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At least 487 records · Page 27

Evaluation of Gamma Ray Production - Quarterly Report FY22Q2

The LLNL team has performed the first systematic study of the effect of two-body weak currents in β decay rates across the entire mass table. In light and medium-mass nuclei, two-body weak currents from chiral effective field theory account for a significant portion of the phenomenological quenching of Gamow-Teller transition matrix elements. We examined the systematic effects of two-body axial currents on Gamow-Teller strength and β-decay rates in heavy nuclei within energy-density functional theory. We extended the charge-changing finiteamplitude pnFAM code to incorporate the contributions of two-body currents to the usual onebody linear response in the Gamow-Teller channel. We found that the two-body currents, as expected, usually quench both summed Gamow-Teller strength and decay rates, but by an amount that decreases as the neutron excess grows; see Fig. 1. In addition, they can enhance individual low-lying transitions, leading to decay rates that are quite different from those that an energy-independent quenching would produce, particularly in neutron-rich nuclei. This new physics capability is unique and provides the highest-fidelity description of β decay on the market. The underlying computational implementation can be reused to calculate γ-strength functions for finite-range nuclear potentials such as the Gogny force, which will allow us to benchmark some of our future developments against published results. The paper is in print in Phys. Rev. C.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Development and Test of a Large Aperture $Nb_3Sn$ Cos-Theta Dipole Coil with Stress Management

An innovative stress-management (SM) concept for cos-theta (CT) coils (SMCT coil concept) has been proposed at Fermilab. A large-aperture two-layer Nb3Sn SMCT dipole coil was designed and manufactured to validate and test the SM concept including coil design, fabrication technology, and performance. The first large-aperture SMCT coil (SMCT1) was fabricated and assembled with a small-aperture Nb3Sn coil inside a dipole mirror magnet. SMCT1 coil tests in a dipole mirror structure was performed in two configurations - SMCTM1a with only powered two-layer SMCT1 coil and SMCTM1b with the SMCT coil connected in series with an inner two-layer dipole coil. The test goals are to prove the SMCT coil concept in two-layer and four-layer mirror configurations; demonstrate that the magnet can reach the targeted quench current at the established preload; study magnet training, training memory after thermal cycle, ramp rate and temperature dependences of the magnet quench current; and test the SMCT1 coil quench protection parameters. This paper summarizes the SMCT1 coil design and parameters, the coil main fabrication steps, its assembly in the dipole mirror structure. The results of the SMCTM1a/b mirror test are presented and discussed.

43 PARTICLE ACCELERATORS↗

Application of Flex-QA Arrays in HTS Magnet Testing

Flexible PCB quench antennas have been very useful in providing high-quality high-resolution data in low temperature superconducting magnet tests. Similar multi-sensor arrays have been employed recently to cover a high temperature superconductor magnet tested at FNAL. In the present work, data taking conditions and magnet features to support the analysis framework are discussed. Then observations made during complete magnet powering cycles are described and analysis of quench antenna data are presented. Based on results, improvements to instrumentation and data taking are debated. Views on the future of flexible quench antenna sensors for HTS magnet diagnostics and operational support are shared.

Stoynev, S.↗

Canister Centerline Cooling Experiments for DPF5-336 Reference Material Made with ERV3b Salt Simulant

This report provides experimental details and results on the elemental distributions (compositions), crystalline/amorphous phase distribution, and microstructures for DPF5-336 reference materials made with ERV3b salt that were subjected to the canister centerline cooling (CCC) heat treatment process. To fabricate these materials, ammonium dihydrogen phosphate was mixed with ERV3b salt simulant and a dechlorination procedure was run in the generation-2 dechlorinator at the Pacific Northwest National Laboratory up to 600°C in an alumina crucible. After the dechlorination process, the product was removed from the crucible, lightly crushed, loaded into a new alumina crucible, Fe 2 O 3 was added, and this was vitrified at 1100°C for 1 hour and quenched. The quenched material was mostly amorphous but showed some small diffraction peaks attributed to Li 3 Fe 2 (PO 4 ) 3 . This quenched material was ground to a fine particle size in a milling chamber, and this was subjected to the CCC cooling profile in duplicate within alumina and fused quartz crucibles. The CCC experiment is designed to simulate the slowest cooling profile (the vertical centerline) of a 0.61-m diameter canister where the slower cooling profile often results in the production of a variety of different crystalline phases upon formation of which result in a residual glass of unknown composition and properties. The information gleaned from these types of experiments will lead to improved composition-property predictions for materials with similar compositions. The results of the alumina and fused quartz experiments show different microstructures but similar diffraction patterns providing evidence of similar crystalline phases being present in each sample. Both samples had monazite [i.e., (Ce,Nd)PO 4 ] and mixtures of phases containing P, Fe, and alkali metal elements. This report completes the milestone M4FT-23PN030104042 with details provided in Appendix B.

36 MATERIALS SCIENCE↗

Effect of Initial Microstructure on the Toughness of Coarse-Grained Heat-Affected Zone in a Microalloyed Steel

Toughness of the coarse-grained-heat-affected-zone (CGHAZ) strongly depends on the prior austenite grain size. The prior austenite grain size is affected not only by chemical composition, thermal cycle, and dissolution of second-phase particles, but also by the initial microstructure. The effect of base metal microstructure (ferrite/pearlite obtained by air cooling and martensite obtained by water-quenching) on Charpy impact toughness of the CGHAZ has been investigated for different heat inputs for high-heat input welding of a microalloyed steel. A welding thermal cycle with a heat input of 100 kJ/cm and 400 kJ/cm were simulated on the MMS-300 system. Despite a similar microstructure in the CGHAZ of both the base metals, the average Charpy impact energy for the air-cooled base metal was found to be higher than the water-quenched base metal. Through thermo-kinetic simulations, it was found that a higher enrichment of Mn/C at the ferrite/austenite transformation interface of the CGHAZ of water-quenched base metal resulted in stabilizing austenite at a lower A1 temperature, which resulted in a coarser austenite grain size and eventually lowering the toughness of the CGHAZ.

36 MATERIALS SCIENCE↗

Resolved Molecular Gas Observations of MaNGA Post-starbursts Reveal a Tumultuous Past

Post-starburst (PSB) galaxies have recently and rapidly quenched their star formation; thus, they are an important way to understand how galaxies transition from star-forming late types to quiescent early types. The recent discovery of large cold gas reservoirs in PSB galaxies calls into question the theory that galaxies must lose their gas to become quiescent. Optical Integral Field Spectroscopy (IFS) surveys have revealed two classes of PSB galaxies: central PSB (cPSB) galaxies with central quenching regions and ring PSB (rPSB) galaxies with quenching in their outskirts. We analyze a sample of 13 nearby (z < 0.1) PSB galaxies with spatially resolved optical IFS data from the Mapping Nearby Galaxies at Apache Point Observatory survey and matched resolution Atacama Large Millimeter/submillimeter Array observations of 12 CO(1–0). Disturbed stellar kinematics in 7/13 of our PSB galaxies and centrally concentrated molecular gas is consistent with a recent merger for most of our sample. In galaxies without merger evidence, alternate processes may funnel gas inward and suppress star formation, which may include outflows, stellar bars, and minor mergers or interactions. The star formation efficiencies of the PSB regions in nearly half our galaxies are suppressed while the gas fractions are consistent with star-forming galaxies. Active galactic nucleus (AGN) feedback may drive this stabilization, and we observe AGN-consistent emission in the centers of 5/13 galaxies. Finally, our cPSB and rPSB galaxies have similar properties except the ionized and molecular gas in cPSB galaxies is more disturbed. Overall, the molecular gas in our PSB galaxies tends to be compact and highly disturbed, resulting in concentrated gas reservoirs unable to form stars efficiently.

79 ASTRONOMY AND ASTROPHYSICS↗

Discovery and Characterization of Two Ultrafaint Dwarfs outside the Halo of the Milky Way: Leo M and Leo K

Abstract We report the discovery of two ultrafaint dwarf galaxies, Leo M and Leo K, that lie outside the halo of the Milky Way (MW). Using Hubble Space Telescope imaging of the resolved stars, we create color–magnitude diagrams reaching the oldest main-sequence turnoff of each system and (i) fit for structural parameters of the galaxies; (ii) measure their distances using the luminosity of the horizontal branch stars; (iii) estimate integrated magnitudes and stellar masses; and (iv) reconstruct the star formation histories. Based on their location in the Local Group, neither galaxy is currently within the halo of the MW although Leo K is located ∼26 kpc from the low-mass galaxy Leo T and these two systems may have had a past interaction. Leo M and Leo K have stellar masses of 1.8 − 0.2 + 0.3 × 10 4 M ⊙ and 1.2 ± 0.2 × 10 4 M ⊙ , and were quenched 10.6 − 1.1 + 2.2 Gyr and 12.8 − 4.2 + 0.1 Gyr ago, respectively. Given that the galaxies are at farther distances from the MW, it is unlikely that they were quenched by environmental processing. Instead, given their low stellar masses, their early quenching timescales are consistent with the scenario that a combination of reionization and stellar feedback shut down star formation at early cosmic times.

Astronomy & Astrophysics↗

The SAGA Survey. VI. The Size–Mass Relation for Low-mass Galaxies Across Environments

We investigate how Milky Way (MW)–like environments influence the sizes and structural properties of low mass galaxies by comparing satellites of MW analogs from the Satellites Around Galactic Analogs (SAGA) Survey with two control samples: an environmentally agnostic population from the SAGA background sample and isolated galaxies from the Sloan Digital Sky Survey NASA-Sloan Atlas. All sizes and structural parameters are measured uniformly using pysersic to ensure consistency across samples. We find the half-light sizes of SAGA satellites are systematically larger than those of isolated galaxies, with the magnitude of the offset ranging from 0.05 to 0.12 dex (10%–24%) depending on the comparison sample and completeness cuts. This corresponds to physical size differences between 85 and 200 pc at log 10 (M$_{{\star}}$/M ⊙ ) = 7.5 and 220–960 pc at log 10 (M$_{{\star}}$/M ⊙ ) = 10. This offset persists among star-forming galaxies, suggesting that environment can influence the structure of low-mass galaxies even before it impacts quenching. The intrinsic scatter in the size–mass relation is lower for SAGA satellites than isolated galaxies, and the Sérsic index distributions of satellites and isolated galaxies are similar. In comparison to star-forming satellites, quenched SAGA satellites have a slightly shallower size–mass relation and rounder morphologies at low mass, suggesting that quenching is accompanied by structural transformation and that the processes responsible differ between low- and high-mass satellites. Our results show that environmental processes can imprint measurable structural differences on satellites in MW-mass halos.

Asali, Yasmeen [Yale Univ., New Haven, CT (United ↗

Computational Fermi Level Engineering and Doping-Type Conversion of Ga2O3 Via Three-Step Processing

Ga2O3 is being actively explored for power electronics, deep-ultraviolet optoelectronics, and other applications due to its ultra-wide bandgap and low projected fabrication cost of large-size and high-quality crystals. N-type doping of Ga2O3 can be achieved and tuned, but p-type doping faces fundamental obstacles due to deep character of acceptor levels and polaron transport of resulting holes. However, successful engineering of Ga2O3 based devices requires critical control of doping density, Fermi level position, and free carrier concentration, providing opportunities for predictive process simulation. We use first-principles defect theory and defect equilibrium calculations to simulate a 3-step growth-annealing-quench protocol for hydrogen assisted Mg doping in Ga2O3, taking into account the hydrogen-oxygen-water gas phase equilibrium. We predict type conversion to a net p-type regime following O-rich annealing after growth under reducing conditions in the presence of H2. This process is similar to the Mg acceptor activation by H removal in GaN. We show that there is an optimal temperature that maximizes the net acceptor density during the equilibrium annealing step for a given Mg doping level. Quenching of non-equilibrium annealed samples then results in a Fermi level EF below mid-gap down to about EV +1.5 eV, creating a significant number of uncompensated neutral MgGa0 acceptors. The resulting free hole concentration in quenched samples is very low (109 – 1012 cm-3) due to deep energy level of these Mg acceptors, but this type converted Ga2O3 material can create a significant built-in field in a p-n junction with an adjoining n-type material. Additionally, the electron concentration is greatly suppressed in such acceptor-doped Ga2O3, which could enable the use as a current blocking layer to fabricate normally-off (enhancement-mode) vertical Ga2O3 based metal-oxide-semiconductor field effect transistors (MOSFETs), and as a guard ring for edge termination in MOSFETs and Schottky barrier diodes (SBDs) with increased breakdown voltage.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS,M↗

Characterization of Alloy 709 Commercial Heats

The creep-resistant austenitic stainless steel Alloy 709 (Fe-20Cr-25Ni (wt%) based steel) is being investigated as a candidate structural material for the next generation of advanced reactors. Unlike conventional solid solution strengthened austenitic stainless steels, Alloy 709 develops a variety of precipitates during aging at different temperatures and times. In this study, precipitate evolution during short-term aging at 775°C was characterized. The effect of aging time (e.g., 10 vs. 100 hours) and cooling after aging (e.g., water quench vs. air cool) on grain size and precipitates have been investigated using light optical microscopy (OM), electron backscatter diffraction (EBSD), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). MX (Ni,Tb)(C,N) and M23C6 (Cr,Mo)C precipitates were observed in all the statically-aged samples. The grain size distribution in the sample aged for 10 hours and water quenched (10Q) versus the one aged for 100 hours and air cooled (100A) were comparable. This indicates that grain structure was fairly stable when aging at 775°C for up to 100 hours. In contrast, the sample aged for 10 hours and air cooled (10A) showed the smallest and the most uniform grain size distribution. This phenomenon was observed in only one sample. More studies on duplicate samples are needed to confirm the results obtained. The cooling medium (e.g., water quench vs. air cool) was not observed to impact the size nor the distribution of the MX and M23C6 precipitates. Increasing the aging time resulted in the following: (1) a decrease in dislocations as well as the number density of small precipitates; (2) an increase in the ratio of free precipitates that were not pinning dislocations; (3) relatively higher N, Nb, and Ti concentration in MX precipitate; (4) some increase in length of M23C6 carbides which were located on the coherent boundaries; and (5) the introduction of Sienriched M6X precipitates. The tensile tests at room temperature showed similar properties for each of the static aging treatments, indicating that the differences observed in the microstructural analysis did not have a significant impact on the tensile properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fiber-optic diagnostic system for future accelerator magnets

The next generation high energy physics accelerators will require magnetic fields at ~20 T. HTS coils will be an essential component of future accelerator magnets and several efforts are currently dedicated on designing 20 T HTS- LTS hybrid magnets. Among the existing challenges, there is the lack of a robust quench detection system for hybrid magnet technology. Another big challenge is represented by the high number of training quenches required by Nb3Sn magnets to reach performance level. In this framework it is important to find a tool that allow local real-time monitoring of magnet strain and temperature. In this paper, we propose the use of fiber optics sensors for diagnostic and quench detection in future accelerator superconducting magnets. Discrete and distributed fiber optic sensors have demonstrated to be a promising tool. The goal is to instrument hundreds of accelerator superconducting magnets and to move beyond the proof-of-concept level. Significant developments are still needed. Here, we are going to present the most recent results and discuss the most urgent technical developments in order to make those sensors a robust and reliable diagnostic tool for accelerator superconducting magnets over the next 10 year. We foresee that discrete fiber sensors will be a stable diagnostic probe for superconducting magnets over the next 3 to 5 years. More R&D work will be necessary for distributed fibers. The most urgent needs are the increase of sample rate and sensitivity. Close collaboration with vendors will be necessary to improve mechanical properties and fabrication processes in order to produce hundreds of meters of fiber and instrument a large number of accelerator superconducting magnets. Those R&D efforts will last up to 10 years with a founding level that spans between 5-10 M$.

43 PARTICLE ACCELERATORS↗

(Towards) DNS of a Laboratory Lean CH4/H2 Low-Swirl Flame Impinging on an Inclined Wall

Due to downsizing trends, flame-wall interaction (FWI) is increasingly prominent in gas turbines (GTs). FWI has direct consequences on flame stabilization and pollutant emissions, but it is not well understood in turbulent flows representative of GTs. We present results from a direct numerical simulation (DNS) of a turbulent CH4/H2 model GT low-swirl laboratory-scale flame interacting with an inclined wall. The results from the laboratory flame include simultaneous measurements of velocity using stereo particle imaging velocimetry and OHxCH2O planar laser induced fluorescence. The adaptive-mesh refinement solver PeleLMeX is used, with 24-species, 105-reaction reduced Aramco chemical kinetics mechanism. The premixed fuel-air mixture consists of hydrogen-enriched methane with 70% hydrogen volume fraction and 0.4 equivalence ratio. The inflow is prescribed to match experimental measurements at the burner exit. Karlovitz and turbulent Reynolds numbers are 300 and 400, respectively. The simulation and experimental results show excellent agreement. The flame features a bowl-shape stabilization, with a corrugated, continuous flame front at the leading edge, followed by fragmented reaction zones downstream. A large diffuse cloud of CH2O is formed downstream of the quenching point. The simulation results indicate that the cloud of CH2O is the result of incomplete methane combustion, with CH2O "leaking" from the locally quenched reaction zones.The DNS provides fine-grain resolution of turbulence-flame-wall interaction that cannot be captured with experimental measurements. With access to the entire solution vector at each cell of the computational domain, the local quenching.

flame-wall interactions↗

Stereoscopic detection of hot spots in superfluid 4 He (He II) for accelerator-cavity diagnosis

Superconducting radio-frequency (SRF) cavities cooled by superfluid 4He (He II) are building blocks of many modern particle accelerators due to their high quality factor. However, Joule heating from sub-millimeter surface defects on cavities can lead to cavity quenching, which limits the maximum acceleration gradient of the accelerators. Developing a non-contacting detection technology to accurately locate these surface hot spots is the key to improve the performance of SRF cavities and hence the accelerators. In a recent proof-of-concept experiment, we demonstrated that a molecular tagging velocimetry (MTV) technique based on the tracking of a He molecular tracer line created nearby a surface hot spot in He II can be utilized to locate the hot spot. In order to make this technique practically useful, here we describe our further development of a stereoscopic MTV setup for tracking the tracer line’s motion in three-dimensional (3D) space. We simulate a quench spot by applying a transient voltage pulse to a small heater mounted on a substrate plate. Images of the drifted tracer line, taken with two cameras from orthogonal directions, are used to reconstruct the line profile in 3D space. Here, a new algorithm for analyzing the 3D line profile is developed, which incorporates the finite size effect of the heater. We show that the center location of the heater can be reproduced on the substrate surface with an uncertainty of only a few hundred microns, thereby proving the practicability of this method.

43 PARTICLE ACCELERATORS↗

The major trimeric antenna complexes serve as a site for qH-energy dissipation in plants

Plants and algae are faced with a conundrum: harvesting sufficient light to drive their metabolic needs while dissipating light in excess to prevent photodamage, a process known as nonphotochemical quenching. A slowly relaxing form of energy dissipation, termed qH, is critical for plants’ survival under abiotic stress; however, qH location in the photosynthetic membrane is unresolved. Here, we tested whether we could isolate subcomplexes from plants in which qH was induced that would remain in an energy-dissipative state. Interestingly, we found that chlorophyll (Chl) fluorescence lifetimes were decreased by qH in isolated major trimeric antenna complexes, indicating that they serve as a site for qH-energy dissipation and providing a natively quenched complex with physiological relevance to natural conditions. Next, we monitored the changes in thylakoid pigment, protein, and lipid contents of antenna with active or inactive qH but did not detect any evident differences. Finally, we investigated whether specific subunits of the major antenna complexes were required for qH but found that qH was insensitive to trimer composition. Because we previously observed that qH can occur in the absence of specific xanthophylls, and no evident changes in pigments, proteins, or lipids were detected, we tentatively propose that the energy-dissipative state reported here may stem from Chl–Chl excitonic interaction.

59 BASIC BIOLOGICAL SCIENCES↗

Characterization of 6 Li-loaded pulse-shape-discriminating plastic scintillators

Lithium-loaded organic plastic scintillators combine sensitivity to γ rays with the ability to detect both fast and slow neutrons, making them valuable for applications in nuclear security and in basic nuclear and particle physics. The goal of this work is to characterize the neutron response of two custom lithium-loaded organic plastic scintillators developed at Lawrence Livermore National Laboratory. Both are ternary polystyrene-based formulations containing 1.5 wt.% 6 Li salts of isobutyric acid, but they differ in their primary and secondary dye compositions: one uses m-terphenyl as the primary fluor and with Exalite 404 as the wavelength shifter, whereas the other uses 2,5-diphenyloxazole (PPO) and 9,10-diphenyl-anthracene, respectively. The temporal response of the scintillators was measured via time-correlated single photon counting for γ-ray and neutron events. The proton light yield was measured using the double time-of-flight technique from 1.3 to 15 MeV at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory. For the slow neutron response, an AmBe source moderated with polyethylene was used, and the light output from the 6 Li(n,α)t reaction was characterized. Differences in ionization quenching and temporal response were observed between the two materials with the PPO-containing scintillator exhibiting higher ionization quenching. These results provide performance benchmarks that can guide the design and optimization of future lithium-loaded plastic scintillators for use in basic science and applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Measurement of substructure-dependent suppression of large-radius jets with charged particles in Pb+Pb collisions with ATLAS

Measurements of jet substructure in Pb+Pb collisions provide key insights into the mechanism of jet quenching in the hot and dense QCD medium created in these collisions. This Letter presents a measurement of the suppression of large-radius jets with a radius parameter of $R = 1.0$ and its dependence on the jet substructure. The measurement uses 1.72 nb$^{-1}$ of Pb+Pb data and 255 pb$^{-1}$ of $pp$ data, both at $\sqrt{s_{_\mathrm{NN}}} = 5.02$ TeV, recorded with the ATLAS detector at the Large Hadron Collider. Large-radius jets are reconstructed by reclustering $R = 0.2$ calorimetric jets and are measured for transverse momentum above $200$ GeV. Jet substructure is evaluated using charged-particle tracks, and the overall level of jet suppression is quantified using the jet nuclear modification factor ($R_\mathrm{AA}$). The jet $R_\mathrm{AA}$ is measured as a function of jet $p_{\mathrm{T}}$, the charged $k_t$ splitting scale ($\sqrt{d_{12}}$), and the angular separation ($dR_{12}$) of two leading sub-jets. The jet $R_\mathrm{AA}$ gradually decreases with increasing $\sqrt{d_{12}}$, implying significantly stronger suppression of large-radius jets with larger $k_t$ splitting scale. The jet $R_\mathrm{AA}$ gradually decreases for $dR_{12}$ in the range $0.01{-}0.2$ and then remains consistent with a constant for $ΔR_{12} \gtrsim 0.2$. The observed significant dependence of jet suppression on the jet substructure will provide new insights into its role in the quenching process.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Fluorescence Enhancement in the Solid State by Isolating Perylene Fluorophores in Metal–Organic Frameworks

Polycyclic aromatic hydrocarbons such as perylene, pyrene, and their derivatives are highly emissive fluorophores in solution. Furthermore, the practical applications of these materials in the field of molecular electronic and light emitting devices are often hindered by self-quenching effects due to the formation of non-fluorescent aggregates in concentrated solutions or in the solid state. Herein, we demonstrate that aggregation caused quenching of perylenes can be minimalized by molecular incorporation into metalorganic frameworks (MOFs). This study utilized a stable Zr 6 cluster-based MOF, UiO-67, as a matrix. Linear linkers containing the photo-responsive moieties were designed and incorporated into the parent UiO-67 scaffold through the partially replacement of the non-fluorescent linkers of a similar length, forming mixed-linker MOFs. Here, the average distance between perylene moieties was tuned by changing the linker ratios, thus controlling the fluorescence intensity, emission wavelength, and quantum yield. Molecular modeling was further adopted to correlate the number of isolated perylene linkers within the framework to the ratio between the two linkers, therefore rationalizing the change in the observed fluorescent properties. Taking advantage of the tunable fluorescence, inherent porosity, and high chemical stability of this MOF platform, it was applied as a fluorescent sensor for oxygen detection in the gas phase, a model reaction, showing fast response and good recyclability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor

Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗