreased by 1.48% and 0.68%, respectively. For the esophagus, the volume receiving 19.5Gy (V19.5) reduced by 1.37%. Meanwhile, the maximum dose dropped off by 2.87% for spinal cord and 4.80% for esophagus. Conclusion: Our experimental results demonstrate that adaptive re-planning for lung SBRT has the potential to minimize the dosimetric effect of inter-fraction deformation and thus improve target coverage while reducing the risk of toxicity to nearby normal tissues.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2014

SU-E-J-229: Quantitative Assessment for Timely Adaptive Re-Planning Using Weekly Dose Monitoring for Head and Neck Cancer

Purpose: For patients with head and neck (HN) cancer, mid-course adaptive radiation therapy (ART) is a common practice in our institution to accommodate anatomic changes. The aim of the study is to evaluate whether dose re-calculation on weekly verification images can provide quantitative assessment for timely adaptive re-planning with daily image-guided intensity modulated radiotherapy (IMRT). Methods: We retrospectively selected sixty daily verification images acquired on CT-on-rail/CBCT from ten HN patients. These image sets were typically a week apart. Among these patients, six patients received a mid-course ART. Contours of the tumors and organ-at-risks (OARs) were manually delineated by a physician on each verification CT. After placing the treatment iso-center on the verification CTs according to the recorded clinical shifts, daily dose was re-calculated with the same beam configuration as the original plan. For the purpose of this study, electron densities for both verification CTs and planning CTs were set to 1.0 g/cm3. Results: Two patients had D99 of the CTV < 97% of the planned dose for more than three fractions due to remarkable tumor volume shrinkages. D-max of the spinal cord exceeded a tolerance of 45 Gy for four fractions in additional two patients. D-mean of the parotid increased within 25% of the planned value. D-max of the brainstem and D-mean of the oral cavity did not show significant variation. If the re-planning criteria included D99 of the CTV < 97% of the planned dose and D-max of the spinal cord > 45 Gy, two out ten patients required ART at week 2 and two patients required ART at week 3, respectively. Conclusion: Weekly dose monitoring with re-calculation on verification images can provide quantitative dose guidance for timely adaptive re-planning. Future work will include accumulative dose analysis for the decision of adaptive re-planning. The study is supported in part by Siemens Medical Solutions.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2022

Evaluation of 186 WS 2 target material for production of high specific activity 186 Re via proton irradiation: separation, radiolabeling and recovery/recycling

Enriched tungsten disulfide ( 186 WS 2 ) was evaluated at increasing proton beam currents (20-50 µA) and times (up to 4 h) on a GE PETtrace cyclotron for production of high specific activity (HSA) 186 Re. The HSA 186 Re was separated from the irradiated target as [ 186 Re][ReO 4 ] - by a liquid-liquid extraction method and radiolabeled with a new N 2 S 2 ligand (222-MAMA-N-ethylpropionate). The enriched 186 W was recovered from the extraction process, analyzed for purity and enrichment, and converted back to the disulfide ( 186 WS 2 ). The results demonstrate that the 186 WS 2 is an easily pressed target material that can withstand relatively high currents and can be readily recovered and recycled. The 186 Re produced was isolated in high specific activity and readily formed the radiotracers [ 186 Re][ReO(222-MAMA-N ethylpropionate)] and [ 186 Re][Re(CO) 3 (OH 2 ) 3 ] + .

186Re,N2S2 ligand↗

DOE OSTI2022

FY2022 Progress Report for Advanced Re-fabrication/Re-instrumentation Capability Development

In support of performing follow-on irradiation experiments with previously irradiated materials, the Halden Reactor Project developed unique and state of the art capabilities to refabricate and re-instrument previously irradiated materials. Such materials were used in in-pile tests at the Halden reactor, and out-of-pile tests for example using furnaces as a heat source. The decision to close the Halden Reactor Project results in the loss of this refabrication and re-instrumentation capability. As a result, the United States (U.S.) Department of Energy (DOE) has determined to develop refabrication and re-instrumentation capability at the unique shielded facilities at Idaho National Laboratory (INL). The development of refabrication capability has been completed and demonstrated. This report focuses on the complementary aspects of reinstrumentation and the progress to-date. Halden spent nearly 30 years developing both refabrication and re-instrumentation. Collaboration with Halden is allowing Idaho National Laboratory (INL) to develop this capability much more rapidly. In FY-21 the results include development of the capability to drill annular center holes in ceramic UO2 fuel pellets, development of fuel rod end caps with feedthroughs for centerline instrumentation inside the rodlet, The procurement of both fuel drilling and welding demonstration equipment from Halden, evaluation of surface thermocouple attachments to support better understanding of temperature measurement uncertainties, and finally, the conceptual design of a new shielded enclosure where advanced refabrication and re-instrumentation equipment can be housed. In FY-22, the results include; Completing set up of the drilling and welding modules procured from Halden, and early experimental trials using that equipment.; Completing set up of an out-of-cell circumferential weld system to allow for further weld development to take place and support fabrication of fuel for fresh fuel experiments.; Evaluation of the Hot Fuel Examination Facility (HFEF) infrastructure to support future installation of advanced re-fabrication/re-instrumentation equipment, specifically related to necessary infrastructure for cryo-drilling.; Developments in dry-drilling alternative. Including experimental studies showing cordierite is the most suitable surrogate for UO 2 for performing drilling studies. That drilling performance is enhanced when a fuel-clad bonding condition is simulated.; Conceptual design completed for attaching surface thermocouples to irradiated fuel in support of TWIST capsule experiments. The authors would like to thank the numerous colleagues at INL and Halden who provided support in accomplishing this work. Their support both material and intellectual is invaluable in advancing the state of the art and establishing the capabilities for refabrication and re-instrumentation at INL.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2018

Atomistic model of xenon gas bubble re-solution rate due to thermal spike in uranium oxide

Atomistic simulations are performed to study the response of Xe gas bubbles in UO 2 to ionizing fission products through the thermal spike approximation. A portion of the total electronic stopping power (S e ) is taken as the thermal spike energy through a ratio variable ζ. The thermal spike energy causes extreme melting within the fission track cylindrical region. Molecular dynamics is employed to quantify the probability of a Xe gas atom to be re-solved (re-dissolved) back into the UO 2 matrix. Subsequently, a re-solution model is developed and parametrized as a function of bubble radius (R), off-centered distance (r), and thermal spike energy (ζS e ). The off-centered distance measures the shift of the thermal spike axis from the bubble center. To evaluate the re-solution model, independent fission product yield of U-235 fission due to thermal neutrons (0.0253 eV), taken from the JEFF-3.3 database, is used. The kinetic energy of the fission products is taken from the EXFOR database. Subsequently, the decay of Se over distance for each fission product is simulated. Finally, the evaluated re-solution rate (re-solution probability per second) is presented as a function of bubble radius for a range of ζ.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2016

Closure of Fracture Due to Cover Stress Re-establishment After Coal Mining

In situ measurements of deformations, stresses, and closure of fractures, affecting water inflow following coal mining, are challenging due to the inaccessibility of fractured rock. Here, the authors studied the closure process of the fractured rock mass with the cover stress re-establishment based on a theoretical analysis and a scale model testing. A quantitative analysis is used to study the fracture distribution in the fractured zone. A function to describe a fracture aperture distribution in the fractured zone is proposed, which takes into account the curvature and thickness of the fractured rock. The theoretical analysis and a scale model testing both indicate that the cover stress re-establishment with mining distance increasing and the relationship between the fracture closure and cover stress re-establishment both satisfy a logarithmic function. The scale model test also shows the following features: (1) the fracture ratio (which is the fracture area divided by the total area of fracture and intact rock with a unit width in the vertical or horizontal direction) in the lower part of the fractured rock mass is greater than that in the upper part; (2) the initially fast decreased of fracture ratios is then followed by a slower decrease during the cover stress re-establishment process; (3) in the upper part of the rock mass, the vertical directional fractures with small apertures are being closed with cover stress re-establishment, which indicates an increase in the water resistance reducing the seepage from these parts of the fractured zone. This study improves the general understanding of the fracture closure process and cover stress re-establishment in the fractured rock mass after coal mining ceased, and provides a theoretical basis for water resource protection in case of underground coal mining.

58 GEOSCIENCES↗

DOE OSTI2016

Evaluating the role of re-adsorption of dissolved Hg 2+ during cinnabar dissolution using isotope tracer technique

Cinnabar dissolution is an important factor controlling mercury (Hg) cycling. Recent studies have suggested the co-occurrence of re-adsorption of the released Hg during the course of cinnabar dissolution. However, there is a lack of feasible techniques that can quantitatively assess the amount of Hg re-adsorbed on cinnabar when investigating cinnabar dissolution. In this study, a new method, based on isotope tracing and dilution techniques, was developed to study the role of Hg re-adsorption in cinnabar dissolution. The developed method includes two key components: (1) accurate measurement of both released and spiked Hg in aqueous phase and (2) estimation of re-adsorbed Hg on cinnabar surface via the reduction in spiked 202 Hg 2+ . By adopting the developed method, it was found that the released Hg for trials purged with oxygen could reach several hundred g L –1 , while no significant cinnabar dissolution was detected under anaerobic condition. Cinnabar dissolution rate when considering Hg re-adsorption was approximately 2 times the value calculated solely with the Hg detected in the aqueous phase. Lastly, these results suggest that ignoring the Hg re-adsorption process can significantly underestimate the importance of cinnabar dissolution, highlighting the necessity of applying the developed method in future cinnabar dissolution studies.

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2017

Scale-up of high specific activity 186g Re production using graphite-encased thick 186 W targets and demonstration of an efficient target recycling process

Production of high specific activity 186g Re is of interest for development of theranostic radiopharmaceuticals. Previous studies have shown that high specific activity 186g Re can be obtained by cyclotron irradiation of enriched 186 W via the 186 W(d,2n) 186g Re reaction, but most irradiations were conducted at low beam currents and for short durations. In this paper, enriched 186 W metal targets were irradiated at high incident deuteron beam currents to demonstrate production rates and contaminants produced when using thick targets. Full-stopping thick targets, as determined using SRIM, were prepared by uniaxial pressing of powdered natural abundance W metal or 96.86% enriched 186 W metal encased between two layers of graphite flakes for target material stabilization. An assessment of structural integrity was made on each target preparation. To assess the performance of graphite-encased thick 186 W metal targets, along with the impact of encasing on the separation chemistry, targets were first irradiated using a 22 MeV deuteron beam for 10 min at 10, 20, and 27 μA, with an estimated nominal deuteron energy of 18.7 MeV on the 186 W target material (after energy degradation correction from top graphite layer). Gamma-ray spectrometry was performed post EOB on all targets to assess production yields and radionuclidic byproducts. The investigation also evaluated a method to recover and recycle enriched target material from a column isolation procedure. Material composition analyses of target materials, pass-through/wash solutions and recycling process isolates were conducted with SEM, FTIR, XRD, EDS and ICP-MS spectrometry. Finally, to demonstrate scaled-up production, a graphite-encased 186 W target made from recycled 186 W was irradiated for ~2 h with 18.7 MeV deuterons at a beam current of 27 μA to provide 0.90 GBq (24.3 mCi) of 186g Re, decay-corrected to the end of bombardment. ICP-MS analysis of the isolated 186g Re solution provided data that indicated the specific activity of 186g Re in this scaled-up production run was 2.6±0.5 GBq/μg (70±10 Ci/mg).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2020

Use of the Tool to Support Renewable Energy Auctions Processes (RE Data Explorer)

Renewable energy auctions are now a common competitive approach to procure low-cost renewable power around the world. Ensuring a successful auction process increasingly depends on the capabilities of auction designers and participants to identify actionable and defensible insights from large data sets (on renewable energy resources and complementary data) to both attract potential investors and address stakeholder concerns. The Renewable Energy (RE) Data Explorer is a user-friendly geospatial analysis tool for analyzing renewable energy potential and informing decisions. Developed by the National Renewable Energy Laboratory (NREL) and supported by the U.S. Agency for International Development (USAID), RE Data Explorer performs visualization and analysis of renewable energy potential that can be customized for different scenarios. RE Data Explorer can support prospecting, integrated planning, policymaking, and other decision-making activities to accelerate renewable energy deployment. The broader RE Explorer website provides guidance and information to link the RE Data Explorer geospatial analysis tool to key decision areas. This document provides information on how the RE Data Explorer can be used to support renewable energy auction processes.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2025

Vehicular Re-Identification from Uncontrolled Multiple Views

Vehicle re-identification (re-ID) across disparate sensing modalities remains a fundamental challenge for transportation research. In this work, we introduce a deep multi-view vehicle re-ID framework that leverages Siamese networks to compare pairs of vehicle images and produce matching scores, enabling robust association across drastically different viewpoints such as those from UAVs, surveillance cameras, and ground sensors. The model exploits convolutional neural networks to learn features that remain discriminative under changes in angle, distance, and illumination, supporting more generalizable re-ID performance. As part of this effort, we also developed an automated pipeline to synchronize roadside and UAV video streams, producing a multi-perspective dataset that complements preexisting real collections and a synthetic dataset generated in this study. Together, these contributions advance the capability to re-identify vehicles across wide viewing baselines; establish a foundation for scalable, reproducible research in vehicle re-ID; and open pathways for future applications, such as inferring routine behaviors, movement patterns, and daily habits of the individual associated with the vehicle.

convolutional neural networks↗

DOE OSTI2018

Pulse-Burst PIV of an Impulsively Started Cylinder in a Shock Tube for Re > 10 5

Here, the impulsive start of a circular cylinder in a shock tube was characterized with time-resolved particle image velocimetry measurements (TR-PIV) using a pulse-burst laser. Three Reynolds numbers Re of 1.07 × 10 5 , 1.63 × 10 5 and 2.46 × 10 5 were studied adding insight into the transient process in the vicinity of the drag crisis. One symmetric vortex pair was shed from the cylinder at the lower Reynolds number prior to the wake going asymmetric in a fashion analogous to studies at lower Re. At Re ≥ 1.63 × 10 5 , two or more symmetric vortex pairs occurred prior to asymmetry and the eventual transition to a von Kármán vortex street. The non-dimensional rise time for vortex shedding to begin, as quantified by wavelet analysis, was found to be lower at the two higher Re. Finally, the study indicates a transformation in the impulsive wake to occur at Re near the critical regime and may serve as a benchmark for high Re numerical solutions.

42 ENGINEERING↗

DOE OSTI2023

Activity model for 36 elements in Fe-Ni-Si-S-C liquids with application to terrestrial planet accretion and mantle geochemistry: New data for Ru, Re, Pt, Os, Ti, Nb, and Ta

Understanding siderophile element partitioning between metal and silicate melts under diverse conditions can be used to place important constraints on the materials and conditions of planetary accretion and core formation, as well as post core formation processes. However, the effects of Si on the partitioning and activity coefficients for these elements are not well known, despite Si likely being one of the dominant light elements in Earth’s core. To address this gap in understanding, we have undertaken a systematic study of the highly siderophile elements Re, Pt, Os, and Ru, and the refractory lithophile elements Nb, Ta and Ti at 1600 °C and 1 GPa, to derive epsilon interaction parameters for these elements in FeSi metallic liquids. Positive epsilon interaction parameters were measured for Nb, Ta, Ti, Ru, Re, Pt, and Os, indicating that dissolved Si in Fe liquids causes a decrease in their metal/silicate partition coefficients (or ‘silicophobic’ behavior). Furthermore, ε$_{Re, Os, or Ru}^{Si}$ > ε$_{Re, Os, or Ru}^{S}$ which means Si causes a larger decrease in D(metal/silicate) than S, and the chalcophile behavior expected from some elements will be completely masked by the presence of Si in a metallic liquid. The new parameters are used to update an activity model that now includes 36 siderophile elements in Fe-Ni-Si-S-C liquids (27 trace elements considered here). Systematic assessment of these 27 elements shows which have the strongest affinity for Si, C, and S, and also how activity coefficients for these elements would vary during accretion and core formation in Earth, Mars, and Mercury of widely differing fO 2 and core compositional conditions. The activity model is combined with new partitioning expressions for Mo, W, Cr, Re Ru, Pt, and Os and applied to aspects of post core formation mantle geochemistry of Earth, Mars, and Mercury. Our updated expressions show that the BSE Mo/W ratio can easily be achieved with metal/silicate partitioning during growth of the Earth, whereas Re, Os and Ru become lower than and highly fractionated compared with BSE values during core formation and accretion, and thus nearly 99% of their BSE abundances are likely contributed by late accretion. Ru isotopes should be a very good indicator of the source material for the late accretion. The high Pt/Os and Re/Os developed in a deepening magma ocean during the growth of the Earth, indicates 186 Os and 187 Os isotopes could be coupled if this ancient material remained isolated and subsequently became entrained in mantle plumes and measured in surficial lavas. The extent to which this occurred will be limited by the low Os content of this ancient material, thus requiring mixing as a major component in plume sources. Martian mantle Hf/W ratio stays low during accretion and core formation modelling, suggesting that W isotope anomalies are more likely due to solid/liquid silicate fractionation than to core formation. Finally, Ti contents measured by MESSENGER at Mercury’s surface can be explained by segregation of either a metallic core (IW-6 to -8) or metallic core + sulfide (IW-4 to -7.5) followed by mantle melting.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO) 3 L 0/+ core by flash photolysis

The photoprocesses of three rhenium(I) tricarbonyl complexes, fac-Re(NN)(CO) 3 L 0/+ , bearing an azo/hydrazone ligand, NN, and L = Cl, Br or CH 3 CN as axial ligand, were studied by time-resolved spectroscopic techniques. Flash irradiation of deaerated solutions of the complexes in acetonitrile photogenerated intermediates with intense optical absorptions in the UV–vis spectral region of the hydrazone ligand. The decay of the intermediates photogenerated with the Cl, Br and CH 3 CN ligands in the axial position proceeds by three different mechanisms. For the fac-Re(NN)(CO) 3 Cl, a three-step mechanism involving isomerization, tautomerization and rotation accounts for the spectroscopic transformations. In contrast to the flash photolysis result, the continuous photolysis of the complex in acetonitrile does not show spectroscopic changes associated with the generation of a stable product, i.e., the complex exhibits a photoreversible behavior. The first step observed in the flash irradiation of fac-Re(NN)(CO) 3 Cl, is missing in the decay of the photogenerated intermediates with fac-Re(NN)(CO) 3 Br and fac-[Re(NN)(CO) 3 CH 3 CN] + . A possible reason for this absence is that the process is too fast for the time-response of the flash photolysis set-up. Time-resolved spectra and associated reaction rate data for the Re(I) complexes are communicated and discussed. Finally, DFT calculations support a plausible E → Z mechanism with thermal back-isomerization mediated by tautomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

The RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1) series revisited. Synthesis, crystal chemistry, and magnetic susceptibilities

This study is concerned with the ternary compounds RELi{sub x}Sn{sub 2} (RE=La–Nd, Sm, and Gd; 0≤x<1), which have been previously thought to be the stoichiometric RELiSn{sub 2} phases. These materials crystallize with the base-centered orthorhombic space group Cmcm (No. 63), and can be formally assigned with the CeNiSi{sub 2} structure type (Pearson symbol oC16). Our systematic single-crystal X-ray diffraction studies revealed substantial Li-deficiencies in all cases, with SmSn{sub 2} (space group Cmmm, ZrGa{sub 2} structure type, Pearson symbol oC12) and GdSn{sub 2} (space group Cmcm, ZrSi{sub 2} structure type, Pearson symbol oC12) being completely lithium-free. The structure refinements also uncovered positional disorder on the Sn site neighboring the vacancies. The Sn-disorder and the Li-deficiency correlate, and vary monotonically with the decreased size of the rare-earth atoms in the order RE=La–Nd. The SmSn{sub 2} and GdSn{sub 2} structures are devoid of any disorder. Temperature-dependent studies of the magnetic response of the title compounds are also presented and discussed. -- Graphical abstract: RELi{sub x}Sn{sub 2} (RE=La–Nd, 0≤x<1) crystallize in a defect variants of the CeNiSi{sub 2} structure type (a). The Sn-disorder and the Li-deficiency correlate, and vary monotonically with the decreased size of the rare-earth atoms in the order RE=La–Nd. The SmSn{sub 2} (b) and GdSn{sub 2} (c) structures are devoid of any disorder. Highlights: • The crystal structures of the RELi{sub x}Sn{sub 2} (RE=La–Nd, 0≤x<1) compounds are revised using single-crystal X-ray diffraction data. • The structure is a filled derivative of the ZrSi{sub 2} structure type or defect variant of the CeNiSi{sub 2} structure type. • SmSn{sub 2} is isotypic with the ZrGa{sub 2} structure, while RESn{sub 2} (RE=Gd–Lu) are isotypic with the ZrSi{sub 2} structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗