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Results for “conditional neutrality”

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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Band Energy Dependence of Defect Formation in the Topological Semimetal Cd3As2

Cadmium Arsenide (Cd3As2) is a prototypical Dirac semimetal that manifests topological properties in a 3D bulk material. In defect-free Cd3As2, the Fermi level lies at a minimum in the density of states at the Dirac point, but experimentally it forms with excess electron carriers and an elevated EF, thereby masking the topological features. To computationally study the self-doping of Cd3As2, we combine density functional theory (DFT) calculations for defect formation energies with quasi-particle self-consistent GW (QSGW) electronic structure calculations. We demonstrate an innate dependence of the point defect formation energies on carrier concentrations and use the QSGW calculated density of states to extrapolate formation energies to arbitrary electron concentrations. This approach allows the quantitative modeling of thermodynamic defect equilibria in topological semimetals and is used to predict how Cd3As2 growth conditions affect the position of EF relative to the Dirac point.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗
DOE OSTI2021

Role of Low Molecular Weight Polymers on the Dynamics of Silicon Anodes During Casting

This work probes the slurry architecture of a high silicon content electrode slurry with and without low molecular weight polymeric dispersants as a function of shear rate to mimic electrode casting conditions for poly(acrylic acid) (PAA) and lithium neutralized poly(acrylic acid) (LiPAA) based electrodes. Rheology coupled ultra-small angle neutron scattering (rheo-USANS) was used to examine the aggregation and agglomeration behavior of each slurry as well as the overall shape of the aggregates. The addition of dispersant has opposing effects on slurries made with PAA or LiPAA binder. With a dispersant, there are fewer aggregates and agglomerates in the PAA based silicon slurries, while LiPAA based silicon slurries become orders of magnitude more aggregated and agglomerated at all shear rates. The reorganization of the PAA and LiPAA binder in the presence of dispersant leads to a more homogeneous slurry and a more heterogeneous slurry, respectively. This reorganization ripples through to the cast electrode architecture and is reflected in the electrochemical cycling of these electrodes.

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

Attribution of NAO Predictive Skill Beyond 2 Weeks in Boreal Winter

Weeks 3–6 averaged winter North Atlantic Oscillation (NAO) predictive skill in a state-of-the-art coupled climate prediction system is attributed to two principle sources: upper and lower boundary conditions linked to the stratosphere and El Niño-Southern Oscillation (ENSO), respectively. A 20-member ensemble of 45-day reforecasts over 1999–2015 is utilized, together with uninitialized simulations with the atmospheric component of the prediction system forced with observed radiative forcing and lower boundary conditions. NAO forecast skill for lead times out to 6 weeks is higher following extreme stratospheric polar vortex conditions (weak and strong vortex events) compared to neutral states. Enhanced weeks 3-6 NAO predictive skill for weak vortex events results primarily from stratospheric downward coupling to the troposphere, while enhanced skill for strong vortex events can be partly attributed to lower boundary forcing related to the ENSO phenomenon. Implications for forecast system development and improvement are discussed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Simulations of nozzle gas flow and gas-puff Z-pinch implosions on the Weizmann Z-pinch

We present simulations of an oxygen gas puff Z-pinch on a University scale generator at the Weizmann Institute of Science. The work accounts for the detailed geometry of the nozzle, the initial neutral gas density distribution, and the subsequent implosion. The modeling results show significant improvement with data for the current at the time of stagnation in comparison with a previous effort [Rosenzweig et al., Phys. Plasmas 27, 022705 (2020)]. As a first step, we performed simulations of the flow of neutral diatomic oxygen from a plenum through a nozzle within a recessed cathode, across a gap, and into the anode with a recessed grounded honeycomb. These simulations show an agreement with the measured initial gas density profiles within the region not blocked by the recesses and accessible to visible measurements. The computed neutral gas flow profile serves as the initial condition for a radiation magnetohydrodynamic simulation of the implosion using the MACH2-TCRE code. By considering the specific details of the nozzle and chamber geometry, we find agreement with the measured current profile, including the inductive notch. The simulations predict that the plasma undergoes a strong pinch within the hidden anode recess. The simulations also predict the strongest radiation pulse occurs within the anode recess and at the time of the observed inductive notch.

Physics↗
DOE OSTI2024

Charged Biological Membranes Repel Large Neutral Molecules by Surface Dielectrophoresis and Counterion Pressure

Macromolecular crowding is the usual condition of cells. The implications of the crowded cellular environment for protein stability and folding, protein–protein interactions, and intracellular transport drive a growing interest in quantifying the effects of crowding. While the properties of crowded solutions have been extensively studied, less attention has been paid to the interaction of crowders with the cellular boundaries, i.e., membranes. However, membranes are key components of cells and most subcellular organelles, playing a central role in regulating protein channel and receptor functions by recruiting and binding charged and neutral solutes. While membrane interactions with charged solutes are dominated by electrostatic forces, here we show that significant charge-induced forces also exist between membranes and neutral solutes. Using neutron reflectometry measurements and molecular dynamics simulations of poly(ethylene glycol) (PEG) polymers of different molecular weights near charged and neutral membranes, we demonstrate the roles of surface dielectrophoresis and counterion pressure in repelling PEG from charged membrane surfaces. The resulting depletion zone is expected to have consequences for drug design and delivery, the activity of proteins near membrane surfaces, and the transport of small molecules along the membrane surface.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Deep modeling of plasma and neutral fluctuations from gas puff turbulence imaging

The role of turbulence in setting boundary plasma conditions is presently a key uncertainty in projecting to fusion energy reactors. To robustly diagnose edge turbulence, we develop and demonstrate a technique to translate brightness measurements of HeI line radiation into local plasma fluctuations via a novel integrated deep learning framework that combines neutral transport physics and collisional radiative theory for the 3 3 D - 2 3 P transition in atomic helium with unbounded correlation constraints between the electron density and temperature. The tenets for experimental validity are reviewed, illustrating that this turbulence analysis for ionized gases is transferable to both magnetized and unmagnetized environments with arbitrary geometries. Based on fast camera data on the Alcator C-Mod tokamak, we present the first two-dimensional time-dependent experimental measurements of the turbulent electron density, electron temperature, and neutral density, revealing shadowing effects in a fusion plasma using a single spectral line.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Deep modelling of plasma and neutral fluctuations from gas puff turbulence imaging

The role of turbulence in setting boundary plasma conditions is presently a key uncertainty in projecting to fusion energy reactors. To robustly diagnose edge turbulence, we develop and demonstrate a technique to translate brightness measurements of HeI line radiation into local plasma fluctuations via a novel integrated deep learning framework that combines neutral transport physics and collisional radiative theory for the $3^3 D - 2^3 P$ transition in atomic helium. The tenets for experimental validity are reviewed, illustrating that this turbulence analysis for ionized gases is transferable to both magnetized and unmagnetized environments with arbitrary geometries. Based upon fast camera data on the Alcator C-Mod tokamak, we present the first 2-dimensional time-dependent experimental measurements of the turbulent electron density, electron temperature, and neutral density revealing shadowing effects in a fusion plasma using a single spectral line.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Extending the low-recycling, flat temperature profile regime in the lithium tokamak experiment-β (LTX-β) with ohmic and neutral beam heating

Abstract Recent experiments in the lithium tokamak experiment- β (LTX- β ) have extended the duration, performance, operating conditions, and diagnosis of the flat-temperature profile, low-recycling regime first observed in LTX. As expected, Li retains hydrogen and suppresses edge neutral cooling, allowing increased edge electron temperature, roughly equal to the core T e . Flat temperature profiles had been obtained transiently in LTX, as the plasma density decayed following the cessation of edge gas puffing. Careful control over the fueling in LTX- β has now been shown to sustain the flat T e profile and hot edge unique to the low-recycling regime for multiple confinement times in high performance discharges with decaying or steady density. With low density, the flat T e profile is also seen to extend into the scrape-off layer. Neutral beam heating is observed in target discharges with relatively flat electron temperature profiles ( T edge ∼ T core /2), though beam heating is stronger in discharges with higher fueling, higher density, and depressed edge T e . Beam heating produces additional peaking of the T e profile, without degradation of the energy confinement time. Neutral beam heating of target discharges with relatively flat electron temperature profiles similarly results in broad beam heated temperature profiles. Energy confinement in LTX- β generally compares favorably to ohmic and H-mode scalings, frequently exceeding them by factors of 2–4. New and improved diagnostics in LTX- β enable better characterization of this unique regime, including measurements of ion temperature and high field side Thomson scattering profiles. As an initial step toward characterizing turbulence with no T e gradient and roughly equal density and pressure gradient, core fluctuation spectra have been measured in peaked T e discharges using far-forward scattering and fluctuation reflectometry.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Floating platform effects on power generation in spar and semisubmersible wind turbines

The design and financing of commercial-scale floating offshore wind projects require a better understanding of how power generation differs between newer floating turbines and well-established fixed-bottom turbines. In floating turbines, platform mobility causes additional rotor motion that can change the time-averaged power generation. In this work, OpenFAST simulations examine the power generated by the National Renewable Energy Laboratory's 5-MW reference turbine mounted on the OC3-UMaine spar and OC4-DeepCWind semisubmersible floating platforms, subjected to extreme irregular waves and below-rated turbulent inflow wind from large-eddy simulations of a neutral atmospheric boundary layer. For these below-rated conditions, average power generation in floating turbines is most affected by two types of turbine displacements: an average rotor pitch angle that reduces power, caused by platform pitch; and rotor motion upwind-downwind that increases power, caused by platform surge and pitch. The relative balance between these two effects determines whether a floating platform causes power gains or losses compared to a fixed-bottom turbine; for example, the spar creates modest (3.1%–4.5%) power gains, whereas the semisubmersible creates insignificant (0.1%–0.2%) power gains for the simulated conditions. Furthermore, platform surge and pitch motions must be analyzed concurrently to fully capture power generation in floating turbines, which is not yet universal practice. Finally, a simple analytical model for predicting average power in floating turbines under below-rated wind speeds is proposed, incorporating effects from both the time-averaged pitch displacement and the dynamic upwind-downwind displacements.

17 WIND ENERGY↗
DOE OSTI2020

Selective CO 2 electrocatalysis at the pseudocapacitive nanoparticle/ordered-ligand interlayer

Enzymes feature the concerted operation of multiple components around an active site, leading to exquisite catalytic specificity. Realizing such configurations on synthetic catalyst surfaces remains elusive. In this article, we report a nanoparticle/ordered-ligand interlayer that contains a multi-component catalytic pocket for high-specificity CO 2 electrocatalysis. The nanoparticle/ordered-ligand interlayer comprises a metal nanoparticle surface and a detached layer of ligands in its vicinity. This interlayer possesses unique pseudocapacitive characteristics where desolvated cations are intercalated, creating an active-site configuration that enhances catalytic turnover by two orders and one order of magnitude against a pristine metal surface and nanoparticle with tethered ligands, respectively. The nanoparticle/ordered-ligand interlayer is demonstrated across several metals with up to 99% CO selectivity at marginal overpotentials and onset overpotentials of as low as 27 mV, in aqueous conditions. Furthermore, in a gas-diffusion environment with neutral media, the nanoparticle/ordered-ligand interlayer achieves nearly unit CO selectivity at high current densities (98.1% at 400 mA cm -2 ).

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

Etching of Si 3 N 4 induced by electron beam plasma from hollow cathode plasma in a downstream reactive environment

An etching system based on the interaction of electrons extracted from a direct current (DC) hollow-cathode (HC) Ar plasma and injected towards a Si3N4 covered silicon substrate located in the downstream reactive environment created by an additional remote CF 4 /O 2 plasma source was developed and evaluated. By controlling the properties of the injected beam electrons, this approach allows to deliver energy to a surface functionalized by exposure to reactive species, and initiate surface etching. The energy of the primary beam electrons is controlled by the acceleration voltage relative to the HC discharge. Ar atoms flow from the high-pressure HC discharge into the low pressure downstream reactive environment in the process chamber. For an acceleration voltage greater than the ionization potential of Ar and/or process gas species, the energetic primary beam electrons produce a secondary plasma in the process chamber, and can also cause additional dissociation. We have characterized the properties of the secondary plasma and also surface etching of Si 3 N 4 as a function of process parameters, including acceleration voltage (0-80 V), discharge current of the HC discharge (1-2 A), pressure (3.5-20 mTorr), source to substrate distance (1.5 to 5 cm), and feed gas composition (20% and 80% O2 in CF 4 /O 2 ). The electron energy probability function (EEPF) measured with a Langmuir probe about 2.5 cm below the extraction ring suggests several major groups of electrons for this situation, including high energy primary beam electrons with an energy that varies as the acceleration voltage is changed and low energy electrons produced by beam electron-induced ionization of the Ar gas in the process chamber. When a remote CF 4 /O 2 plasma is additionally coupled to the process chamber, Si 3 N 4 surfaces can be functionalized, and by varying the energy of the beam electrons, Si 3 N 4 etching can be induced by electron-neutral synergy effect with plasma-surface interaction. For conditions without beam electron injection, the remote plasma etching rate (ER) of Si 3 N 4 depends strongly on the O 2 concentration in the CF 4 /O 2 processing gas mixture and can be suppressed for O 2 -rich process conditions by the formation of a SiONF passivation layer on the Si 3 N 4 surface. The combination of the HC electron beam source with the remote plasma source (HCEB-RP) makes it possible to induce Si 3 N 4 etching for O 2 -rich remote plasma conditions where remote plasma by itself produces negligible Si 3 N 4 etching. The electron enhanced etching of Si 3 N 4 depends strongly on O 2 /CF 4 mixing ratio reflecting changing arrival rates of O and F species at the surface. Optical emission spectroscopy was used to estimate the ratio of gas phase F and O densities and found to be controlled by the gas mixing ratio and independent of HC EB operating conditions. At this time the detailed sequence of events operative in the etching mechanism is unclear. While the increase of the electron energy is ultimately responsible for initiating surface etching, at present we cannot rule out a role of ions from the simultaneously produced secondary plasma in plasma surface interaction mechanisms.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Infrared bands of neutral gas-phase carbon clusters in a broad spectral range

The identification of species in the interstellar medium requires precise and molecule-specific spectroscopic information in the laboratory framework, in broad spectral ranges and under conditions relevant to interstellar environments. In this work, we measure the gas-phase infrared spectra of neutral carbon clusters, C N (N = 6–11), in a molecular beam. The C N distribution is formed by photofragmentation of C 60 molecules, concurrently showing a top-down formation mechanism. A broad spectral range in the infrared between 500–3200 cm -1 (20–3.125 μm) is investigated. We observe strong bands between 5 and 6 μm, in conjunction with novel features in the 3 μm region. Density functional theory calculations reveal that these short wavelength modes correspond to combination bands with significant infrared intensity. Moreover, we identify the N ≤ 10 clusters as linear, while C 11 adopts a ring configuration, placing the linear-to-ring transition at N = 11 under our molecular beam conditions. The linearity of C 10 is discussed based on the formation pathway from larger clusters in energetic conditions. Given the vast and very precise infrared information already been released from the James Webb Space Telescope mission, this infrared spectroscopic data set in conjunction with information on formation mechanisms is of major relevance for identifying neutral carbon clusters in astronomical environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Simulation of plasma and neutral transport in PISCES-RF using SOLPS-ITER

In this research, the fluid plasma transport code SOLPS-ITER is applied and validated against experimental data from the plasma interaction surface component experimental station (PISCES)-RF linear plasma device to establish a physics basis for plasma and neutral transport in its two magnetic field (B-field) geometry setups-(1)the cusp and (2) non-cusp or linear B-field. The main focus of this study is to understand (1) radial plasma transport (2) heat and particle loads on the upstream dump and downstream target plate, and (3) the physics of plasma-neutral interactions in PISCES-RF. The simulation setup adheres to typical PISCES-RF experimental conditions, with a 2D helicon power deposition profile as an input heating source. SOLPS-ITER simulations reproduce experimental conditions with the Bohm diffusion model for both B-field configurations of the PISCES-RF experiment. Major energy loss channels include neutral radiation and power deposited on the wall and dump plate, with only 1% of the input power reaching the target. The ionization front is well confined near the dump plate due to the heating and puffing regions. Additionally, SOLPS-ITER simulation results are also found to be in very good agreement with the particle-in-cell calculations using the code-PICOS++ which supports the validity of SOLPS in low collisionality regime.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

A reduced model for the ITER divertor based on SOLPS solutions for ITER Q = 10 baseline conditions: A. identifying options for the control parameters*

Edge codes such as SOLPS coupled to neutral codes such as EIRENE have become so comprehensive and sophisticated that they now constitute, in effect, 'code-experiments' that, as for actual experiments, can benefit from interpretation using simple models and conceptual frameworks, i.e. reduced models. The first task is the identification of options for the reduced model control parameters that are best suited for control of the action of the divertor, i.e. for control of target power loading and sputter-erosion, primarily. A strong correlation between the electron temperature at the divertor target, T e,t , and the neutral deuterium D 2 density at the target, n D2,t , flux-tube resolved, has recently been reported for a number of code studies including SOLPS-4.3 modeling of a set of ~50 ITER baseline cases: Q DT = 10, q 95 = 3, P SOL = 100 MW, metallic walls, and Ne seeding. This part A of the present study reports new results for largely the same ITER cases, confirming the strong correlations reported earlier between local values of T e,t , and (i) n D2,t , and (ii) normalized volumetric losses of power and pressure in the divertor. Strong correlations have now also been found, and are reported here for the first time, between T e,t and all of the divertor target quantities of practical interest. A physical explanation for this surprising result has not been fully identified; nevertheless it has encouraging implications for reduced modeling of the ITER divertor. For such ITER conditions, (i) the global Ne injection rate, Inj Ne [Ne/s], and (ii) the electron temperature at the location on the target where the peak power deposition occurs, T e,t @q ⊥,pk (eV), are found to be promising reduced model control parameters. In the companion report, part B, a reduced model for the ITER divertor is developed and described in detail, based on reversed-direction 2 point modelling, Rev2PM. The input to the reduced model is a value of the variable pair (T et @q ⟂,pk ,Inj Ne ) and the output are values of the various target as well as divertor-entrance quantities of practical interest, e.g. q ⊥,pk , n e,Xpt (the electron density at the poloidal location of the X-point), etc. In part B the reduced model is quantitatively characterized using one half of the code cases; it is then used to successfully predict (replicate) the code values of e.g. n e,Xpt for the other half of the cases.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

Systematic investigations on iron cycling in phosphorus/siderophore systems: Synergism or antagonism?

Synergisms between microbial exudates on Fe (hydr)oxide dissolution as an effective Fe acquisition pathway have been recently addressed and vigorously debated. However, Fe liberation mechanisms and where siderophores and phosphorus (P) coexist received little attentions. Current study systematically investigated ferrihydrite dissolution in the presence of desferrioxamine B (DFOB) (a kind of fungally-derived siderophores) and inorganic/organic phosphorus (orthophosphate, Pi; myo-inositol hexaphosphate, IHP), as a function of solute pH, reaction time and reagent content. Reacted solids were characterized by N 2 -BET adsorption, zeta (ζ) potential analysis, sequential extraction analysis (SEDEX), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). Our results indicate that upon reaction with P-only or (DFOB + P) systems, interfacial complexation partially switched from monolayer bidentate-binuclear surface complexes to ternary complexes, or laterally transformed into amorphous Fe–P precipitates. The Fe-Pi complex precipitated more readily under acidic conditions, and Fe-IHP complex preferentially nucleated in neutral-alkaline environments. Phosphorus slightly promoted Fe release from minerals and fixation to the leached layer or interfacial liquid zone initially, but subsequently prevented further attacks from protons and DFOB. The co-effects of P and DFOB likely correspond to two successive scenarios: 1) DFOB is preferentially attracted toward ferrihydrite surfaces by negative electrical fields induced by adsorbed phosphorus and can act synergistically with labile P–Fe complexes, resulting in intensive temporal dissolution of Fh; 2) subsequent Fe shuttling to DFOB can be prohibited by stabilized, passive P/Fe–P layers. Finally, our results emphasize the antagonism between P compounds and siderophores (i.e., DFOB here) on ferrihydrite dissolution to improve understanding of the biologically-mediated Fe cycling in natural systems.

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

Three-Dimensional Pore Networks in Miocene Stevens Sandstone of California: Implications for CO 2 Geologic Storage

The Miocene Stevens Sandstone in the San Joaquin Basin of California is increasingly recognized as a promising candidate for CO 2 geological storage due to the enormous storage capacity, proven sealing, and existing infrastructure. In this study, computed microtomography imaging and pore network modeling were employed to investigate the influence of pore geometry and wettability on the CO 2 injectivity and residual trapping. Image analysis revealed that a significant fraction of the cement and matrix consists of microporous regions. The microporosity can substantially increase the overall pore space, yet its contribution to permeability remains modest, particularly in samples with low permeability. The intrinsic heterogeneity of turbidite reservoirs further complicates the reservoir properties among different layers. Two-phase flow simulations under varying wettability conditions (water-wet, weak water-wet, and neutral-wet) demonstrated that the CO 2 injection is predominantly controlled by macropores. CO 2 invades microporous regions only after these larger pores are filled. The presence of microporosity leads to a decrease in both initial and residual CO 2 saturations, with the magnitude of the reduction being influenced by wettability. Neutral-wet scenarios exhibit higher CO 2 mobility and thus lower residual trapping than water-wet scenarios. The results imply that heterogeneity in pore geometry and cement distribution across different layers can result in stratified CO 2 flow pathways, complicating efforts to predict injection performance. Overall, the Stevens Sandstone shows considerable promise for CO 2 geologic storage, but effective implementation will require detailed characterization of the pore structure as well as the integration of reactive fluid flow to account for potential mineral dissolution and fines migration.

fluids↗
DOE OSTI2020

Arsenic Fate in Peat Controlled by the pH-Dependent Role of Reduced Sulfur

Reduced sulfur (S) has a contrasting role in the fate of arsenic (As) in peatlands. Sulfur bridges provide efficient binding of As to organic carbon (C), but the formation of aqueous As–S species, so-called thioarsenates, leads to a low to no sorption tendency to organic C functional groups. Here, we studied how pH changes the role of reduced S in desorption and retention of presorbed As in model peat. Control desorption experiments without S addition revealed that As was mobilized, predominantly as arsenite, in all treatments with relative mobilization increasing with pH (4.5 < 7.0 < 8.5). Addition of sulfide or polysulfide caused substantial As retention at acidic conditions but significantly enhanced As desorption compared to controls at neutral to alkaline pH. Thioarsenates dominated As speciation at pH 7.0 and 8.5 (maximum, 79%) and remained in solution without (re)sorption to peat. Predominance of arsenite in control experiments and no evidence of surface-bound thioarsenates at pH 7.0 suggest mobilization to proceed via arsenite desorption, reaction with dissolved or surface-bound reduced S, and formation of thioarsenates. Our results suggest that natural or management-related increases in pH or increases in reduced S in near-neutral pH environments can turn organic matter from an As sink into a source.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Radicals as Exceptional Electron-Withdrawing Groups: Nucleophilic Aromatic Substitution of Halophenols Via Homolysis-Enabled Electronic Activation

While heteroatom-centered radicals are understood to be highly electrophilic, their ability to serve as transient electron-withdrawing groups and facilitate polar reactions at distal sites has not been extensively developed. Here, we report a new strategy for the electronic activation of halophenols, wherein generation of a phenoxyl radical via formal homolysis of the aryl O-H bond enables direct nucleophilic aromatic substitution of the halide with carboxylate nucleophiles under mild conditions. Pulse radiolysis and transient absorption studies reveal that the neutral oxygen radical (O • ) is indeed an extraor-dinarily strong electron-withdrawing group [σ p - (O • ) = 2.79 vs. σ p - (NO 2 ) = 1.27]. Additional mechanistic and computational studies indicate that the key phenoxyl intermediate serves as an open-shell electron-withdrawing group in these reactions, lowering the barrier for nucleophilic substitution by more than 20 kcal/mol relative to the closed-shell phenol form of the substrate. Finally, by using radicals as transient activating groups, this homolysis-enabled electronic activation strategy provides a powerful platform to expand the scope of nucleophile-electrophile couplings and enable previously challenging transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗