Engineering PapersSearch

SEARCH · Engineering Papers

Results for “PARAMAGNETISM”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7

Magnetic and metallurgical properties of directionally solidified eutectic Bi/MnBi composites - The effects of annealing

Eutectic Bi/MnBi (97.8 a/o Bi) samples have been plane-front directionally solidified. The resultant microstructures consist of elongated, aligned particles of MnBi dispersed in a Bi-matrix. Magnetization as a function of temperature (4.2 to 300 K) and applied field (up to 220 kG) has been used to evaluate solidification parameters and magnetic properties. At room temperature, in addition to the diamagnetic contribution of Bi, one finds a superposition of the ferromagnetic, low temperature (LTP) MnBi phase and paramagnetic phases. At cryogenic temperatures, one of the room temperature paramagnetic phases is ferromagnetic with an intrinsic coercivity of 120 kOe while the other remains paramagnetic for low fields and orders ferromagnetically at high fields in a complicated way. Annealing of as-grown samples was found to produce significant changes in magnetic properties. The origins of the paramagnetic phases and their relation to the mechanisms which control the coercive field of the hard magnetic LTP MnBi phase are discussed.

Pirich, R. G.

A two-stage magnetic refrigerator for astronomical applications with reservoir temperatures above 4 K

We propose a novel adiabatic demagnetization refrigerator (ADR) to produce temperatures as low as 100 mK starting from a high temperature reservoir between 4 and 8 K. The high temperature reservoir for the ADR can be provided by a mechanical cooler or an unpumped liquid helium bath. This refrigerator can be used to cool bolometric infrared detectors for low background astronomy from mountain tops, balloons or satellites as well as to cool cryogenic x-ray detectors. The two-stage ADR consists of a single magnet with a paramagnetic chromic-cesium-alum (CCA) salt pill to produce the low temperature and paramagnetic gadolinium-gallium-garnet (GGG) as the first stage to intercept heat from the high temperature reservoir. Thermal contact between the paramagnets and the reservoir during magnetization is made with a mechanical heat switch. The ADR is suspended with Kevlar chords under tension for high mechanical stiffness and low parasitic heat leak. In a single cycle, the ADR maintains a temperature of 100 mK for 10 to 100 hours. This time depends strongly on the magnetic field and reservoir temperature but not on the volume of the paramagnetic material as long as the heat leak is dominated by the suspension.

Hagmann, C.

Symmetry-mediated quantum coherence of W 5+ spins in an oxygen-deficient double perovskite

Elucidating the factors limiting quantum coherence in real materials is essential to the development of quantum technologies. Here we report a strategic approach to determine the effect of lattice dynamics on spin coherence lifetimes using oxygen deficient double perovskites as host materials. In addition to obtaining millisecond T 1 spin-lattice lifetimes at T ~ 10 K, measurable quantum superpositions were observed up to room temperature. We determine that T 2 enhancement in Sr 2 CaWO 6-δ over previously studied Ba 2 CaWO 6-δ is caused by a dynamically-driven increase in effective site symmetry around the dominant paramagnetic site, assigned as W 5+ via electron paramagnetic resonance spectroscopy. Further, a combination of experimental and computational techniques enabled quantification of the relative strength of spin-phonon coupling of each phonon mode. This analysis demonstrates the effect of thermodynamics and site symmetry on the spin lifetimes of W 5+ paramagnetic defects, an important step in the process of reducing decoherence to produce longer-lived qubits.

36 MATERIALS SCIENCE

Chain Dynamics in Magnetorheological Suspensions

Magnetorheological (MR) suspensions are composed of colloidal particles which acquire dipole moments when subjected to an external magnetic field. At sufficient field strengths and concentrations, the dipolar particles rapidly aggregate to form long chains. Subsequent lateral cross-linking of the dipolar chains is responsible for a rapid liquid-to-solid-like rheological transition. The unique, magnetically-activated rheological properties of MR suspensions make them ideal for interfacing mechanical systems to electronic controls. Additionally, the ability to experimentally probe colloidal suspensions interacting through tunable anisotropic potentials is of fundamental interest. Our current experimental work has focused on understanding the fluctuations of dipolar chains. It has been proposed by Halsey and Toor (HT) that the strong Landau-Peierls thermal fluctuations of dipolar chains could be responsible for long-range attractions between chains. Such interactions will govern the long-time relaxation of MR suspensions. We have synthesized monodisperse neutrally buoyant MR suspensions by density matching stabilized ferrofluid emulsion droplets with D2O. This allows us to probe the dynamics of the dipolar chains using light scattering without gravitational, interfacial, and polydispersity effects to resolve the short-wavelength dynamics of the dipolar chains. We used diffusing wave spectroscopy to measure these dynamics. The particle displacements at short times that show an independence to the field strength, but at long times exhibit a constrained, sub-diffusive motion that slows as the dipole strength is increased. The experiments are in good qualitative agreement with Brownian dynamics simulations of dipolar chains. Although there have been several important and detailed studies of the structure and interactions in MR suspensions, there has not been conclusive evidence that supports or contradicts the HT model prediction that long-range interactions exist between fluctuating chains of dipolar particles. Resolving this issue would contribute greatly to the understanding of these interesting and important materials. We have begun to test the predictions of the HT model by both examining the dynamics of individual chains and by measuring the forces between dipolar chains directly to accurately and quantitatively assess the interactions that they experience. To do so, we employ optical trapping techniques and video-microscopy to manipulate and observe our samples on the microscopic level. With these techniques, it is possible to observe chains that are fluctuating freely in three-dimensions, independent of interfacial effects. More importantly, we are able to controllably observe the interactions of two chains at various separations to measure the force-distance profile. The techniques also allow us to study the mechanical properties of individual chains and chain clusters. Our work to this point has focused on reversibly-formed dipolar chains due to field induced dipoles where the combination of this chaining, the dipolar forces, and the hydrodynamic interactions that dictate the rheology of the suspensions. One can envision, however, many situations where optical, electronic, or rheological behavior may be optimized with magneto-responsive anisotropic particles. Chains of polarizable particles may have the best properties as they can coil and flex in the absence of a field and stiffen and orient when a field is applied. We have recently demonstrated a synthesis of stable, permanent paramagnetic chains by both covalently and physically linking paramagnetic colloidal particles. The method employed allows us to create monodisperse chains of controlled length. We observed the stability, field-alignment, and rigidity of this new class of materials. The chains may exhibit unique rheological properties in an applied magnetic field over isotropic suspensions of paramagnetic particles. They are also useful rheological models as bead-spring systems. These chains form the basis for our current experiments with optical traps.

Gast, A. P.

An Analytical Model for Non-Uniform Magnetic Field Effects on Two-Dimensional Laminar Jet Diffusion Flames

In 1846, Michael Faraday found that permanent magnets could cause candle flames to deform into equatorial disks. He believed that the change in flame shape was caused by the presence of charged particles within the flames interacting with the magnetic fields. Later researchers found that the interaction between the flame ions and the magnetic fields were much too small to cause the flame deflection. Through a force analysis, von Engel and Cozens showed that the change in the flame shape could be attributed to the diamagnetic flame gases in the paramagnetic atmosphere. Paramagnetism occurs in materials composed of atoms with permanent magnetic dipole moments. In the presence of magnetic field gradients, the atoms align with the magnetic field and are drawn into the direction of increasing magnetic field. Diamagnetism occurs when atoms have no net magnetic dipole moment. In the presence of magnetic gradient fields, diamagnetic substances are repelled towards areas of decreasing magnetism. Oxygen is an example of a paramagnetic substance. Nitrogen, carbon monoxide and dioxide, and most hydrocarbon fuels are examples of diamagnetic substances. In order to evaluate the usefulness of these magnets in altering flame behavior, a study has been undertaken to develop an analytical model to describe the change in the flame length of a laminar diffusion jet in the presence of a nonuniform magnetic field.

Calvert, M. E.

Novel Applications of Magnetic Fields for Fluid Flow Control and for Simulating Variable Gravity Conditions

Static and dynamic magnetic fields have been used to control convection in many materials processing applications. In most of the applications, convection control (damping or enhancement) is achieved through the Lorentz force that can be tailored to counteract/assist dominant system flows. This technique has been successfully applied to liquids that are electrically conducting, such as high temperature melts of semiconductors, metals and alloys, etc. In liquids with low electrical conductivity such as ionic solutions of salts in water, the Lorentz force is weak and hence not very effective and alternate ways of flow control are necessary. If the salt in solution is paramagnetic then the variation of magnetic susceptibility with temperature and/or concentration can be used for flow control. For thermal buoyancy driven flows this can be accomplished in a temperature range below the Curie point of the salt. The magnetic force is proportional to the magnetic susceptibility and the product of the magnetic field and its gradient. By suitably positioning the experiment cell in the magnet, system flows can be assisted or countered, as desired. A similar approach can be extended to diamagnetic substances and fluids but the required magnetic force is considerably larger than that required for paramagnetic substances. The presentation will provide an overview of work to date on a NASA fluid physics sponsored project that aims to test the hypothesis of convective flow control using strong magnetic fields in protein crystal growth. The objective is to understand the nature of the various forces that come into play, delineate causative factors for fluid flow and to quantify them through experiments, analysis, and numerical modeling. The seminar will report specifically on the experimental results using paramagnetic salts and solutions in magnetic fields and compare them to analytical predictions. Applications of the concept to protein crystallization studies will be discussed. The use of strong magnetic fields for terrestrially simulating variable gravity environments and applications supporting the NASA Exploration Initiative will also be briefly discussed.

Ramachandran, N.

Pumping Liquid Oxygen by Use of Pulsed Magnetic Fields

An effort is underway to develop a method of pumping small amounts of liquid oxygen by use of pulsed magnetic fields. This development is motivated by a desire to reduce corrosion and hazards of explosion and combustion by eliminating all moving pump parts in contact with the pumped oxygen. The method exploits the known paramagnetism of liquid oxygen. Since they both behave similarly, the existing theory of ferrofluids (liquids with colloidally suspended magnetic particles) is directly applicable to paramagnetic liquid oxygen. In general, the force density of the paramagnetic interaction is proportional to the magnetic susceptibility multiplied by the gradient of the square of the magnitude of the magnetic field. The local force is in the direction of intensifying magnetic field. In the case of liquid oxygen, the magnetic susceptibility is large enough that a strong magnetic-field gradient can lift the liquid in normal Earth gravitation.

Youngquist, Robert

Controlling Nb(IV) Defects in SrNbO 2 N Oxygen Evolution Photocatalyst by Ammonolysis With Dinitrogen–Ammonia Mixtures

Strontium niobium oxynitride (SrNbO 2 N) is a promising, corrosion resistant semiconductor for the visible light-driven water splitting reaction, a non-photovoltaic pathway to green hydrogen fuel. However, SrNbO 2 N materials made by ammonolysis usually contain Nb 4+ defect states that cause electron–hole recombination. Here, in this work, we demonstrate that such defects can be minimized by synthesizing SrNbO 2 N from metal oxides in a mixed 13%:87% (vol) NH 3 /N 2 atmosphere. According to electron paramagnetic resonance (EPR), SrNbO 2 N made in pure NH 3 contains paramagnetic impurities with g = 2.002 and 2.195, which can be assigned to lattice and surface Nb 4+ defects. These states also cause broad optical absorptions centered at 800 and 1020 nm, respectively, and the lattice defect produces a 1.55–1.63 eV signal in surface photovoltage spectra. The improved SrNbO 2 N contains five times fewer lattice Nb 4+ defects (8.95 × 10 15 cm −3 ), based on the integrated EPR signal intensity, and supports a water oxidation photocurrent of 1.07 mA cm −2 at 1.23 V versus RHE under simulated sunlight and an apparent quantum efficiency of 5.1% at 400 nm during photocatalytic oxygen evolution. Based on earlier results with LaTiO 2 N and BaTaO 2 N, dilution of NH 3 during synthesis appears generally beneficial to transition metal oxynitrides.

electron paramagnetic resonance

Electronic Spin Relaxation and Clustering in High-Pressure High-Temperature Synthesized Microcrystalline Diamond Particles with Reduced Nitrogen Content

The negatively charged nitrogen-vacancy (NV – ) color center in diamonds is widely studied because of numerous applications of this unique quantum system in sensing and quantum information sciences. While substitutional nitrogen is required to form the NV – centers in diamond, it also yields other paramagnetic defects─primarily the neutrally charged substitutional nitrogen centers (P1)─that decrease NV – spin coherence, which in turn degrades performance in applications. Herein, we investigate high-pressure high-temperature synthesized diamond microparticles (ca. 140–185 μm) having lower─ranging from 3 to 38 ppm─than the typical nitrogen content of type 1b diamond ( ca. 100 ppm and higher) typically used for the production of fluorescent diamond particles with NV – centers. A suite of electron paramagnetic resonance, optically detected magnetic resonance, and nuclear magnetic resonance methods are used to characterize spin properties of P1 and NV – centers in the particles. Upon decreasing the nitrogen content from 29 to 3 ppm, the ensemble NV – T 2 relaxation time increased by about 3-fold as measured directly in the Hahn Echo experiment at magnetic field of 1.2 T. Analysis of electronic relaxation of P1 centers revealed the existence of at least two distinct populations of P1 centers, consisting of fast and slower relaxing spins and allowed for an estimation of local concentrations. Even with <10 ppm nitrogen contents, the analysis indicated a highly heterogeneous distribution of P1 centers, suggesting the possibility of P1 spin clustering even at low nitrogen concentrations. The combined data demonstrate that the particles prepared from HPHT diamond with a low nitrogen content offer improved spin properties that are beneficial for NV – sensing applications.

Carbon

Large Hyperfine Coupling Arising from Pseudo- 2 S Ground States in a Series of Lutetium(II) Metallocene Complexes

The synthesis of molecules with strong coupling between electronic and nuclear spins represents an important challenge in molecular quantum information science. Here, we report the synthesis and characterization of the divalent lutetium metallocene complexes Lu(Cp Me 5 )(Cp iPr 5 ) (Cp Me 5 = pentamethylcyclopentadienyl; Cp iPr 5 = pentaisopropylcyclopentadienyl), Lu(Cp iPr 4 Et ) 2 (Cp iPr 4 Et = ethyltetraisopropylcyclopentadienyl), and Lu(Cp iPr 4 ) 2 (Cp iPr 4 = tetraisopropylcyclopentadienyl). The molecular structures of these complexes, as determined through singlecrystal X-ray diffraction, feature a common bent sandwich geometry, with average Cp–Lu–Cp angles ranging from 159.9° to 152.6°. Analysis of continuous-wave electron paramagnetic resonance (EPR) spectra for the complexes reveals nearly isotropic g tensors with only a slight deviation from that of a free electron. Moreover, an extremely large splitting of the eight-line spectra indicates the presence of strong hyperfine coupling, and simulations provide isotropic hyperfine coupling constants of A iso = 4.38, 4.30, and 4.17 GHz across the series, where the value of A iso is found to decrease as the Cp–Lu–Cp angle becomes more acute. Notably, these values are the largest yet observed for any lanthanide complex. Moreover, EPR and computational analysis show that the large values of A iso stem from large s-orbital character up to 41.2% in the corresponding singly occupied molecular orbitals. To our knowledge, this degree of s-character in a molecular orbital is the largest yet reported for an open-shell isolable complex. These results outline a general strategy toward the isolation of paramagnetic molecules with strong hyperfine coupling and highly isotropic doublet electronic ground states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Low-temperature spin Seebeck effect in nonmagnetic vanadium dioxide

The spin Seebeck effect (SSE) is sensitive to thermally driven magnetic excitations in magnetic insulators. Vanadium dioxide in its insulating low-temperature phase is expected to lack magnetic degrees of freedom, as vanadium atoms are thought to form singlets upon dimerization of the vanadium chains. Instead, we find a paramagnetic SSE response in V⁢O 2 films that grows as the temperature decreases below 50 K. The field and temperature-dependent SSE voltage is qualitatively consistent with a general model of paramagnetic SSE response and inconsistent with triplet spin transport. Quantitative estimates find a spin Seebeck coefficient comparable in magnitude to that observed in strongly magnetic materials. Finally, the microscopic nature of the magnetic excitations in V⁢O 2 requires further examination.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Optimizing ensemble NV − spin properties of fluorescent diamond microparticles by systematic low pressure high temperature annealing

Low pressure high temperature annealing is a means for driving nitrogen and defect diffusion in diamond to reduce internal lattice damage without the need for technically complicated high-pressure cells. Herein, we perform a systematic time (5, 15, and 30 min) and temperature (1200 °C–1800 °C) study of effects of low-pressure high temperature annealing on photoluminescence, spin concentrations, and spin relaxation properties of NV centers in ca. 3 μm synthetic type 1b diamond particles. Annealing in the temperature range of ca. 1400 °C–1700 °C for even 5 min leads to a higher optically detected magnetic resonance contrast as compared to standard annealing at 900 °C for 2 h. Particles annealed at 1700 °C for 5 min exhibit a contrast close to about 13% as compared to about 9% for those annealed at 900 °C for 2 h. A reduction in the zero-field splitting strain parameter from E ≈ 4.5 MHz to ≈ 2.5 MHz and spectral linewidth from Δν ≈ 7 MHz to ≈ 4 MHz are observed even after 5 min annealing at 1700 °C. Improvements in these spectral parameters resulted in a roughly 2-fold reduction in the noise level of temperature monitoring experiment utilizing an ensemble of NV centers in the particles. Annealing in the temperature range of 1600 °C for 15 or 30 min or 1700 °C for 5 min resulted in NV T 1 relaxation times approaching ca. 5 ms typically observed for bulk diamond. Quantitative electron paramagnetic resonance (EPR) allowed for estimations of thermal activation energies of paramagnetic center annihilation. Monitoring the primary defect concentration (P1 and other defects with half integer spins) and utilizing second order kinetic modeling, an activation energy of 3.63 ± 0.28 eV was estimated. Alternatively, using the NV half field EPR signal and first order kinetic modeling, a similar activation energy 3.89 ± 0.29 eV was estimated.

NV centers

Plasmonic Ag nanocomposite phosphate glasses produced via γ-ray irradiation as reduction route

This paper reports on the impact of γ-ray irradiation (10, 100 kGy) on melt-quenched Ag + -doped phosphate glass and the effects of subsequent thermal processing leading to the production of plasmonic Ag nanocomposites. The γ-irradiated glasses were characterized alongside the pristine by differential scanning calorimetry (DSC), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, optical absorption, and photoluminescence (PL) spectroscopy. DSC characterization showed consistent glass transition temperatures (T g ) before and after γ-irradiation whereas the crystallization temperatures tended to decrease with increasing γ-ray dose. However, a lack of alteration of the glass network structure was supported by Raman spectroscopy. Room temperature EPR spectra clearly showed the formation of phosphorus oxygen hole center (POHC) defects in the undoped host, in addition to another doublet likely associated with a P 3 defect. The presence of paramagnetic silver species encompassing Ag 2+ and 107/109 Ag 0 atoms was also indicated in the silver-activated glass together with POHC defects. Optical absorption spectra were also consistent with the presence of various radiation-induced centers. Further analyzing the glass absorption edge via Tauc plots suggested the formation of electron center (EC) defects in γ-irradiated samples wherein the silver-doped glass exhibited decreasing band gap energies with increasing γ-ray dose. The PL characterization showed the silver-related radio-PL effect was induced exhibiting broad band emission with two maxima around 500 and 625 nm stemming from various molecular Ag$^{x+}_{n}$ clusters. Emission decay analyses revealed that the longer wavelength emission exhibited slower decay. The highest radiation dose of 100 kGy however resulted in weaker emission and faster decay kinetics attributed to energy transfer between the luminescent silver species and POHC defects. Finally subjecting the γ-irradiated Ag-doped glasses to heat treatment near the T g at 490 °C led to the development of the surface plasmon resonance of Ag nanoparticles (NPs) and the vanishing of the Ag$^{x+}_{n}$ clusters luminescence. In conclusion, the presence of the matrix-related EC defects was deemed accountable for the thermally induced reduction and consequent precipitation of Ag NPs making the plasmonic glasses attractive for photonic applications such as nonlinear optics.

36 MATERIALS SCIENCE

Inversion of dislocation-impurity interactions in α -Fe under magnetic state changes

Here, in this work, we investigate the dislocation-impurity interaction energies and their profiles for various 3d elements —V, Cr, Mn, Cu, Ni, and Co —in and around 1/2 $\langle111\rangle$ screw dislocations in α -Fe using ab initio methods. We consider the ferromagnetic and paramagnetic states, with the latter being modeled through both the disordered local moment model and a spin-wave approach. Our findings reveal that (1) magnetic effects are large compared to size misfit effects of substitutional impurities, and (2) dislocation-impurity interactions are dependent on the magnetic state of the matrix and thermal lattice expansion. In particular, Cu changes from core-attractive in the ferromagnetic state to repulsive in the paramagnetic state.

36 MATERIALS SCIENCE

Resistivity distribution and donor properties of antimony-doped n -type Czochralski silicon ingots

We investigate antimony (Sb)-doped Czochralski-grown silicon as an alternative n-type substrate for photovoltaic applications, and characterize their axial resistivity distribution, donor properties, and mechanical strength. We find that Sb-doped ingots can achieve a more uniform resistivity distribution along the axial direction compared to P-doped counterparts. Dopant concentration profiles in P-doped ingots can be accurately modelled using the standard Scheil's equation, accounting only for dopant segregation during solidification. In contrast, modelling Sb-doped ingots requires consideration of both dopant segregation and evaporation effects to fit the dopant distribution accurately. Using electron paramagnetic resonance spectroscopy at 9 K, we observe two hyperfine lines in P-doped samples, and six hyperfine lines for Sb 121 and eight for Sb 123 isotopes, with the number of hyperfine lines governed by the nuclear spins. We further identify two-atom Sb clustering in the Sb-doped wafers, confirmed through simulations of the additional weak electron paramagnetic resonance peaks. Finally, we find that 140 μm as-cut planar Sb-doped wafers exhibit slightly higher mechanical strength compared to P-doped wafers.

14 SOLAR ENERGY

Etch Products of Copper Atomic Layer Etching by Oxidation and Formic Acid Vapor

Atomic layer etching (ALE) of metals offers a path to greater control of selectivity, etch rate, and etch profile. However, tailoring a process to meet these demands requires an understanding of the volatile etch product, which is challenging to detect due to low product concentrations and the paramagnetism of many metalorganic products. Here, in this work, several complementary analysis techniques were used to determine the volatile etch product and residual surface species of a Cu ALE process based on plasma oxidation and formic acid vapor etching of the oxidized layer. It was shown that the volatile product was copper formate with a Cu 2+ paramagnetic center, in concordance with prior density functional theory (DFT) calculations. While copper formate tetrahydrate was formed, it was determined that the tetrahydrate product was confined to the surface, with anhydrous copper formate being the volatile etch product.

Smith, Taylor G. [Univ. of California, Los Angeles

Electrical Control of Magnetic Resonance in Phase Change Materials

Metal–insulator transitions (MITs) in resistive switching materials can be triggered by an electric stimulus that produces significant changes in the electrical response. When these phases have distinct magnetic characteristics, dramatic changes in the spin excitations are also expected. The transition metal oxide La 0.7 Sr 0.3 MnO 3 (LSMO) is a ferromagnetic metal at low temperatures and a paramagnetic insulator above room temperature. When LSMO is in its metallic phase, a critical electrical bias has been shown to lead to an MIT that results in the formation of a paramagnetic resistive barrier transverse to the applied electric field. Using spin-transfer ferromagnetic resonance spectroscopy, we show that even for electrical biases less than the critical value that triggers the MIT, there is magnetic phase separation, with the spin-excitation resonances varying systematically with applied bias. Therefore, voltage-triggered MITs in LSMO can alter magnetic resonance characteristics, offering an effective method for tuning synaptic weights in neuromorphic circuits.

36 MATERIALS SCIENCE

Photoinduced Electron Transfer Informs on Pathway Coupling in Flavin-Based Electron Bifurcation

Flavin-based electron bifurcation (FBEB) is an enzymatic mechanism that generates extremely high-energy electrons to drive unfavorable chemical reactions. It is utilized by the NADHdependent ferredoxin:NADP + -oxidoreductase (Nfn) enzyme in hyperthermophile Pyrococcus furiosus to bifurcate electrons from NADPH into the coupled low-potential (endergonic) and highpotential (exergonic) pathways. This process enables P. furiosus to live in harsh and uninviting environments. Despite its biological importance, the mechanisms used by Nfn to facilitate exceptional directional control over short-lived, high-energy electrons and to prevent undesired transfer, particularly along the low-potential pathway, are still not well understood. To elucidate how the protein environment contributes to electronic control in the lowpotential pathway, new techniques must be utilized to probe these unstable intermediates. In this study, we have adapted lowtemperature photoexcitation combined with electron paramagnetic resonance (EPR) to accumulate the short-lived intermediate and place it in the context of the other cofactors involved in the low-potential pathway of Nfn. We observed coincident growth of both the radical intermediate and its nearby [4Fe-4S] cluster over 4.5 h of illumination with NADPH at cryogenic temperatures. The photogenerated paramagnetic species were stable in LN 2 storage indefinitely and recombined when warmed to higher temperatures. The results provide insights into the electron transfer steps and cofactor interactions along the low potential pathway, facilitating a more robust mechanistic understanding of the high-energy events of electron bifurcation. Furthermore, through comparison of cryogenic and room temperature experiments, a potential gating step involving the movement of key residues important for the reversibility of electron flow along this pathway is suggested.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH