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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Celestial amplitudes from UV to IR

Celestial amplitudes represent 4D scattering of particles in boost, rather than the usual energy-momentum, eigenstates and hence are sensitive to both UV and IR physics. We show that known UV and IR properties of quantum gravity translate into powerful constraints on the analytic structure of celestial amplitudes. For example the soft UV behavior of quantum gravity is shown to imply that the exact four-particle scattering amplitude is meromorphic in the complex boost weight plane with poles confined to even integers on the negative real axis. Would-be poles on the positive real axis from UV asymptotics are shown to be erased by a flat space analog of the AdS resolution of the bulk point singularity. The residues of the poles on the negative axis are identified with operator coefficients in the IR effective action. Far along the real positive axis, the scattering is argued to grow exponentially according to the black hole area law. Exclusive amplitudes are shown to simply factorize into conformally hard and conformally soft factors. The soft factor contains all IR divergences and is given by a celestial current algebra correlator of Goldstone bosons from spontaneously broken asymptotic symmetries. The hard factor describes the scattering of hard particles together with the boost-eigenstate clouds of soft photons or gravitons required by asymptotic symmetries. These provide an IR safe S-matrix for the scattering of hard particles.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

The Interventional Radiology (IR) Gender Gap: A Prospective Online Survey by the Cardiovascular and Interventional Radiological Society of Europe (CIRSE)

AimA prospective online survey was conducted by the Cardiovascular Interventional Radiological Society of Europe (CIRSE) to evaluate the gender gap within interventional radiology (IR) and the barriers facing women in IR.Materials and MethodsA questionnaire (“Appendix”) was devised by the authors and the CIRSE communication and publication team and sent electronically to 750 identifiable female members of CIRSE. Responses were collected from 7 August to 24 August 2017.ResultsThe response rate was 19.9% (n = 149) with highest responses from UK (18%), Italy (11%), Germany (11%), Spain (7%), Netherlands (5%), France (5%), Sweden (4%), USA (4%). 91% of the respondents were between 31 and 46 years, 83% work full time, 62% spend > 50% of their working time in IR, and 67% practice in a university or tertiary referral institution. 85% were in the minority in their department. 52% had no leadership role in their department, but 67% expressed willingness to consider a leadership position. Their main concerns were work/family life balance, the risks of radiation exposure, the effect of pregnancy on training and practice and the male-dominated work environment.ConclusionThis survey highlights issues experienced by women in IR. Clear guidance on concerns regarding radiation exposure particularly during pregnancy is needed. Structured and supportive training is required for female IRs who may wish to train or work flexibly. The male-dominated environment is discouraging, and a scheme to promote female IRs would encourage women to take on senior leadership positions and attract more women into the specialty.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2026

Ohmic contact formation at the Au/Sr 3 Ir 2 O 7 interface

Here, using X-ray photoelectron spectroscopy (XPS), we show that Au forms an Ohmic contact with the surface of the narrow-bandgap Mott insulator Sr 3 Ir 2 O 7 thin films. XPS reveals no significant binding energy shift with increasing Au overlayer thickness on epitaxial Sr 3 Ir 2 O 7 (001) thin films, consistent with the linear current-voltage (I-V) behavior and indicative of negligible band bending. The absence of Schottky barrier formation at the Au/Sr 3 Ir 2 O 7 interface corroborates the metallic surface character of the Sr 3 Ir 2 O 7 thin film, as observed in angle-resolved photoemission spectroscopy (ARPES) studies, suggesting that the interface behaves effectively as a metal-on-metal contact. Furthermore, XPS points to the presence of distinct surface/interface and bulk electronic states for Sr 3 Ir 2 O 7 . This study provides critical material information for designing iridate-based electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Experimental study of the partitioning of some platinum group elements (Pd and Ir) between orthopyroxene and silicate melt

Past experiments and observations on natural samples have largely focused on the roles of olivine and chromite in controlling the behaviour of the platinum-group elements (PGE) during melting and solidification, whereas other phases, such as pyroxene, have gone largely uncharacterized. Here, to address this, experiments have been done to measure the partitioning of Pd (with a subset of results for Ir), between orthopyroxene and silicate melt at 1340 °C, 0.1 MPa and log fO 2 of FMQ - 1 to FMQ + 6 (FMQ = Fayalite-Magnetite-Quartz). The X-ray Absorption Near-Edge Structure (XANES) was measured in a subset of experiment glasses. Glass concentrations of Pd (corrected to unit Pd activity) increase from ~6 to ~650 ug/g over the fO 2 range of experiments. The slope of the solubility-fO 2 relation is consistent with Pd 1+ as the dominant oxidation state, with evidence for Pd 0 and Pd 2+ at the lowest and highest experiment fO 2 , respectively. Consistent with this result, the XANES reveal spectral features similar to Pd 0 and Pd 2+ spectral reference materials (specRM) at the most reduced and oxidized synthesis conditions, respectively. Other lines of evidence require the presence of a third melt species, here interpreted to be Pd 1+ . Values of orthopyroxene/melt partition coefficients for Pd (D Pd Opx/melt ) are 0.0051 (+/-0.006) at log fO 2 < ΔFMQ + 3, increasing with fO 2 to a maximum of 0.013 at ~FMQ + 6. Sodium partition coefficients, expected to be similar to Pd, range from 0.0061 (+/-0.00061) at FMQ + 3, increase to 0.007–0.009 at higher fO 2 , but with no clear systematic trend. A value for D Ir Opx-melt of ~0.6 was measured at ~FMQ + 4, indicating significantly more compatible behaviour for Ir relative to Pd. Partitioning results are interpreted in the context of the Blundy-Wood elastic strain model in which the variation in partitioning is related to ionic radius mismatch to an optimal crystallographic site size. Based on the trend in ionic radius with oxidation state, the estimated ionic radius of Pd 1+ in octahedral coordination is similar to Na 1+ , and comparison to previous orthopyroxene-melt partitioning experiments suggests D Pd1+ opx/melt and DNaopx/melt should be nearly identical, consistent with the results of this study. The ionic radius of VI-fold Pd 2+ is close to the optimal M2 site size, so an increased proportion of this species with fO 2 accounts for the larger values of D Pd opx/melt at the highest fO 2 investigated. The much larger partition coefficient for Ir is consistent with the presence of Ir 2+ , whose estimated ionic radius is close to Fe 2+ and Mg 2+ , as well as predictions for the optimal M1 site size. With the assumption that D Pd opx/melt = D Na opx/melt , combined with a revised value for the Pd content of the primitive mantle, a melting model is presented that better reproduces the Pd concentration of high degree melts from sulfide-free mantle sources.

58 GEOSCIENCES↗
DOE OSTI2021

Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution

Our previously reported ‘blue solution’ oxygen-evolution catalyst consists of an isomeric mixture of coordination complexes containing the (pyalk)Ir IV –O–Ir IV (pyalk) core unit and is thus entirely molecular but only when formed from organometallic precursors such as Cp*Ir(pyalk)Cl or Ir(pyalk)(CO) 2 (pyalk = (2-pyridyl)-2-propanolate). We now show that attempts to form it from such obvious coordination precursors as Na[Ir(pyalk)Cl 4 ] or Na[IrCl 2 (pyalk)(O 2 CPh) 2 ], under a variety of conditions, always fail in our hands, leading to a mixture of molecular ‘blue solution’ species and IrO x nanoparticles, rather than the purely homogeneous catalyst formed from organometallic precursors. The loss of the pyalk ligand during the oxidative activation is associated with the nanoparticle generation. External chelating ligands also failed to stop the nanoparticle formation. This work implies the paradoxical conclusion that organometallic complexes are effective as catalyst precursors, even when coordination complexes are the catalytically active species, since the inner-sphere organometallic ligands, although ultimately lost or degraded, may nevertheless have a stabilizing effect sufficient to suppress undesirable nanoparticle production pathways in the activation of the catalyst precursor. Finally, a key aspect of the present study is that organometallic complexes in general may be useful catalyst precursors even if the organometallic ligands are lost in the activation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Ternary rare-earth ruthenium and iridium germanides RE{sub 3}M{sub 2}Ge{sub 3} (RE=Y, Gd–Tm, Lu; M=Ru, Ir)

Through arc-melting reactions of the elements and annealing at 800 °C, the ternary rare-earth germanides RE{sub 3}Ru{sub 2}Ge{sub 3} and RE{sub 3}Ir{sub 2}Ge{sub 3} have been prepared for most of the smaller RE components (RE=Y, Gd–Tm, Lu). In the iridium-containing reactions, the new phases RE{sub 2}IrGe{sub 2} were also generally formed as by-products. Powder X-ray diffraction revealed orthorhombic Hf{sub 3}Ni{sub 2}Si{sub 3}-type structures (space group Cmcm, Z=4) for RE{sub 3}M{sub 2}Ge{sub 3} (M=Ru, Ir) and monoclinic Sc{sub 2}CoSi{sub 2}-type structures (space group C2/m, Z=4) for RE{sub 2}IrGe{sub 2}. Full crystal structures were determined by single-crystal X-ray diffraction for all members of RE{sub 3}Ru{sub 2}Ge{sub 3} (a=4.2477(6) Å, b=10.7672(16) Å, c=13.894(2) Å for RE=Y; a=4.2610(3)–4.2045(8) Å, b=10.9103(8)–10.561(2) Å, c=14.0263(10)–13.639(3) Å in the progression of RE from Gd to Lu) and for Tb{sub 3}Ir{sub 2}Ge{sub 3} (a=4.2937(3) Å, b=10.4868(7) Å, c=14.2373(10) Å). Both structures can be described in terms of CrB- and ThCr{sub 2}Si{sub 2}-type slabs built from Ge-centred trigonal prisms. However, band structure calculations on Y{sub 3}Ru{sub 2}Ge{sub 3} support an alternative description for RE{sub 3}M{sub 2}Ge{sub 3} based on [M{sub 2}Ge{sub 3}] layers built from linked MGe{sub 4} tetrahedra, which emphasizes the strong M–Ge covalent bonds present. The temperature dependence of the electrical resistivity of RE{sub 3}Ru{sub 2}Ge{sub 3} generally indicates metallic behaviour but with low-temperature transitions visible for some members (RE=Gd, Tb, Dy) that are probably associated with magnetic ordering of the RE atoms. Anomalously, Y{sub 3}Ru{sub 2}Ge{sub 3} exhibits semiconductor-like behaviour of uncertain origin. Magnetic measurements on Dy{sub 3}Ru{sub 2}Ge{sub 3} reveal antiferromagnetic ordering at 3 K and several unusual field-dependent transitions suggestive of complex spin reorientation processes. - Graphical abstract: RE{sub 3}M{sub 2}Ge{sub 3} (M=Ru, Ir) adopts the Hf{sub 3}Ni{sub 2}Si{sub 3}-type structure containing slabs built up from Ge-centred trigonal prisms. - Highlights: • Crystal structures of RE{sub 3}Ru{sub 2}Ge{sub 3} (RE=Y, Gd–Tm, Lu) and Tb{sub 3}Ir{sub 2}Ge{sub 3} were determined. • Strong M–Ge covalent bonds were confirmed by band structure calculations. • Most RE{sub 3}Ru{sub 2}Ge{sub 3} members except Y{sub 3}Ru{sub 2}Ge{sub 3} exhibit metallic behaviour. • Dy{sub 3}Ru{sub 2}Ge{sub 3} displays unusual field-dependent magnetic transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

New precious metal containing normal spinels: LiRhRu 1-x Ir x O 4 , LiFeIr 1-x Ru x O 4 , and LiCoIr 1-x Ru x O 4

Large spin-orbit-coupled cations in geometrically frustrated crystal structures have the most suitable setting for exploring novel exotic states of matter. Spinel oxides (AM 2 O 4 ) are well-known examples of geometrically frustrated systems. In this study, we report for the first time the synthesis of compositions LiRhRu 1-x Ir x O 4 (x = 0–0.5), LiFeIr 1-x Ru x O 4 (x = 0–0.5), and LiCoIr 1-x Ru x O 4 (x = 0–0.3) containing precious metal cations on edge-sharing octahedral M-sites, and systematically investigate their magnetic and electrical properties. 57 Fe Mössbauer spectroscopy revealed that iron is trivalent in all LiFeIr 1-x Ru x O 4 solid solutions. Magnetic measurements indicate deviations from theoretical spin-only magnetic moment values, indicating the influence of spin-orbit coupling owing to the presence of 4d and 5d block elements. The LiFeIr 1-x Ru x O 4 series shows spin-glass-like freezing behavior with T g ≈ 20 K, and a small frustration index (f ≈ 1-2), indicating that the frustration originates from site disorder. LiRhRu 1-x Ir x O 4 and LiCoIr 1-x Ru x O 4 exhibit strongly geometrically frustrated magnetism. Electrical resistivity measurements as a function of temperature indicate that all phases are semiconducting. Seebeck coefficient measurements show that LiRhRu 1-x Ir x O 4 and LiFeIr 1-x Ru x O 4 are p-type semiconductors with holes as the major charge carriers. A sign reversal of the Seebeck coefficient indicates both holes and electrons as carriers for LiCoIr 1-x RuxO 4 (x = 0–0.2), but only holes as major carriers for x = 0.3. Here, the Seebeck coefficient and power factor increase drastically in the LiRhRu 1-x Ir x O 4 solid solution with Ir substitution, reaching a maximum of ≈ +125 μV/K and ≈2.3×10 -6 W/mK 2 at ∼650 K for x = 0.5.

Charge carriers↗
DOE OSTI2021

Vaporization behavior of Ir 4 (CO) 12 and Re 2 (CO) 10 measured by torsion effusion gravimetric method

Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD is used for deposition of high-purity metallic and alloy coatings for which vapor pressure data is essential. In this study, we report vapor pressures of solid Ir 4 (CO) 12 and Re 2 (CO) 10 carbonyls measured by using the Knudsen Cell methodology using a torsion effusion thermogravimetric system. The vapor pressure of the Ir 4 (CO) 12 exhibited incongruent vaporization, as the molecular weight (MW) of the effusing species was determined as 128 g/mol as compared to the theoretical MW of 1105 g/mol. It is proposed that the Ir 4 (CO) 12 (s) partially decomposed (~66%) to Ir 4 (CO) 12 (g), Ir(s), and CO(g). The Re 2 (CO) 10 on the other hand, showed congruent behavior with Re 2 (CO) 10 (s) vaporizing to Re 2 (CO) 10 (g) in the measured temperature range. The raw data for vapor pressures was measured using two sets of Knudsen cells with different orifice sizes, and the equilibrium vapor pressures were calculated using Whitman-Motzfeldt methodology. The equilibrium vapor pressures of these carbonyls, partial pressures of gaseous species in case of decomposition, average molecular weights of the effusing gasses were determined. The vapor pressures and Gibbs energies of vaporization reactions of the two above mentioned carbonyls, as well as comparison of vaporization thermodynamics these two carbonyls with other carbonyls from Group VIB to VIIIB are presented in this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Investigation of Mass Transfer and Sorption in CO 2 /Brine/Rock Systems via In Situ FT-IR

CO 2 geological storage in deep saline formations is considered a promising method to mitigate anthropogenic CO 2 emissions and, thereby, minimize changes to the Earth’s atmosphere. A fundamental understanding of CO 2 mass transfer and sorption phenomena in brine-saturated reservoir formations is necessary to understand the long-term fate of injected CO 2 as it is subjected to different (physical, dissolution, and mineral) trapping mechanisms. In this work, we investigate CO 2 sorption in brine-saturated and dry Mt. Simon sandstone samples via in-situ Fourier Transform infrared spectroscopy (FT-IR) at elevated pressures, ranging from 0.3 MPa to 8.3 MPa, at a temperature of 50 ⁰C. The FT-IR spectra of bulk-phase CO 2 were simultaneously recorded under the same conditions. For bulk-phase CO 2 , we observed, in agreement with past studies, a doublet peak at 2361 cm -1 and 2336 cm -1 and another peak (ν 2 bending mode) at 667 cm -1 . With increasing pressure, the position of the peak at 667 cm -1 remains invariant, however, when crossing into the supercritical region the doublet peak degenerates onto a single peak at 2336 cm -1 with a barely visible shoulder at 2361 cm -1 . The bulk CO 2 data provide a perfect fit for Beer’s law for the whole range of pressure conditions. For the dry sample, the IR spectrum is experimentally indistinguishable from the bulk CO 2 spectrum, signifying that if physical adsorption occurs to any significant extent, the adsorbed CO 2 molecules are not substantially more rotationally constrained than the dense bulk CO 2 molecules. For the brine-saturated sample, we observe a strong band centered at 2342 cm -1 and a small companion peak at 2360-2361 cm -1 that degenerates into a barely visible shoulder peak at the higher pressures. The 2342 cm -1 band has been previously observed by other investigators for CO 2 dissolved in bulk water/brine as well during its adsorption on a variety of other wet natural porous media. We observe no peaks corresponding to bicarbonate or carbonate bulk species, which correlates well with the prior literature on similar low-pH aqueous solutions. The integrated peak area for the CO 2 sorbed in the brine-saturated sample correlates linearly with its solubility in the same bulk brine, as measured separately via a PVT-cell approach. Here, this validates the accuracy of both techniques, and the potential of the FT-IR method to be used in the study of mass transfer and adsorption in such systems. To that effect, a simple mathematical model is presented to analyze the FT-IR data to determine the CO 2 effective diffusivity in the brine-saturated sandstone sample.

58 GEOSCIENCES↗
DOE OSTI2020

Ultrahigh Oxygen Evolution Reaction Activity Achieved Using Ir Single Atoms on Amorphous CoO x Nanosheets

Developing efficient electrocatalysts for an oxygen evolution reaction (OER) is important for renewable energy storage. Here, we design high-density Ir single-atom catalysts supported by CoO x amorphous nanosheets (ANSs) for the OER. Experimental results show that Ir single atoms are anchored by abundant surface-absorbed O in CoO x ANSs. Ir single-atom catalysts possess ultrahigh mass activity that is 160-fold of commercial IrO 2 . The OER of IrCoO x ANSs reached a record low onset overpotential of less than 30 mV. In situ X-ray absorption spectroscopy reveals that Ir-O-Co pairs directly boosted the OER efficiency and enhanced the Ir stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Microwave-Assisted Synthesis of Classically Immiscible Ag–Ir Alloy Nanoparticle Catalysts

In this work, we present the synthesis of Ag–Ir alloys in the form of solid-solution nanoparticles (NPs). Ag and Ir are classically immiscible in the bulk and therefore the physical properties of Ag–Ir alloys are unknown. A convenient microwave-assisted, solution-phase method that employs readily available Ag(NO 3 ) and IrCl 3 precursors enables the preparation of small (2.5–5.5 nm) Ag–IrNPs with alloyed structures. Ag $x$ Ir (100–$x$) NPs can be obtained by this method between $x$ = 6–31. The Ag–IrNPs resist dealloying upon heating up to 300 °C. Ir-rich Ag–IrNPs dispersed on amorphous silica are significantly more active gas-phase alkene hydrogenation catalysts than pure IrNPs. Density functional theory (DFT) and theoretical modeling studies reveal that the Ag–IrNPs—which are consistently larger than monometallic IrNPs prepared under the same conditions—have comparatively fewer strong H-binding edge sites. This promotes faster H atom transfer to coadsorbed alkenes. Ag–IrNPs supported on amorphous Co 3 O 4 show a linear composition dependence in the selective hydrogenation of C$=$O versus C$=$C bonds: more Ag-rich Ag–IrNPs are more selective toward C$=$O hydrogenation of the α,β-unsaturated aldehyde crotonaldehyde, yielding the industrially desirable crotyl alcohol. Furthermore, deposition of Ag–IrNPs inside Co 3 O 4 mesopores results in an additional ~56% selectivity enhancement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Active and stable Ir@Pt core–shell catalysts for electrochemical oxygen reduction

Electrochemical oxygen reduction is an important reaction for many sustainable energy technologies, such as fuel cells and metal–air batteries. Kinetic limitations of this reaction, expensive electrocatalysts, and catalyst instability, however, limit the commercial viability of such devices. Herein, we report an active Ir@Pt core–shell catalyst that combines platinum overlayers with nanostructure effects to tune the oxygen binding to the Pt surface, thereby achieving enhanced activity and stability for the oxygen reduction reaction. Ir@Pt nanoparticles with several shell thicknesses were synthesized in a scalable, inexpensive, one-pot polyol method. Electrochemical analysis demonstrates the activity and stability of the Ir@Pt catalyst, with specific and mass activities increasing to 2.6 and 1.8 times that of commercial Pt/C (TKK), respectively, after 10 000 stability cycles. Furthermore, activity enhancement of the Ir@Pt catalyst is attributed to weakening of the oxygen binding to the Pt surface induced by the Ir core.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2023

Silica Supported Organometallic Ir I Complexes Enable Efficient Catalytic Methane Borylation

Catalytic C–H borylation is an attractive method for the conversion of the most abundant hydrocarbon, methane (CH 4 ), to a mild nucleophilic building block. However, existing CH 4 borylation catalysts often suffer from low turnover numbers and conversions, which is hypothesized to result from inactive metal hydride agglomerates. Herein we report that the heterogenization of a bisphosphine molecular precatalyst, [(dmpe)Ir(cod)CH 3 ], onto amorphous silica dramatically enhances its performance, yielding a catalyst that is 12-times more efficient than the current standard for CH 4 borylation. The catalyst affords over 2000 turnovers at 150 °C in 16 h with a selectivity of 91.5% for mono- vs diborylation. Higher catalyst loadings improve yield and selectivity for the monoborylated product (H 3 CBpin) with 82.8% yield and >99% selectivity being achieved with 1255 turnovers. X-ray absorption and dynamic nuclear polarization-enhanced solid-state NMR spectroscopic studies identify the supported precatalyst as an Ir I species, and indicate that upon completion of catalysis, multinuclear Ir polyhydrides are not formed. This is consistent with the hypothesis that immobilization of the organometallic Ir species on a surface prevents bimolecular decomposition pathways. Importantly, immobilization of the homogeneous Ir I fragment onto amorphous silica represents a unique and simple strategy to improve the TON and longevity of a CH 4 borylation catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Water of Hydration Dynamics in Minerals Gypsum and Bassanite: Ultrafast 2D IR Spectroscopy of Rocks

Water of hydration plays an important role in minerals, determining their crystal structures and physical properties. In this work, ultrafast nonlinear infrared (IR) techniques, twodimensional infrared (2D IR) and polarization selective pump-probe (PSPP) spectroscopies, were used to measure the dynamics and disorder of water of hydration in two minerals, gypsum (CaSO 4 ·2H 2 O) and bassanite (CaSO 4 ·0.5H 2 O). 2D IR spectra revealed that water arrangement in freshly precipitated gypsum contained a small amount of inhomogeneity. Following annealing at 348 K, water molecules became highly ordered; the 2D IR spectrum became homogeneously broadened (motional narrowed). PSPP measurements observed only inertial orientational relaxation. In contrast, water in bassanite’s tubular channels is dynamically disordered. 2D IR spectra showed a significant amount of inhomogeneous broadening caused by a range of water configurations. At 298 K, water dynamics cause spectral diffusion that sampled a portion of the inhomogeneous linewidth on the timescale of ~30 ps, while the rest of inhomogeneity is static on the time scale of the measurements. At higher temperature, the dynamics become faster. Spectral diffusion accelerates, and a portion of the lower temperature spectral diffusion became motionally narrowed. At sufficiently high temperature, all of the dynamics that produced spectral diffusion at lower temperatures became motionally narrowed and only homogeneous broadening and static inhomogeneity were observed. Water angular motions in bassanite exhibit temperaturedependent diffusive orientational relaxation in a restricted cone of angles. The experiments were made possible by eliminating the vast amount of scattered light produced by the granulated powder samples using phase cycling methods.

14 SOLAR ENERGY↗
DOE OSTI2019

Mitotic regulators and the SHP2-MAPK pathway promote IR endocytosis and feedback regulation of insulin signaling

Insulin controls glucose homeostasis and cell growth through bifurcated signaling pathways. Dysregulation of insulin signaling is linked to diabetes and cancer. The spindle checkpoint controls the fidelity of chromosome segregation during mitosis. Here, we show that insulin receptor substrate 1 and 2 (IRS1/2) cooperate with spindle checkpoint proteins to promote insulin receptor (IR) endocytosis through recruiting the clathrin adaptor complex AP2 to IR. A phosphorylation switch of IRS1/2 orchestrated by extracellular signal-regulated kinase 1 and 2 (ERK1/2) and Src homology phosphatase 2 (SHP2) ensures selective internalization of activated IR. SHP2 inhibition blocks this feedback regulation and growth-promoting IR signaling, prolongs insulin action on metabolism, and improves insulin sensitivity in mice. We propose that mitotic regulators and SHP2 promote feedback inhibition of IR, thereby limiting the duration of insulin signaling. Targeting this feedback inhibition can improve insulin sensitivity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Magnetotransport of Sm 2 Ir 2 O 7 across the pressure-induced quantum-critical phase boundary

Rare-earth pyrochlore iridates host two interlocking magnetic sublattices of corner-sharing tetrahedra and can harbour a unique combination of frustrated moments, exotic excitations and highly correlated electrons. They are also the first systems predicted to display both topological Weyl semimetal and axion insulator phases. We have measured the transport and magnetotransport properties of single-crystal Sm 2 Ir 2 O 7 up to and beyond the pressure-induced quantum critical point for all-in-all-out (AIAO) Ir order at p c = 63 kbar previously identified by resonant X-ray scattering and close to which Weyl semimetallic behavior has been previously predicted. Our findings overturn the accepted expectation that the suppression of AIAO order should lead to metallic conduction persisting down to zero temperature. Instead, the resistivity-minimum temperature, which tracks the decrease in the AIAO ordering temperature for pressures up to 30 kbar, begins to increase under further application of pressure, pointing to the presence of a second as-yet unidentified mechanism leading to non-metallic behavior. The magnetotransport does track the suppression of Ir magnetism, however, with a strong hysteresis observed only within the AIAO phase boundary, similar to that found for Ho 2 Ir 2 O 7 and attributed to plastic deformation of Ir domains. Around pc we find the emergence of a new type of electronic phase, characterized by a negative magnetoresistance with small hysteresis at the lowest temperatures, and hysteresis-free positive magnetoresistance above approximately 5K. The temperature dependence of our low-temperature transport data are found to be best described by a model consistent with a Weyl semimetal across the entire pressure range.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Ir 6 In 32 S 21 , a polar, metal-rich semiconducting subchalcogenide

Subchalcogenides are uncommon, and their chemical bonding results from an interplay between metal–metal and metal–chalcogenide interactions. Herein, we present Ir 6 In 32 S 21 , a novel semiconducting subchalcogenide compound that crystallizes in a new structure type in the polar P31m space group, with unit cell parameters a = 13.9378(12) Å, c = 8.2316(8) Å, α = β = 90°, γ = 120°. The compound has a large band gap of 1.48(2) eV, and photoemission and Kelvin probe measurements corroborate this semiconducting behavior with a valence band maximum (VBM) of –4.95(5) eV, conduction band minimum of –3.47(5) eV, and a photoresponse shift of the Fermi level by ~0.2 eV in the presence of white light. X-ray absorption spectroscopy shows absorption edges for In and Ir do not indicate clear oxidation states, suggesting that the numerous coordination environments of Ir 6 In 32 S 21 make such assignments ambiguous. Electronic structure calculations confirm the semiconducting character with a nearly direct band gap, and electron localization function (ELF) analysis suggests that the origin of the gap is the result of electron transfer from the In atoms to the S 3p and Ir 5d orbitals. DFT calculations indicate that the average hole effective masses near the VBM (1.19m e ) are substantially smaller than the average electron masses near the CBM (2.51m e ), an unusual feature for most semiconductors. The crystal and electronic structure of Ir 6 In 32 S 21 , along with spectroscopic data, suggest that it is neither a true intermetallic nor a classical semiconductor, but somewhere in between those two extremes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The development of in-situ calibration method for divertor IR thermography in ITER

For the development of the calibration method of the emissivity in IR light on the divertor plate in ITER divertor IR thermography system, the laboratory experiments have been performed by using IR instruments. The calibration of the IR camera was performed by the plane black body in the temperature of 100–600 degC. The radiances of the tungsten heated by 280 degC were measured by the IR camera without filter (2.5–5.1 μm) and with filter (2.95 μm, 4.67 μm). The preliminary data of the scattered light of the laser of 3.34 μm that injected into the tungsten were acquired.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗