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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Investigating the p--π ± and p--p--π ± dynamics with femtoscopy in pp collisions at $\sqrt{s}$ = 13 TeV

The interaction between pions and nucleons plays a crucial role in hadron physics. It represents a fundamental building block of the low-energy QCD dynamics and is subject to several resonance excitations. This work studies the p--π ± dynamics using femtoscopic correlations in high-multiplicity pp collisions at $\sqrt{s}$ = 13 TeV measured by ALICE at the LHC. As the final-state interaction between protons and pions is well constrained by scattering experiments and the study of pionic hydrogen, the results give access to information on the particle-emitting source in pp collisions using the femtoscopy methods. The scaling of the source size of primordial protons and pions against their pair transverse mass is extracted. The results are compared with the source sizes studied with p–p, p--K + , and π ± –π ± pairs by ALICE in the same collision system and are found to be in agreement for the different particle pairs. This reinforces recent findings by ALICE of a common emission source for all hadron-pairs in pp collisions at LHC energies. Furthermore, the p--p--π ± systems are studied using three-particle femtoscopy in pp collisions at TeV. The presence of three-body effects is analyzed utilizing the cumulant expansion method. In this formalism, the known two-body interactions are subtracted in order to isolate the three-body effects. For both, p--p--π + and p--p--π – , a non-zero cumulant is found, indicating effects beyond pairwise interactions. These results give information on the coupling of the pion to multiple nucleons.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Multicode benchmark on simulated Ti K-edge x-ray absorption spectra of Ti-O compounds

X-ray absorption spectroscopy (XAS) is an element-specific materials characterization technique that is sensitive to structural and electronic properties. First-principles simulated XAS has been widely used as a powerful tool to interpret experimental spectra and draw physical insights. Recently, there has also been growing interest in building computational XAS databases to enable data analytics and machine learning applications. However, there are non-trivial differences among commonly used XAS simulation codes, both in underlying theoretical formalism and in technical implementation. Reliable and reproducible computational XAS databases require systematic benchmark studies. In this work, we benchmarked Ti K-edge XAS simulations of ten representative Ti-O binary compounds, which we refer to as the Ti-O-10 dataset, using three state-of-the-art codes: XSPECTRA, OCEAN and exciting. We systematically studied the convergence behavior with respect to the input parameters and developed a workflow to automate and standardize the calculations to ensure converged spectra. Our benchmark comparison considers a 35 eV spectral range starting from the K-edge onset, representative of widely used near-edge spectra. Quantitative comparison over this range is based on Spearman’s rank correlation score (r sp ). Our results show: (1) the two Bethe-Salpeter equation (BSE) codes (OCEAN and exciting) have excellent agreement with an average $r$ $sp$ of 0.998; (2) good agreement is obtained between the core-hole potential code (XSPECTRA) and BSE codes (OCEAN and exciting) with an average $r$ $sp$ of 0.990, and this smaller $r$ $sp$ reflects the noticeable differences in the main edge spectral shape that can be primarily attributed to the difference in the strength of the screened core-hole potential; (3) simulations from both methods overall reproduce well the main experimental spectral features of rutile and anatase, and the different treatments of the screened core-hole potential have visible impact on pre-edge intensities and the peak ratio of the main edge; (4) there exist moderate differences in the relative edge alignment of the three codes with a standard deviation of about 0.2 eV, which arise from multiple contributions including the frozen core approximation, final state effects, and different approximations used for the self-energy correction. In conclusion, our benchmark study provides important standards for first-principles XAS simulations with broad impact in data-driven XAS analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Rotational excitations in rare-earth nuclei: A comparative study within three cranking models with different mean fields and treatments of pairing correlations

High-spin rotational bands in rare-earth Er (Z = 68), Tm (Z = 69), and Yb (Z = 70) isotopes are investigated by three different nuclear models. These are (i) the cranked relativistic Hartree-Bogoliubov (CRHB) approach with approximate particle number projection by means of the Lipkin-Nogami (LN) method, (ii) the cranking covariant density functional theory (CDFT) with pairing correlations treated by a shell-model-like approach (SLAP) or the so-called particle-number conserving (PNC) method, and (iii) cranked shell model (CSM) based on the Nilsson potential with pairing correlations treated by the PNC method. A detailed comparison between these three models in the description of the ground-state rotational bands of even-even Er and Yb isotopes is performed. The similarities and differences between these models in the description of the moments of inertia, the features of band crossings, and equilibrium deformations and pairing energies of the even-even nuclei under study are discussed. These quantities are considered as a function of rotational frequency and proton and neutron numbers. The changes in the properties of the first band crossings with increasing neutron number in this mass region are investigated. On average, a comparable accuracy of the description of available experimental data is achieved in these models. However, the differences between model predictions become larger above the first band crossings. Because of the time-consuming nature of numerical calculations in the CDFT-based models, a systematic study of the rotational properties of both ground-state and excited-state bands in odd-mass Tm nuclei is carried out only by the PNC-SCM. With few exceptions, the rotational properties of experimental 1-quasiparticle and 3-quasiparticle bands in 165,167,169,171 Tm are reproduced reasonably well. As a result, the appearance of backbendings or upbendings in these nuclei is well understood from the analysis of the variations of the occupation probabilities of the single-particle states and their contributions to total angular momentum alignment with rotational frequency.

150 ≤ A ≤ 189↗
DOE OSTI2022

Long–Cycling Sulfide–Based All–Solid–State Batteries Enabled by Electrochemo–Mechanically Stable Electrodes

Anode significantly determines the energy density of all-solid-state Lithium batteries (ASLBs). Silicon (Si) and Lithium (Li) metal are two of the most attractive anodes because of their ultrahigh theoretical capacities. However, most investigations focus on Li metal; the great potential of Si is underrated. This study investigates Si anode's stability, processability, and cost in ASLBs and compares them with Li metal. Moreover, the single-crystal LiNi 0.8 Co 0.1 Mn 0.1 O 2 is stabilized with a lithium silicate (Li 2 SiO x ) through a scalable sol-gel method. ASLBs with a cell-level energy density of 285 Wh kg -1 are obtained through sandwiching Si anode, thin sulfide solid-state electrolyte membrane, and interface stabilized LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The full cell delivered a high capacity of 145 mAh g -1 at C/3 and maintained stability for 1000 cycles. This work inspires commercializing the ASLBs on a large scale with exciting manufacturing lines for large-scale, safe, and economical energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

Applications of reduced-basis methods to the nuclear single-particle spectrum

Reduced-basis methods provide a powerful framework for building efficient and accurate emulators. Although widely applied in many fields to simplify complex models, reduced-basis methods have only been recently introduced into nuclear physics. In this Letter we build an emulator to study the single-particle structure of atomic nuclei. By scaling a suitable mean-field Hamiltonian, a “universal” reduced basis is constructed capable of accurately and efficiently reproduce the entire single-particle spectrum of a variety of nuclei. Indeed, the reduced-basis model reproduces both ground- and excited-state energies as well as the associated wave functions with remarkable accuracy. Here our results bode well for more demanding applications that use Bayesian optimization to calibrate nuclear energy density functionals.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS2018

ALMA Spectral Line and Imaging Survey of a Low and a High Mass-Loss Rate AGB Star Between 335 and 362 GHz

Context. Low and intermediate mass stars are known to power strong stellar winds when evolving through the asymptotic giant branch (AGB) phase. Initial mass, luminosity, temperature, and composition determine the pulsation characteristics of the star and the dust species formed in the pulsating photospheric layers. Radiation pressure on these grains triggers the onset of a stellar wind. However, as of today, we still cannot predict the wind mass-loss rates and wind velocities from first principles neither do we know which species are the first to condense in the upper atmospheric regions. Aims. We aim to characterise the dominant physical, dynamical, and chemical processes in the inner wind region of two archetypical oxygen-rich (C/O<1) AGB stars, that is, the low mass-loss rate AGB star R Dor (M~ 1x10(exp 7) M☉/yr) and the high mass-loss rate AGB star IK Tau (M~5x10(exp 6) M☉/yr). The purpose of this study is to observe the key molecular species contributing to the formation of dust grains and to cross-link the observed line brightnesses of several species to the global and local properties of the star and its wind. Methods. A spectral line and imaging survey of IK Tau and R Dor was made with ALMA between 335 and 362 GHz (band 7) at a spatial resolution of ~150 mas, which corresponds to the locus of the main dust formation region of both targets. Results. Some two hundred spectral features from 15 molecules (and their isotopologues) were observed, including rotational lines in both the ground and vibrationally excited states (up to v=5 for SiO). Detected species include the gaseous precursors of dust grains such as SiO, AlO, AlOH, TiO, and TiO2.We present a spectral atlas for both stars and the parameters of all detected spectral features. A clear dichotomy for the sulphur chemistry is seen: while CS, SiS, SO, and SO2 are abundantly present in IK Tau, only SO and SO2 are detected in R Dor. Also other species such as NaCl, NS, AlO, and AlOH display a completely different behaviour. From some selected species, the minor isotopologues can be used to assess the isotopic ratios. The channel maps of many species prove that both large and small-scale inhomogeneities persist in the inner wind of both stars in the form of blobs, arcs, and/or a disk. The high sensitivity of ALMA allows us to spot the impact of these correlated density structures in the spectral line profiles. The spectral lines often display a half width at zero intensity much larger than expected from the terminal velocity, v1, previously derived for both objects (36 km/s versus v(∞)~17.7 km/s for IK Tau and 23 km/s versus v(∞)~5.5 km/s for R Dor). Both a more complex 3D morphology and a more forceful wind acceleration of the (underlying) isotropic wind can explain this trend. The formation of fractal grains in the region beyond _400 mas can potentially account for the latter scenario. From the continuum map, we deduce a dust mass of ~3.7 x 10(exp 7) M☉ and ~2 x 10(ex0 8) M☉ for IK Tau and R Dor, respectively. Conclusions. The observations presented here provide important constraints on the properties of these two oxygen-dominated AGB stellar winds. In particular, the ALMA data prove that both the dynamical and chemical properties are vastly different for this high mass-loss rate (IK Tau) and low mass-loss rate (R Dor) star.

Stars: AGB and post-AGB, Stars: mass loss, Stars: ↗
NASA NTRS2018

ALMA Spectral Line and Imaging Survey of a Low and a High Mass-Loss Rate AGB Star Between 335 and 362 GHz

Context. Low and intermediate mass stars are known to power strong stellar winds when evolving through the asymptotic giant branch (AGB) phase. Initial mass, luminosity, temperature, and composition determine the pulsation characteristics of the star and the dust species formed in the pulsating photospheric layers. Radiation pressure on these grains triggers the onset of a stellar wind. However, as of today, we still cannot predict the wind mass-loss rates and wind velocities from first principles neither do we know which species are the first to condense in the upper atmospheric regions. Aims. We aim to characterise the dominant physical, dynamical, and chemical processes in the inner wind region of two archetypical oxygen-rich (C/O < 1) AGB stars, that is, the low mass-loss rate AGB star R Dor (M’ ∼ 1 × 10(exp −7) M/yr) and the high mass-loss rate AGB star IK Tau (M’ ∼ 5 × 10(exp −6) M/yr). The purpose of this study is to observe the key molecular species contributing to the formation of dust grains and to cross-link the observed line brightnesses of several species to the global and local properties of the star and its wind. Methods. A spectral line and imaging survey of IK Tau and R Dor was made with ALMA between 335 and 362 GHz (band 7) at a spatial resolution of ∼150 mas, which corresponds to the locus of the main dust formation region of both targets. Results. Some two hundred spectral features from 15 molecules (and their isotopologues) were observed, including rotational lines in both the ground and vibrationally excited states (up to v = 5 for SiO). Detected species include the gaseous precursors of dust grains such as SiO, AlO, AlOH, TiO, and TiO2. We present a spectral atlas for both stars and the parameters of all detected spectral features. A clear dichotomy for the sulphur chemistry is seen: while CS, SiS, SO, and SO2 are abundantly present in IK Tau, only SO and SO2 are detected in R Dor. Also other species such as NaCl, NS, AlO, and AlOH display a completely different behaviour. From some selected species, the minor isotopologues can be used to assess the isotopic ratios. The channel maps of many species prove that both large and small-scale inhomogeneities persist in the inner wind of both stars in the form of blobs, arcs, and/or a disk. The high sensitivity of ALMA allows us to spot the impact of these correlated density structures in the spectral line profiles. The spectral lines often display a half width at zero intensity much larger than expected from the terminal velocity, v∞, previously derived for both objects (36 km/s versus v(∞) ∼ 17.7 km/s for IK Tau and 23 km/s versus v(∞) ∼ 5.5 km/s for R Dor). Both a more complex 3D morphology and a more forceful wind acceleration of the (underlying) isotropic wind can explain this trend. The formation of fractal grains in the region beyond ∼400 mas can potentially account for the latter scenario. From the continuum map, we deduce a dust mass of ∼3.7 × 10(exp −7) Mand ∼2 × 10(exp −8) M for IK Tau and R Dor, respectively. Conclusions. The observations presented here provide important constraints on the properties of these two oxygen-dominated AGB stellar winds. In particular, the ALMA data prove that both the dynamical and chemical properties are vastly different for this high mass-loss rate (IK Tau) and low mass-loss rate (R Dor) star.

L. Decin↗
DOE OSTI2024

Two-electron interference in two-photon attosecond double ionization of neon

The pump-probe experiments enabled by x-ray free-electron lasers (XFEL) will allow us to directly observe correlated electronic motion with attosecond time resolution by detecting photoelectron pairs in coincidence. In helium, the transition between the nonsequential and sequential regime in two-photon double ionization (TPDI) is well explained by a virtual-sequential model. Much less is known, however, about the TPDI process in more complex atoms. Recently, we extended the virtual-sequential model to arbitrary light pulses [Chattopadhyay Phys. Rev. A 108, 013114 (2023)]. This extension employs multichannel scattering states for the single ionization of both the neutral and the ionized target, which we initially applied to helium. In the present study, we show that our extended virtual-sequential model reproduces the qualitative features of the angularly integrated observables with available experimental results for neon, a considerably more complex target. We observe an intriguing feature of inverted two-particle interference in the joint-energy distribution of Ne compared to He. Finally, this phenomenon, attributable to the presence of a final doubly ionized state with triplet symmetry coupled to the two photoelectrons, should be observable with current experimental technologies.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Majorana Edge Modes in Isolated Wires

Topological superconductors are believed to host exotic quasiparticle excitations known as Majorana zero modes (MZMs), with much of the evidence based on BCS mean-field theory. The direct application of mean-field arguments is tenuous in finite, isolated systems relevant in some experiments. Here, we develop a new correlation-based method for identifying MZMs in interacting, number-conserving systems. Using the density matrix renormalization group, we study fermion number-conserving models with long-range interactions, which under periodic boundary conditions exhibit robust topological and nontopological superconductivity, tuned by the strength of interaction [Ortiz et al., Phys. Rev. Lett. 113, 267002 (2014)]. We find evidence that, on the topological side, Majorana edge modes appear in open chains, manifesting as the vanishing of the energy splitting between odd- and even-parity ground states with increasing system size. Additionally, off-diagonal two-point correlation functions show nonlocal, parity-dependent edge effects. These correlations reveal the spatial structure of Majorana modes in the many-body wave function. We show that the correlation diagnostic applies broadly, including to short-range interacting models, where topological superconductivity is more fragile due to the absence of a bulk excitation gap.

Thomas-Markarian, Jaden↗
DOE OSTI2025

Lanczos algorithm for lattice QCD matrix elements

Recent work [M. L. Wagman, Lanczos, the transfer matrix, and the signal-to-noise problem, .] found that an analysis formalism based on the Lanczos algorithm allows energy levels to be extracted from Euclidean correlation functions with faster ground-state convergence than effective masses, convergent estimators for multiple states from a single correlator, and two-sided error bounds. After filtering out spurious eigenvalues and using outlier-robust estimators within a nested bootstrap framework, Lanczos estimators behave more like multistate fit results than effective masses—but without involving statistical fitting. We extend this formalism to the determination of matrix elements from three-point correlation functions and provide a physical picture of “spurious-state filtering” involving restriction to a Hermitian subspace. We demonstrate similar advantages for matrix elements as for spectroscopy through example applications to noiseless mock-data and (bare) forward matrix elements of the strange scalar current between both ground and excited states with the quantum numbers of the nucleon.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Comparison of excitation temperature of a laser-produced plasma by combining emission and absorption spectroscopy

Measurement of the temporal evolution of laser-produced plasma temperature is very important for many of its applications, and several plasma diagnostic tools are routinely used by researchers. However, it is very challenging to measure the properties of the plasma at the early and late times of its evolution using a single diagnostic tool. In this study, we combined emission and laser absorption spectroscopy to compare the excitation temperatures of a laser-produced uranium plasma system. Several U I transitions in the near-infrared spectral range (775–800 nm) were considered, and the Boltzmann plot method was used to measure the excitation temperatures using both emission and absorption spectroscopy. Emission spectroscopy provided early-time temperature measurements of the plasma up to times 2–20 µs, while absorption spectroscopy provided temperature measurements at late times of plasma evolution (for times 5–80 µs). The emission and absorbance of U I transitions were found to follow the Boltzmann distribution, indicating the plasma is likely in the state of local thermodynamic equilibrium even at late times of its lifetime. The emission and absorption-based time-resolved excitation temperatures demonstrated good agreement at earlier times (≤15 µs) in the overlapped temporal region, while a deviation in the measured values was seen at times (≥15 µs), and potential reasons for such a disagreement are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1996

Comparison of System Identification Techniques for the Hydraulic Manipulator Test Bed (HMTB)

In this thesis linear, dynamic, multivariable state-space models for three joints of the ground-based Hydraulic Manipulator Test Bed (HMTB) are identified. HMTB, housed at the NASA Langley Research Center, is a ground-based version of the Dexterous Orbital Servicing System (DOSS), a representative space station manipulator. The dynamic models of the HMTB manipulator will first be estimated by applying nonparametric identification methods to determine each joint's response characteristics using various input excitations. These excitations include sum of sinusoids, pseudorandom binary sequences (PRBS), bipolar ramping pulses, and chirp input signals. Next, two different parametric system identification techniques will be applied to identify the best dynamical description of the joints. The manipulator is localized about a representative space station orbital replacement unit (ORU) task allowing the use of linear system identification methods. Comparisons, observations, and results of both parametric system identification techniques are discussed. The thesis concludes by proposing a model reference control system to aid in astronaut ground tests. This approach would allow the identified models to mimic on-orbit dynamic characteristics of the actual flight manipulator thus providing astronauts with realistic on-orbit responses to perform space station tasks in a ground-based environment.

Morris, A. Terry↗
NASA NTRS1992

Multi-disciplinary optimization of aeroservoelastic systems

The purpose of the research project was to continue the development of new methods for efficient aeroservoelastic analysis and optimization. The main targets were as follows: to complete the development of analytical tools for the investigation of flutter with large stiffness changes; to continue the work on efficient continuous gust response and sensitivity derivatives; and to advance the techniques of calculating dynamic loads with control and unsteady aerodynamic effects. An efficient and highly accurate mathematical model for time-domain analysis of flutter during which large structural changes occur was developed in cooperation with Carol D. Wieseman of NASA LaRC. The model was based on the second-year work 'Modal Coordinates for Aeroelastic Analysis with Large Local Structural Variations'. The work on continuous gust response was completed. An abstract of the paper 'Continuous Gust Response and Sensitivity Derivatives Using State-Space Models' was submitted for presentation in the 33rd Israel Annual Conference on Aviation and Astronautics, Feb. 1993. The abstract is given in Appendix A. The work extends the optimization model to deal with continuous gust objectives in a way that facilitates their inclusion in the efficient multi-disciplinary optimization scheme. Currently under development is a work designed to extend the analysis and optimization capabilities to loads and stress considerations. The work is on aircraft dynamic loads in response to impulsive and non-impulsive excitation. The work extends the formulations of the mode-displacement and summation-of-forces methods to include modes with significant local distortions, and load modes. An abstract of the paper,'Structural Dynamic Loads in Response to Impulsive Excitation' is given in appendix B. Another work performed this year under the Grant was 'Size-Reduction Techniques for the Determination of Efficient Aeroservoelastic Models' given in Appendix C.

Karpel, Mardechay↗
DOE OSTI2025

Electron density measurements and calculations in a helium capacitively-coupled radio-frequency plasma

We report a comparison of inferred electron density (n e ) in a He capacitively-coupled plasma, deduced from laser-collision induced fluorescence measurements, with values computed using a hybrid simulation framework based on particle-in-cell/Monte Carlo collisions simulations and a fluid model for excited He atoms. The studies were carried out for gas pressures between 50 mTorr and 1000 mTorr and peak-to-peak radio-frequency (13.56 MHz) voltages between 150 V and 350 V, in a highly symmetric source equipped with plane-parallel electrodes. A good agreement is found between the experimental and modeling results for n e except at the lowest operating voltages and gas pressures. The (effective) electron temperature (T e ) values derived by the two methods agree as well reasonably within the plasma bulk. The simulation results are used to compare the density distributions of He + and various He excited levels and their major populating and de-populating channels at 100 mTorr and 1000 mTorr.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Linearized frequency domain Landau-Lifshitz-Gilbert equation formulation

We present a general finite element linearized Landau-Lifshitz-Gilbert equation (LLGE) solver for magnetic systems under weak time-harmonic excitation field. The linearized LLGE is obtained by assuming a small deviation around the equilibrium state of the magnetic system. Inserting such expansion into LLGE and keeping only first order terms gives the linearized LLGE, which gives a frequency domain solution for the complex magnetization amplitudes under an external time-harmonic applied field of a given frequency. We solve the linear system with an iterative solver using generalized minimal residual method. We construct a preconditioner matrix to effectively solve the linear system. The validity, effectiveness, speed, and scalability of the linear solver are demonstrated via numerical examples.

36 MATERIALS SCIENCE↗
NASA NTRS1986

Differential excitation cross section of atomic oxygen by electron impact - (3P-1D transition)

Results of an electron impact experiment in which a crossed-beam method was used to determine the differential excitation cross sections of atomic oxygen (3P-1D transition) are reported. The measurements cover energies of 7, 10, 15, 20, and 30 eV, with the angular range varying from 30 to 150 deg in 15-deg increments. The results are consistent, both in shape and in magnitude, with theoretical predictions, providing a direct confirmation of the theoretical total excitation cross sections of O(1D) state. Details of the experimental equipment and procedure are given.

Shyn, T. W.↗
NASA NTRS1995

The FOSTER Project: Teacher Enrichment Through Participation in NASA's Airborne Astronomy Program

NASA's airborne astronomy program offers a unique opportunity for K-12 science teacher enrichment and for NASA to reach out and serve the educational community. Learning from a combination of summer workshops, curriculum supplement materials, training in Internet skills and ultimately flying on NASA's C-141 airborne observatory, the teachers are able to share the excitement of scientific discovery with their students and convey that excitement from first hand experience rather than just from reading about science in a textbook. This year the program has expanded to include teachers from the eleven western states served by NASA Ames Research Center's Educational Programs Office as well as teachers from communities from around the country where the scientist who fly on the observatory reside. Through teacher workshops and inservice presentations, the FOSTER (Flight Opportunities for Science Teacher EnRichment) teachers are sharing the resources and experiences with many hundreds of other teachers. Ultimately, the students are learning first hand about the excitement of science, the scientific method in practice, the team work involved, the relevance of science to their daily lives and the importance of a firm foundation in math and science in today's technologically oriented world.

Koch, David↗
DOE OSTI2021

Synthetic and Mechanistic Implications of Chlorine Photoelimination in Nickel/Photoredox C(sp 3 )–H Cross-Coupling

In recent years, the development of light-driven reactions has contributed numerous advances in synthetic organic chemistry. A particularly active research area combines photoredox catalysis with nickel catalysis to accomplish otherwise inaccessible cross-coupling reactions. In these reactions, the photoredox catalyst absorbs light to generate an electronically excited charge-transfer state that can engage in electron or energy transfer with a substrate and the nickel catalyst. Our group questioned whether photoinduced activation of the nickel catalyst itself could also contribute new approaches to cross-coupling. Over the past 5 years, we have sought to advance this hypothesis for the development of a suite of mild and site-selective C(sp 3 )–H cross-coupling reactions with chloride-containing coupling partners via photoelimination of a Ni–Cl bond. On the basis of a report from the Nocera laboratory, we reasoned that photolysis of a Ni(III) aryl chloride species, generated by single-electron oxidation of a typical Ni(II) intermediate in cross-coupling, might allow for the catalytic generation of chlorine atoms. Combining this with the ability of Ni(II) to accept alkyl radicals, we hypothesized that photocatalytically generated chlorine atoms could mediate hydrogen atom transfer (HAT) with C(sp 3 )–H bonds to generate a substrate-derived alkyl radical that is captured by the Ni center in cross-coupling. A photoredox catalyst was envisioned to promote the necessary single-electron oxidation and reduction of the Ni catalyst to facilitate an overall redox-neutral process. Overall, this strategy would offer a visible-light-driven mechanism for chlorine radical formation enabled by the sequential capture of two photons. As an initial demonstration, we developed a Ni/photoredox-catalyzed α-oxy C(sp 3 )–H arylation of cyclic and acyclic ethers. This method was extended to a mild formylation of abundant and complex aryl chlorides through selective 2-functionalization of 1,3-dioxolane. Seeking to develop a suite of reactions that introduce carbon at all different oxidation states, we explored C(sp 3 )–H cross-coupling with trimethyl orthoformate, a common laboratory solvent. We found that trimethyl orthoformate serves as a source of methyl radical for a methylation reaction via β-scission from a tertiary radical generated upon chlorine-mediated HAT. Since chlorine radical is capable of abstracting unactivated C(sp 3 )–H bonds, our efforts have also been directed at cross-coupling with a range of feedstock chemicals, such as alkanes and toluenes, along with late-stage intermediates, using chloroformates as coupling partners. Overall, this platform enables access to valuable synthetic transformations with (hetero)aryl chlorides, which despite being the most ubiquitous and inexpensive aryl halide coupling partners, are rarely reactive in Ni/photoredox catalysis. Little is known about the photophysics and photochemistry of organometallic Ni complexes relevant to cross-coupling. We have conducted mechanistic investigations, including computational, spectroscopic, emission quenching, and stoichiometric oxidation studies, of Ni(II) aryl halide complexes common to Ni/photoredox reactions. These studies indicate that chlorine radical generation from excited Ni(III) is operative in the described C(sp 3 )–H functionalization methods. More generally, the studies illustrate that the photochemistry of cross-coupling catalysts cannot be ignored in metallaphotoredox reactions. We anticipate that further mechanistic understanding should facilitate catalyst design and lead to the development of new synthetic methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗