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DOE OSTI2026

Interpretable Deep Learning for Advancing Field-Enhanced Catalysis

This DOE Early Career project developed a physics-informed, interpretable AI-and-modeling framework to understand and exploit electric-field effects in heterogeneous catalysis, with ammonia cracking and synthesis as a representative pathway. The team built and validated methods to map local electric fields on metal surfaces and nanoparticles, showing that low-coordination features (tips/edges/corners) can concentrate fields by several-fold relative to flat facets. Using DFT-generated datasets, the project created physics-guided machine learning models that rapidly predict local electric fields and field-dependent adsorption energetics with near-DFT accuracy while reducing computational cost by orders of magnitude. These predictions were integrated with microkinetic modeling to quantify how field-dipole interactions reshape reaction energetics and mechanisms, enabling large increases in predicted catalytic rates and substantial reductions in operating temperature under favorable field conditions. To accelerate discovery of earth-abundant catalysts, the project combined interpretable ML screening (with electronic-structure descriptors identified as key drivers) with a generative inverse-design workflow based on diffusion models and physics constraints. The resulting closed-loop approach, linking simulation, mechanistic modeling, and AI, provides reusable tools and datasets for designing catalysts and operating conditions in field-enhanced catalysis, with broad relevance to electrostatic catalysis, plasma catalysis, electrocatalysis, and other energy-related chemical transformations.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2026

Balancing moisture and oxygen can match the crystallization dynamics of inert halide perovskite processing

Understanding crystallization in ambient environments is essential for scaling the fabrication of halide perovskite solar cells. Antisolvent-free perovskite deposition offers improved compatibility with high-throughput processing but introduces distinct crystallization dynamics relative to the more ubiquitous use of antisolvents in lab-scale perovskite fabrication. These dynamics are driven by interactions between solutes, solvent and the deposition environment. Using in situ wide-angle X-ray scattering during spin-coating and annealing, we demonstrate how relative humidity (RH) and oxygen, can be tuned to drive polytype evolution during ambient crystallization of formamidinium lead iodide to match that of inert synthesis and achieve comparable film and device quality. In an inert (N 2 ) environment, we find that perovskite films follow a well-established 2H → 3C phase transformation with a short period of coexistence of the 4H and 6H phase during heating. During crystallization in dry air (RH 0%), the added presence of oxygen leads to the dominance of 4H intermediate for an extended duration, establishing a 2H → 4H → 3C pathway. Introducing low humidity (RH 10%) suppresses the 4H phase to a short-lived intermediate above 100 °C, facilitating a more direct transition to the desired 3C phase and almost replicating the crystallization behavior observed under inert conditions. Interestingly, films crystallized under RH 10% show a lower onset temperature for the perovskite 3C phase than under N 2 . At higher humidity (RH 40%), the strong interaction of oxygen and moisture with iodoplumbates appears to stabilize higher order polytypes (4H and 6H). Devices fabricated under RH 10% achieve higher efficiency and enhanced stability compared to those produced under inert atmosphere. These findings provide mechanistic insight into crystallization pathways in different environments and provide a framework to transfer processes from inert to ambient conditions. The results highlight the critical role of controlled humidity in tuning antisolvent-free perovskite crystallization for scalable processing.

Hossain, Maimur [Univ. of California, San Diego, C↗

DOE OSTI2026

Characterization of Organosulfates and Organonitrates in Vertically Resolved Aerosols over the Southern Great Plains Field Campaign Report

Aerosol is the largest individual source of uncertainty in assessing the Earth’s radiative balance due to poorly understood aerosol processes and aerosol-cloud interactions. Thus, to constrain aerosol’s climate impacts, it is critical to understand aerosol compositions at high elevations. Organic material accounts for about 20-80% of total aerosol mass in the atmosphere and is known to play a key role in aerosol processes and cloud formation. In prior research, characterization of aerosol molecular composition has been mostly carried out at ground level. In these ground-level measurements, total speciated organosulfates and organonitrates may contribute significantly to organic aerosol mass on the order of 10-40%, most of which are from abundant biogenic volatile organic compounds such as isoprene and monoterpenes. Organosulfates and organonitrates have also been shown to be present in substantial amounts in cloud water, suggesting that they can be transported and/or directly formed at high elevations. On the other hand, the less common and more expensive aircraft studies have performed high-altitude measurements, but were often limited in the number of different altitudes sampled and in sample collection under consistent conditions. Therefore, the vertical distributions of key aerosol components such as organosulfates and organonitrates are not well understood and have not been extensively studied. Nevertheless, it is important to understand how organosulfates and organonitrates in aerosols are distributed, transformed, participate in aqueous-phase processes, and interact with high-altitude clouds.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Steering the Methane Dry Reforming Reactivity of Ni/La 2 O 3 Catalysts by Controlled In Situ Decomposition of Doped La 2 NiO 4 Precursor Structures

The influence of A- and/or B-site doping of Ruddlesden-Popper perovskite materials on the crystal structure, stability, and dry reforming of methane (DRM) reactivity of specific A 2 BO 4 phases (A = La, Ba; B = Cu, Ni) has been evaluated by a combination of catalytic experiments, in situ X-ray diffraction, X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and aberration-corrected electron microscopy. At room temperature, B-site doping of La 2 NiO 4 with Cu stabilizes the orthorhombic structure ( Fmmm ) of the perovskite, while A-site doping with Ba yields a tetragonal space group ( I 4/ mmm ). We observed the orthorhombic-to-tetragonal transformation above 170 °C for La 2 Ni 0.9 Cu 0.1 O 4 and La 2 Ni 0.8 Cu 0.2 O 4 , slightly higher than for undoped La 2 NiO 4 . Loss of oxygen in interstitial sites of the tetragonal structure causes further structure transformations for all samples before decomposition in the temperature range of 400 °C-600 °C. Controlled in situ decomposition of the parent or A/B-site doped perovskite structures in a DRM mixture (CH 4 :CO 2 = 1:1) in all cases yields an active phase consisting of exsolved nanocrystalline metallic Ni particles in contact with hexagonal La 2 O 3 and a mixture of (oxy)carbonate phases (hexagonal and monoclinic La 2 O 2 CO 3 , BaCO 3 ). Differences in the catalytic activity evolve because of (i) the in situ formation of Ni-Cu alloy phases (in a composition of >7:1 = Ni:Cu) for La 2 Ni 0.9 Cu 0.1 O 4 , La 2 Ni 0.8 Cu 0.2 O 4 , and La 1.8 Ba 0.2 Ni 0.9 Cu 0.1 O 4 , (ii) the resulting Ni particle size and amount of exsolved Ni, and (iii) the inherently different reactivity of the present (oxy)carbonate species. Based on the onset temperature of catalytic DRM activity, the latter decreases in the order of La 2 Ni 0.9 Cu 0.1 O 4 ~ La 2 Ni 0.8 Cu 0.2 O 4 ≥ La 1.8 Ba 0.2 Ni 0.9 Cu 0.1 O 4 > La 2 NiO 4 > La 1.8 Ba 0.2 NiO 4 . Simple A-site doped La 1.8 Ba 0.2 NiO 4 is essentially DRM inactive. The Ni particle size can be efficiently influenced by introducing Ba into the A site of the respective Ruddlesden-Popper structures, allowing us to control the Ni particle size between 10 nm and 30 nm both for simple B-site and A-site doped structures. Hence, it is possible to steer both the extent of the metal-oxide-(oxy)carbonate interface and its chemical composition and reactivity. Counteracting the limitation of the larger Ni particle size, the activity can, however, be improved by additional Cu-doping on the B-site, enhancing the carbon reactivity. Exemplified for the La 2 NiO 4 based systems, we show how the delicate antagonistic balance of doping with Cu (rendering the La 2 NiO 4 structure less stable and suppressing coking by efficiently removing surface carbon) and Ba (rendering the La 2 NiO 4 structure more stable and forming unreactive surface or interfacial carbonates) can be used to tailor prospective DRM-active catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

Abstract Transforming polyolefin waste into liquid alkanes through tandem cracking‐alkylation reactions catalyzed by Lewis‐acid chlorides offers an efficient route for single‐step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C−C bonds and forming C−C bonds in alkylation. Here, we show that efficient and selective deconstruction of low‐density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl 3 ) and gallium chloride (GaCl 3 ). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline‐range liquid alkanes over 70 %. AlCl 3 showed an exceptional conversion rate of 5000 , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.

Zhang, Wei↗

DOE OSTI2024

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Tuning acidity in silica-overcoated oxides for hydroalkoxylation

Mixed oxides are ubiquitious solid acid catalysts for a number of transformations. Here, the chemistry of mixed oxide interfaces was experimentally probed by constructing model SiO 2 on MO x interfaces using a liquid-phase, stoichiometrically-controlled deposition of tetraethyl orthosilicate (TEOS). Catalytically active Brønsted sites were generated in four series of overcoated SiO 2 on metal oxide materials prepared by depositing TEOS onto Al 2 O 3 , anatase TiO 2 , Nb 2 O 5 , and ZrO 2 . Pyridine DRIFTS studies indicate that the acidity of deposited silanol groups was enhanced by interaction with the metal oxide surface, suggesting that pseudo-bridging silanol type structures were formed. Trimethylphosphine oxide (TMPO) 31 P NMR experiments showed that Brønsted acid strength varied in the overcoated materials, with increasing strength in the following order: SiO 2 /ZrO 2 < SiO 2 /TiO 2 < SiO 2 /Nb 2 O 5 < SiO 2 /Al 2 O 3 . This order correlated with the Lewis acidity and chemical hardness of the underlying metal oxides. The catalytic performance of the materials was evaluated in the liquid-phase hydroalkoxylation of dihydropyran with n-octanol, revealing that activity was highly dependent on SiO 2 loading, which impacted the density of acid sites, and scaled exponentially with Brønsted acid strength, determined by the core metal oxide identity. Brønsted acid strength appears to be the key driver of the materials’ activity, with the highest areal rate of 2.2 mmol / m 2 – h being measured over SiO 2 /Al 2 O 3 . Furthermore, this study shows that SiO 2 -overcoated materials are a systematically tunable class of catalysts that can be applied to acid catalyzed reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Thermocatalytic Heat Pipes for Geothermal Resource Recovery

Heat pipes are an important technology that allow orders of magnitude faster heat transfer than simple conduction. However, operating principles in heat pipes place fundamental bounds on their performance (critical heat flux and efficiency). Conventional heat pipe functionality is inherently tied to vaporization and condensation of the working fluid charged in the heat pipe. These fluids each have different operating temperature ranges based on the capillary, entrainment, sonic, and boiling limits of the heat pipe design. These limits, typically the capillary limit, dictate the maximum heat flux a heat pipe can carry, and most importantly for geothermal systems, the distance over which the pipes can operate (100 to 200 m maximum under optimum conditions). A thermocatalytic heat pipe breaks the inherent limitations of phase change thermo- and hydrodynamics and can transform heat pipe technology as a potentially more efficient means of extracting heat from a geothermal resource. The thermocatalytic heat pipe uses a working fluid to transport both sensible and chemical heat. An endothermic chemical reaction at depth removes heat from the reservoir and produces reactive intermediates, which are transported to the surface and used to run a reverse exothermic reaction that releases heat for use in power generation or other useful purposes. This technology offers two distinct advantages over conventional geothermal heat recovery technologies: (1) lower heat loss to the rock outside of the geothermal reservoir, and (2) higher heat transfer rates to the well field within the geothermal reservoir. Both advantages offer opportunity to reduce risks and lower costs of geothermal energy recovery. In this report, we discuss an initial effort to assess the efficacy and limitations of this technology for extracting heat from both porous/permeable and nominally impermeable geothermal reservoirs. Numerical simulation capabilities of the STOMP-GT code were enhanced to enable simulations of thermochemical heat pipes traversing geothermal reservoirs. An array of potential thermochemical reaction systems was evaluated and screened. Of these, an ethanol dehydration reaction was most promising in the vapor-liquid reaction set. A solid-phase dehydration reaction (CuSO4·5H2O) showed the highest reaction enthalpy per unit volume but would require development of a nonaqueous carrier fluid to implement it in a heat pipe. Subsurface reservoir simulations predicted long-term performance of the heat pipes for each geothermal reservoir type. The performance of U-shaped wells and coaxial wells was evaluated for a suite of reactions for both hydrothermal and hot dry rock reservoirs and was compared with a baseline case of simply pumping water through the wells. The heat pipe technology was additionally evaluated for an enhanced geothermal system (EGS) with an injection borehole, production borehole, and intervening hydraulically conductive fracture. All reservoir types showed significant improvement in heat recovered over a 20-year operating period ranging from a 1.8X increase for the hot dry rock case to more than 2.5X more energy recovered for the EGS case.

15 GEOTHERMAL ENERGY↗

DOE OSTI2021

Signatures of two-dimensional superconductivity emerging within a three-dimensional host superconductor

Significance We report signatures of a new phenomenon wherein a hidden “interdimensional” order emerges from a bulk three-dimensional superconductor tuned to approach a phase transition to an insulator. Prior electrical transport measurements found that the superconductor–insulator transition of BaPb 1− x Bi x O 3 demonstrated critical scaling behavior but inexplicably required parameters consistent only with two dimensions. Here, we directly image the three-dimensional superconducting state as it approaches an insulating phase and discover that signatures of a two-dimensional granular superconducting phase spontaneously emerge at the transition. Moreover, the properties of this phase precisely match the theory of emergent electronic granularity specific to two-dimensional materials. These findings posit that a three-dimensional superconductor electronically reorganizes itself into a two-dimensional granular superconductor before ultimately transforming to an insulator.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2023

Robust highly durable solid oxide fuel cell cathodes – Improved materials compatibility & self-regulating surface chemistry

Solid oxide fuel cells (SOFCs) are electrochemical conversion devices that directly transform hydrogen or hydrocarbon fuels to electricity, with energy efficiencies as high as 90%, coupled with reduced emissions. Several factors, however, remain to be addressed when considering scale-up of SOFC technology, including the need to overcome decreased performance due to sluggish rates of the oxygen reduction reaction (ORR) at the cathode under reduced temperatures and susceptibility to degradation in performance from surface poisoning e.g. from chromia, while limiting the use of critical raw materials (lanthanides and transition metals) present in high performing mixed ionic electronic conducting electrodes like (La,Sr)CoO 3 (LSC). In this project we explored the key descriptors for determining ORR activity in SOFC electrodes and tried to recover performance degradation by applying them to SOFC electrodes. In order to do this, we first selected a model mixed ionic electronic conducting (MIEC) oxide, Pr-doped CeO 2 (Pr 0.1 Ce 0.9 O 2-δ , PCO), which is a chemically stable fluorite and free of inherent poison sources (e.g. Sr segregation in LSC) that potentially react with external impurities such as Cr-species vaporized from the interconnect. The three approaches originally planned in this project are as follows: 1) evaluation of scavenger exsolution characteristics, 2) study of scavengers gettering efficacy following Cr and Si poisoning and 3) integration of new compositions into porous electrodes. Among them, exceptional progress has been made in 2) and 3), especially understanding the role of surface infiltrants in impacting electrode performance and degradation of PCO materials. We found that the Smith acidity scale for binary oxides serves as a powerful descriptor for tuning and predicting the oxygen exchange kinetics on MIEC PCO surfaces. As a result, with infiltration with binary oxides, ranging from strongly basic (Li 2 O) to strongly acidic (SiO 2 ) onto the surface of porous PCO, it was possible to systematically vary the chemical surface exchange coefficient (k chem ) by 6 orders of magnitude! L i2 O increased k chem by nearly 1,000 times over that of pristine PCO, while SiO 2 decreased k chem by nearly the same factor. Strikingly, although the pre-exponential of k chem scales linearly with the acidity of the infiltrated binary oxide, there is nearly no change in the activation energy. With this insight, we attributed the origin of these dramatic changes in k chem values to the systematic increase and decrease in the surface electron density induced by infiltrated binary oxides. More interestingly, although both Cr 2 O 3 and SiO 2 were determined to be acidic by Smith, suggesting that this feature could likely be the primary reason that these compounds serve to poison the ORR on SOFC cathodes, the effect of poisoning could be subsequently tuned by adding multiple infiltrants and controlling their relative surface acidities. We also systematically examined the effect of serial infiltration of basic and acidic oxides. It turned out that serial infiltration of Li not only recovers approximately 20-fold degraded k chem of PCO by acidic Cr 2 O 3 but its k chem is enhanced even beyond that of the non-infiltrated PCO by more than three orders of magnitude. This was further verified with a screen-printing PCO symmetric cell in terms of the electrode performance (area-specific resistance, ASR) related to approach 3). These observations point to acidity as a key descriptor not only in tuning and predicting the ORR activity of SOFC cathodes that largely determines the overall performance of SOFC, but in mitigating and reactivating poisoned electrode performance. This work provides novel guidelines for making the electrode performance much more active and robust in SOFCs, which can further be applied to all applications requiring oxygen exchange reaction, such as electrolyzers, permeation membranes and gas sensors.

30 DIRECT ENERGY CONVERSION↗

DOE OSTI2021

A new hypothesis for the origin of Amazonian Dark Earths

Amazonian Dark Earths (ADEs) are unusually fertile soils characterised by elevated concentrations of microscopic charcoal particles, which confer their distinctive colouration. Frequent occurrences of pre-Columbian artefacts at ADE sites led to their ubiquitous classification as Anthrosols (soils of anthropic origin). However, it remains unclear how indigenous peoples created areas of high fertility in one of the most nutrient-impoverished environments on Earth. Here, we report new data from a well-studied ADE site in the Brazilian Amazon, which compel us to reconsider its anthropic origin. The amounts of phosphorus and calcium—two of the least abundant macronutrients in the region—are orders of magnitude higher in ADE profiles than in the surrounding soil. The elevated levels of phosphorus and calcium, which are often interpreted as evidence of human activity at other sites, correlate spatially with trace elements that indicate exogenous mineral sources rather than in situ deposition. Stable isotope ratios of neodymium, strontium, and radiocarbon activity of microcharcoal particles also indicate exogenous inputs from alluvial deposition of carbon and mineral elements to ADE profiles, beginning several thousands of years before the earliest evidence of soil management for plant cultivation in the region. Our data suggest that indigenous peoples harnessed natural processes of landscape formation, which led to the unique properties of ADEs, but were not responsible for their genesis. If corroborated elsewhere, this hypothesis would transform our understanding of human influence in Amazonia, opening new frontiers for the sustainable use of tropical landscapes going forward.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Structural Damage and Recrystallization Response of Garnet Crystals to Intense Electronic Excitation

Here, the susceptibility to irradiation-induced damage, the fundamental mechanism of the relaxation kinetics, and the corresponding recrystallization effect related to the cation radius ratio are comprehensively investigated for Y 3 Al 5 O 12 and Gd 3 Ga 5 O 12 garnet crystals under 645 MeV Xe 35+ irradiation with different fluences of 5 × 10 11 –3 × 10 12 ions cm –2 . Regarding different lattice distortion and swelling levels, the observed microstructure transformations to disordered and amorphous phases, and corresponding hillock dimensions, consistently confirm that Gd 3 Ga 5 O 12 has a higher susceptibility to radiation damage than Y 3 Al 5 O 12 . Combined with iTS model calculations, although Y 3 Al 5 O 12 has higher atomic temperature and energy deposition than Gd 3 Ga 5 O 12 under the same ion velocity and electronic energy loss, the relatively high thermal conductivity and specific heat coefficient of Y 3 Al 5 O 12 crystals enhance the conduction and dissipation of deposition energy, and Gd 3 Ga 5 O 12 , with a higher cation-radius-ratio (r A /r B ), is more easily damaged to amorphous phase due to the less favorable kinetics of ordering and recovery of a melted track region to the crystalline phase. Additionally, the significant bandgap modification in spectral ranges of 5.88–6.75 eV for Y 3 Al 5 O 12 and 4.83–5.41 eV for Gd 3 Ga 5 O 12 , and the enhancement of defect-assisted-related luminescence are achieved, providing a basis to design novel optoelectronic devices in microelectronics fields.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Hilbert space multireference coupled cluster tailored by matrix product states

In the past decade, the quantum chemical version of the density matrix renormalization group method has established itself as the method of choice for strongly correlated molecular systems. However, despite its favorable scaling, in practice, it is not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist; in our group, we focused on the tailored coupled cluster (TCC) approach. This method works well in many situations; however, in exactly degenerate cases (with two or more determinants of equal weight), it exhibits a bias toward the reference determinant representing the Fermi vacuum. Although sometimes it is possible to use a compensation scheme to avoid this bias for energy differences, it is certainly a drawback. In order to overcome this bias of the TCC method, we have developed a Hilbert-space multireference version of tailored CC, which can treat several determinants on an equal footing. We have implemented and compared the performance of three Hilbert-space multireference coupled cluster (MRCC) variants—the state universal one and the Brillouin–Wigner and Mukherjee’s state specific ones. We have assessed these approaches on the cyclobutadiene and tetramethyleneethane molecules, which are both diradicals with exactly degenerate determinants at a certain geometry. We have also investigated the sensitivity of the results on the orbital rotation of the highest occupied and lowest unoccupied molecular orbital (HOMO–LUMO) pair, as it is well known that Hilbert-space MRCC methods are not invariant to such transformations.

Chemistry↗

DOE OSTI2021

Imposing equilibrium on experimental 3-D stress fields using Hodge decomposition and FFT-based optimization

Here, we present a methodology to impose micromechanical constraints, i.e. stress equilibrium at grain and sub-grain scale, to an arbitrary (non-equilibrated) voxelized stress field obtained, for example, by means of synchrotron X-ray diffraction techniques. The method consists in finding the equilibrated stress field closest (in L 2 -norm sense) to the measured non-equilibrated stress field, via the solution of an optimization problem. The extraction of the divergence-free (equilibrated) part of a general (non-equilibrated) field is performed using the Hodge decomposition of a symmetric matrix field, which is the generalization of the Helmholtz decomposition of a vector field into the sum of an irrotational field and a solenoidal field. The combination of: a) the Euler–Lagrange equations that solve the optimization problem, and b) the Hodge decomposition, gives a differential expression that contains the bi-harmonic operator and two times the curl operator acting on the experimental stress field. These high-order derivatives can be efficiently performed in Fourier space. The method is applied to filter the non-equilibrated parts of a synthetic piecewise constant stress fields with a known ground truth, and stress fields in Gum Metal, a beta-Ti-based alloy measured in-situ using Diffraction Contrast Tomography (DCT). In both cases, the largest corrections were obtained near grain boundaries.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Mechanistic Studies of an Iron-Catalyzed Intermolecular C–H Amination Reaction under Catalytic Conditions and Having a Large KIE

The conversion of C–H bonds into amines by nitrene insertion is an attractive transformation since it is both atom- and step-economical, and provides a direct route to functionalizing hydrocarbons. Using an iron catalyst [{( tBu pyrr) 2 pyr}Fe(OEt 2 )] (1-OEt 2 ) (( tBu pyrr) 2 pyr 2– = 3,5- t Bu 2 -bis(pyrrolyl)pyridine), we recently demonstrated the catalytic conversion of weak C–H bonds into secondary amines using aryl azides as the nitrene source [Zars, E.; Angew. Chem., Int. Ed. 2023, 62, e202311749]. Here, we describe detailed mechanistic studies of this intermolecular C–H amination reaction under catalytic conditions. We find by Variable Time Normalization Analysis (VTNA) that the conversion of xanthene (2-H 2 ) and 2,4,6-trimethyl-phenyl azide ( Me 3) catalyzed by 1-OEt 2 is an overall 3/2 order process, being 1 st order in 2-H 2 and half order in Me 3. A kinetic isotope effect study (KIE) using 2-d 2 results in a significant decrease in the rate (KIE = 61(15)), which clearly implicates the C–H insertion step as rate-determining. Furthermore, treatment of 1-OEt 2 with one equivalent of N 3 -2,6- i Pr 2 –C 6 H 3 yields the mixed-valence C–N coupled product [( tBu pyrr) 2 pyrFe-N═C(2,6 i Pr 2 –Ph)═N-(2,6 i Pr 2 –Ph))Fe tBu pyrrpyr(2-H-pyrr)] (5 iPr ). Quantum chemical calculations confirm the electronic structure of the mixed-valence dimer in 5 iPr and rationalize the Hammett correlation by a delicate balance in the dinuclearization of the catalytically active monomers. Calculations further indicate significant tunneling for the pivotal H atom abstraction by the iron-imidyl complex. Combining all these results allows us to propose a mechanism consisting of imido formation in equilibrium with a radical-coupled diiron system, followed by stepwise C–H insertion via a linear H atom abstraction transition state and subsequent radical rebound.

azides↗

DOE OSTI2026

The quantum evolutions of the diffractive transverse-momentum dependent gluon distribution

Using the Colour Glass Condensate description of electron-nucleus collisions at high energy, we study the diffractive production of a pair of jets with transverse momenta much larger than the nuclear saturation momentum Q s . At leading order in the QCD coupling, the di-jet cross-section exhibits transverse-momentum dependent (TMD) factorisation, with a gluon diffractive TMD distribution (DTMD) which is controlled by gluon saturation and describes the transverse-momentum imbalance between the produced jets. The next-to-leading corrections generate the various quantum evolutions of the diffractive gluon distribution. We focus on the Collins-Soper-Sterman (CSS) evolution which describes the change in the gluon DTMD when increasing the “hard scale” (the typical transverse momentum of the di-jets). We consider two different representations for this equation, one in transverse-momentum space, the other one in transverse-coordinate space. They are not fully equivalent with each other (despite being related by a Fourier transform) because of the respective boundary conditions. These conditions encode the essential physics of gluon saturation together with the effects of two other types of quantum evolution: the BK/JIMWLK evolution over the rapidity gap (“inside the Pomeron”) and the DGLAP evolution outside the rapidity gap (“within the diffractive system”). We demonstrate that, due to gluon saturation, one can compute both the boundary conditions and the CSS solutions mostly from first principles, without the need for a non-perturbative Sudakov. We numerically find a good agreement between the CSS solutions in the two aforementioned representations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2020

Low-Temperature Crystal Structure and Mean-Field Modeling of Er x Dy 1- x Al 2 Intermetallics

Low-temperature crystal structure of the Er x Dy 1-x Al 2 alloys with x = 0.45, 0.67, 0.90 was examined using temperature-dependent powder X-ray diffraction. The Er-rich sample, Er 0.9 Dy 0.1 Al 2 , exhibits a rhombohedral distortion associated with the magnetic ordering that occurs around 20 K. The rhombohedral distortion is suppressed in Er 0.67 Dy 0.33 Al 2 , while a weak low-temperature tetragonal distortion is observed in Er 0.45 Dy 0.55 Al 2 . The mean-field theory supports the correlation between the type of structural distortion and the variable easy magnetization axis in Er x Dy 1-x Al 2 intermetallics.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Transforming an Ionic Conductor into an Electronic Conductor via Crystallization: In Situ Evolution of Transference Numbers and Structure in (La,Sr)(Ga,Fe)O 3–x Perovskite Thin Films

Mixed-conducting perovskites are workhorse electrochemically active materials, but typical high-temperature processing compromises their catalytic activity and chemo-mechanical integrity. Low-temperature pulsed laser deposition of amorphous films plus mild thermal annealing is an emerging route to form homogeneous mixed conductors with exceptional catalytic activity, but little is known about the evolution of the oxide-ion transport and transference numbers during crystallization. Here the coupled evolution of ionic and electronic transport behavior and structure in room-temperature-grown amorphous (La,Sr)(Ga,Fe)O 3-x films as they crystallize is explored. In situ ac-impedance spectroscopy with and without blocking electrodes, simultaneous capturing-synchrotron-grazing-incidence X-ray diffraction, dc polarization, transmission electron microscopy, and molecular dynamics simulations to evaluate isothermal and non-isothermal crystallization effects and the role of grain boundaries on transference numbers is combined. Ionic conductivity increases by ≈2 orders of magnitude during crystallization, with even larger increases in electronic conductivity. Consequently, as crystallinity increases, LSGF transitions from a predominantly ionic conductor to a predominantly electronic conductor. The roles of evolving lattice structural order, microstructure, and defect chemistry are examined. Grain boundaries appear relatively nonblocking electronically but significantly blocking ionically. The results demonstrate that ionic transference numbers can be tailored over a wide range by tuning crystallinity and microstructure without having to change the cation composition.

36 MATERIALS SCIENCE↗