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DOE OSTI2022

The impacts of charge transfer, localization, and metallicity on hydrogen retention and transport capacity

Solid state hydrides such as early transition metal hydrides are of inestimable importance for the future of hydrogen energy and are actively being investigated for energy conversion and storage applications such as fuel cells, solid-state batteries and neutron moderators. The retention and transport behavior of hydrogen in these hydrides has a huge role on the extended performance of components. While early transition-metal-based compounds exhibit many peculiar properties due to their unique correlated electronic signatures arising from -orbital electrons, the fundamental chemistry and transport behavior of hydrogen in such hydrides is not well understood. In the present work, using density functional theory, a highly intricate bonding feature is revealed through the theoretical investigation of the electronic structure of early transition metal hydrides YH 2 and ZrH 2 . In particular, a pronounced charge transfer from the transition element to H, results in localized electron densities at deep energy levels. The interplay between intrinsic charge transfer, charge localization, and metallicity in YH 2 and ZrH 2 leads to strong chemical bonding between metal and hydrogen atoms and large energy barriers for the migration of hydrogen vacancies. Specifically, hydrogen vacancies are found to be stable in the neutral state due to electron screening effects, accompanied by substantially high migration barriers between 0.8–1.2 eV along different crystallographic directions. In contrast, recent literature shows the migration barrier for charged H vacancies in insulating s-block metal hydrides lie between 0.1–0.4 eV, which is suitable for fast conduction applications. This pivotal electron structure difference exploited between early transition metal hydrides and alkali/alkaline earth metal hydrides determines extended hydrogen retention in these early transition metal hydrides. Finally, this work explains fundamental differences between the electronic structure of s-block and d-block metal hydrides, and its impact on the mobility of hydrogen vacancies.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Advancing Grid Resilience through Smart Charge Management: Findings from Maryland’s Pilot

This report presents research findings from a four-year Smart Charge Management (SCM) pilot program conducted by Maryland’s largest electric utilities—Baltimore Gas and Electric (BGE), Potomac Electric Power Company (Pepco), and Delmarva Power & Light (DPL)—to evaluate strategies for optimizing electric vehicle (EV) charging loads and enhancing grid stability. Supported by the U.S. Department of Energy (DOE), Argonne National Laboratory collaborated with all project partners and examined the effectiveness of Time-of-Use (TOU) and Load Balancing (LB) strategies in managing peak demand, deferring costly infrastructure upgrades, and reducing grid constraints at the feeder level. Using charging data from over 4,600 EV drivers, the study analyzed SCM’s impact on the distribution systems of BGE and Pepco, which consists of over 2000 feeders. Unlike prior research that focused on system-wide trends or synthetic feeders, this analysis offers granular, feeder-level insights based on real-world operational data. It highlights how transformer density, load profiles, and infrastructure constraints influence smart charging performance. Results show feeder-level conditions play a crucial role in SCM effectiveness, with most feeders benefiting more from LB, while TOU-based SCM may be sufficient for others. By 2035, LB reduced peak charging loads by 27% on average, compared to 23% under TOU-based SCM, though some feeders saw reductions exceeding 35%, while others experienced minimal impact. Feeders with higher transformer utilization and limited capacity benefited more from LB, which more effectively distributed charging demand during off-peak hours. Beyond reducing grid constraints, SCM offers long-term operational and financial benefits. By shifting EV charging demand strategically, utilities can optimize asset utilization, delay infrastructure investments, and enhance grid performance. In terms of infrastructure upgrade deferrals, at the feeder level, LB consistently reduced peak charging loads and resulting infrastructure upgrade costs, particularly in high EV enrollment areas, decreasing the number of overloaded transformers by up to 35%, while TOU-based SCM achieved 20-30% reductions depending on feeder characteristics. At the system level, LB has the potential to defer total upgrade costs by $\$$186 million for BGE, compared to $\$$159 million under TOU-based SCM. For Pepco, TOU-based SCM performed slightly better, deferring upgrade costs by $\$$30 million, compared to $\$$29 million under LB. Section 4.5 reviews some of the system differences between BGE and Pepco. However, as EV adoption scales, TOU-based SCM will introduce secondary peak charging loads, reinforcing the need for more advanced, adaptive SCM approaches to prevent new grid challenges. As EV adoption continues to grow, feeder-level managed charging strategies will be essential for mitigating grid stress, improving infrastructure efficiency, and maintaining energy affordability for consumers. This report provides critical insights for utilities, Public Utility Commissions (PUCs), and state agencies on the role of feeder-specific smart charging in infrastructure planning, policy development, and grid modernization. The findings underscore the importance of tailored, data-driven SCM solutions that align with local grid conditions, ensuring a resilient, cost-effective transition to increasing EV adoption while safeguarding distribution system performance.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2022

Hubbard-corrected oxide formation enthalpies without adjustable parameters

A density functional theory (DFT) approach to computing transition metal oxide heat of formation without adjustable parameters is presented. Different degrees of d-electron localization in oxides are treated within the DFT+U approach with site-dependent, first-principles Hubbard U-parameters obtained from linear response theory, and delocalized states in the metallic phases are treated without Hubbard corrections. Comparison of relative stabilities of these differently treated phases is enabled by a local d-electron density matrix-dependent model, which was found by genetic programming against experimental reference formation enthalpies. This mathematically simple model does not explicitly depend on the Hubbard-corrected ionic species and is shown to reproduce the heats of formation of the Mott insulators Ca 2 RuO 4 and Y 2 Ru 2 O 7 within ~3% of experimental results, where the experimental training data did not contain Ru oxides. This newly developed method thus absolves from the need for element-specific corrections fitted to experiments in existing Hubbard-corrected approaches to the prediction of reaction energies of transition metal oxides and metals. The absence of fitting parameters opens up here the possibility to predict relative thermodynamic stabilities and reaction energies involving d-states of varying degree of localization at transition metal oxide interfaces and defects, where site-dependent U-parameters will be particularly important and devising a fitting scheme against experimental data with predictive power would be exceedingly difficult.

transition metal oxides↗

DOE OSTI2021

Excited Rydberg states in MoSe 2 /WSe 2 heterostructures

The functional form of Coulomb interactions in the transition metal dichalcogenides (TDMs) and other van der Waals solids is critical to many of their unique properties, e.g. strongly-correlated electron states, superconductivity and emergent ferromagnetism. This paper presents measurements of key excitonic energy levels in MoSe 2 /WSe 2 heterostructures. These measurements are obtained from resonance Raman experiments on specific Raman peaks only observed at excited states of the excitons. This data is used to validate a model of the Coulomb potential in these structures which predicts the exciton energies to within ~5 meV. This model is used to determine the effect of heterostructure formation on the single-particle band gaps of the layers and will have a wide applicability in designing the next generation of more complex TDM structures.

Materials Science↗

DOE OSTI2022

Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li 7 RuO 6 via Intercalation Reactions

The push to increase the capacity of oxides to store charge as Li-ion battery cathodes has challenged our knowledge of the boundaries of redox chemistry and its relationship to the atomic structure. Layered phases with Ru are now classical models in the quest for refined theories. Current understanding dictates that the highest formal state that can be reached in them is Ru(V), after which activity centered at the oxide anions is triggered. Yet, this picture is challenged by this investigation of the intercalation chemistry of Li 7 RuO 6 . Coupling structural and spectroscopic analysis with computational simulations, we show that Li 7 RuO 6 is capable of highly reversible lithiation to Li 8 RuO 6 through the Ru(V)/Ru(IV) redox couple. Further, Li 7 RuO 6 can also undergo anodic Li deintercalation, showing clear evidence of the reversible formation of Ru(VI) with octahedral coordination, an unusual state that is not accessible in other layered oxides. The results highlight the versatility of the Ru-O bond to undergo distinct redox transitions depending on the specific layered arrangements. They enrich our understanding of redox chemistry in solids while underscoring the need for descriptions of charge compensation that reflect the nuance of covalent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Ecosystems and Networks Integrated with Genes and Molecular Assemblies (ENIGMA): Component 5: Imaging Protein Conformations, Shapes & Assemblies in Solution & Administration project (Final Scientific/Technical Report, Subcontract No. 6974584)

We set ambitious goals to examine microorganism communities and measure both their chemical input and output as a read out of specific biochemical activity. These scientific goals are driving the development of sophisticated algorithms to analyze large amounts of experimental measurements made using high throughput technologies to explain and predict how the environment influences biological function at multiple scales and how the microbial systems in tum modify the environment. By examining how bacteria communities rely on symbiotic metabolic relationships for survival and reproductive success, and how these relationships consequently affect their biochemical capabilities. This was accomplished using state-of-the-art mass spectrometry-based methods, and metabolic fingerprinting approaches with a high degree of chemical specificity and sensitivity. During this period the original effort transitioned and was consolidated into what is now ENIGMA, the efforts on technology development expanded to include more untargeted metabolomics and its application to organisms on a systems level.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS1994

TOTAL user manual

Semi-Markov models can be used to analyze the reliability of virtually any fault-tolerant system. However, the process of delineating all of the states and transitions in the model of a complex system can be devastatingly tedious and error-prone. Even with tools such as the Abstract Semi-Markov Specification Interface to the SURE Tool (ASSIST), the user must describe a system by specifying the rules governing the behavior of the system in order to generate the model. With the Table Oriented Translator to the ASSIST Language (TOTAL), the user can specify the components of a typical system and their attributes in the form of a table. The conditions that lead to system failure are also listed in a tabular form. The user can also abstractly specify dependencies with causes and effects. The level of information required is appropriate for system designers with little or no background in the details of reliability calculations. A menu-driven interface guides the user through the system description process, and the program updates the tables as new information is entered. The TOTAL program automatically generates an ASSIST input description to match the system description.

Johnson, Sally C.↗

NASA NTRS2015

Space-to-Space Power Beaming Enabling High Performance Rapid Geocentric Orbit Transfer

The use of electric propulsion is more prevalent than ever, with industry pursuing all electric orbit transfers. Electric propulsion provides high mass utilization through efficient propellant transfer. However, the transfer times become detrimental as the delta V transitions from near-impulsive to low-thrust. Increasing power and therefore thrust has diminishing returns as the increasing mass of the power system limits the potential acceleration of the spacecraft. By using space-to-space power beaming, the power system can be decoupled from the spacecraft and allow significantly higher spacecraft alpha (W/kg) and therefore enable significantly higher accelerations while maintaining high performance. This project assesses the efficacy of space-to-space power beaming to enable rapid orbit transfer while maintaining high mass utilization. Concept assessment requires integrated techniques for low-thrust orbit transfer steering laws, efficient large-scale rectenna systems, and satellite constellation configuration optimization. This project includes the development of an integrated tool with implementation of IPOPT, Q-Law, and power-beaming models. The results highlight the viability of the concept, limits and paths to infusion, and comparison to state-of-the-art capabilities. The results indicate the viability of power beaming for what may be the only approach for achieving the desired transit times with high specific impulse.

Dankanich, John W.↗

DOE OSTI2021

Vacancy‐Enabled O3 Phase Stabilization for Manganese‐Rich Layered Sodium Cathodes

Abstract Manganese‐rich layered oxide materials hold great potential as low‐cost and high‐capacity cathodes for Na‐ion batteries. However, they usually form a P2 phase and suffer from fast capacity fade. In this work, an O3 phase sodium cathode has been developed out of a Li and Mn‐rich layered material by leveraging the creation of transition metal (TM) and oxygen vacancies and the electrochemical exchange of Na and Li. The Mn‐rich layered cathode material remains primarily O3 phase during sodiation/desodiation and can have a full sodiation capacity of ca. 220 mAh g −1 . It delivers ca. 160 mAh g −1 specific capacity between 2–3.8 V with >86 % retention over 250 cycles. The TM and oxygen vacancies pre‐formed in the sodiated material enables a reversible migration of TMs from the TM layer to the tetrahedral sites in the Na layer upon de‐sodiation and sodiation. The migration creates metastable states, leading to increased kinetic barrier that prohibits a complete O3‐P3 phase transition.

Xiao, Biwei↗

DOE OSTI2024

High-Pressure Rate Rules for Ether Alkylperoxy Radical Isomerization

The first isomerization reaction of an alkylperoxy (RO 2 ) radical holds significant importance in low-temperature oxidation, as it governs the branching ratios of the hydroperoxyalkyl (QOOH) radicals, which influence the competition between the chain-propagation and chain-branching reactions. In this study, we systematically calculated high-pressure rate rules for the RO 2 isomerization reaction of monoethers, exploring 5-, 6-, 7-, and 8-membered ring transition states. Primary, secondary, and tertiary carbon sites, where both the abstracting peroxy group and the abstracted hydrogen are located, were considered, with particular emphasis on distinguishing between secondary carbons adjacent (alpha) and nonadjacent to the ether functional group. Using the G4//B3LYP/6-311++G(2df,2pd) level of theory and the transition state theory, we estimated the rate constants and the Arrhenius coefficient for over 120 possible isomerization reactions. We examined the effect of ring size and ring atoms, revealing that 6- and 7-membered ring isomerizations were generally the fastest. The impact of the ether functional group on transition states was investigated by comparing reactions with identical ring size, peroxy, and radical positions, but with the ether functional group positioned either outside (i.e., out) or inside (i.e., in) the transition state ring, leading to differences in the rate constants. When comparing to analogous alkane rate constants, differences of up to an order of magnitude were observed, underscoring the need for caution when assigning rate rules by analogy. We applied our rate constants in the di-iso-butyl ether kinetic model and evaluated their influence on low-temperature chemistry finding that they altered the branching ratios by up to a factor of 9, highlighting the significance of site-specific rate constants for more accurate low-temperature modeling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Unfolding of the Villin Headpiece Domain: Revealing Structural Heterogeneity with Time‐Resolved X‐Ray Solution Scattering and Markov State Modeling

Understanding protein folding pathways is crucial to deciphering the principles of protein structure and function. Here, the unfolding dynamics of the 35‐residue villin headpiece (HP35) and a norleucine‐substituted variant (2F4K) using a combination of experimental and computational techniques is investigated. Time‐resolved X‐ray solution scattering coupled with equilibrium molecular dynamics simulations and Markov state modeling reveals distinct unfolding mechanisms between the two variants: HP35 and 2F4K. Specifically, HP35 exhibits a two‐state unfolding process, whereas an intermediate state is identified for the 2F4K mutant. A Markov state model constructed from simulations is used to map atomic‐level transitions to experimental observations, providing insights into the role of sequence variations in modulating folding pathways. The findings underscore the importance of integrating experimental and computational approaches to unravel protein unfolding mechanisms between heterogenous structural ensembles.

Nijhawan, Adam K. [Department of Chemistry Northwe↗

DOE OSTI2021

Tipiracil binds to uridine site and inhibits Nsp15 endoribonuclease NendoU from SARS-CoV-2

SARS-CoV-2 Nsp15 is a uridine-specific endoribonuclease with C-terminal catalytic domain belonging to the EndoU family that is highly conserved in coronaviruses. As endoribonuclease activity seems to be responsible for the interference with the innate immune response, Nsp15 emerges as an attractive target for therapeutic intervention. Here we report the first structures with bound nucleotides and show how the enzyme specifically recognizes uridine moiety. In addition to a uridine site we present evidence for a second base binding site that can accommodate any base. The structure with a transition state analog, uridine vanadate, confirms interactions key to catalytic mechanisms. In the presence of manganese ions, the enzyme cleaves unpaired RNAs. This acquired knowledge was instrumental in identifying Tipiracil, an FDA approved drug that is used in the treatment of colorectal cancer, as a potential anti-COVID-19 drug. Using crystallography, biochemical, and whole-cell assays, we demonstrate that Tipiracil inhibits SARS-CoV-2 Nsp15 by interacting with the uridine binding pocket in the enzyme’s active site. Our findings provide new insights for the development of uracil scaffold-based drugs.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

Anomalies in the electromagnetic response and peculiarities of the domain structure in the magnetic Weyl semimetal Co 3⁢ Sn 2 ⁢S 2

In this paper, we present a comprehensive study of magnetic properties of Co 3 ⁢Sn 2 ⁢S 2 (CoSnS) crystals using macroscopic characterization and observations of the domain structure (DS) in a wide range of easy- and hard-axis fields (𝐻) and temperatures (𝑇). From macroscopic measurements, we derive temperature dependences of the basic magnetic parameters of the material [saturation magnetization 𝑀 𝑠 ⁡(𝑇), uniaxial anisotropy constant 𝐾⁡(𝑇), and exchange stiffness 𝐴⁡(𝑇)] and, based on them, calculate the thermodynamic magnetization 𝑀⁡(𝐻,𝑇) curves and DS parameters for pinning-free samples. We find important qualitative and quantitative differences between the theory and experiment defined by the efficient pinning of domain walls (DWs) in our samples. It turns out that, already at temperatures close to the ferromagnetic transition 𝑇 𝑐 , the DW dynamics falls into the heavy creep regime, resulting in a strong deferral of the DS adjustment into the equilibrium state. Here, we suggest that specific magnetic defects, responsible for pinning and causing field-tuned reproducible domain nucleation patterns observed in our high-quality samples, are pointlike. Recently found magnetic polarons formed around vacancies and impurities, which carry strong diamagnetic moments of spin-orbit nature and are intrinsic for CoSnS and expected in other Weyl semimetals, are a possible source of pinning yielding peculiar 𝑀⁡(𝐻,𝑇) response of CoSnS.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS2016

Performance of International Space Station Alpha Trace Contaminant Control Systems

The analysis presented herein was conducted during the early transitional period between the Space Station Freedom and the International Space Station programs as part of an effort to evaluate key design specifications and standards used by the United States and Russia. The analysis was originally documented under NASA cover letter ED62(36-94) dated August 16, 1994. The analysis was revised and rereleased under NASA cover letter ED62(51-94) dated November 14, 1994. These cover letters are provided here to guide programmatic context for the reader.

Perry, J. L.↗

DOE OSTI2021

Spin–Orbit Natural Transition Orbitals and Spin-Forbidden Transitions

Natural transition orbitals (NTOs) are in widespread use for visualizing and analyzing electronic transitions. Here, the present work introduces the analysis of formally spin-forbidden transitions with the help of complex-valued spin-orbit (SO) NTOs. The analysis specifically focuses on the components in such transitions that cause their intensity to be non-zero because of SO coupling. Transition properties such as transition dipole moments are partitioned into SO-NTO hole-particle pairs, such that contributions to the intensity from specific occupied and unoccupied orbitals are obtained. The method has been implemented within the restricted active space (RAS) self-consistent field wave function theory framework, with SO coupling treated by RAS state interaction. SO-NTOs have a broad range of potential applications, which is illustrated by the T 2 -S 1 state mixing in pyrazine, spin-forbidden vs. spin-allowed 4f–5d transitions in the Tb 3+ ion, and the phosphorescence of tris(2-phenylpyridine) iridium [Ir(ppy) 3 ].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Prediction of O and OH Adsorption on Transition Metal Oxide Surfaces from Bulk Descriptors

In the search for stable and active catalysts, density functional theory and machine learning (ML) based models can accelerate the screening of materials. While stability is conveniently addressed on the bulk level of computation, the modelling of catalytic activity requires expensive surface simulations. Here, in this work, we develop models for the surface adsorption energy of O and OH intermediates across a consistent and extensive dataset of pure transition metal oxide surfaces. We show that adsorption energies across metal oxidation states of +2 to +6 are well captured from the metal-oxygen bond strength extracted from the bulk level calculation. Specifically, we calculate the integrated crystal orbital Hamiltonian population (ICOHP) of the metal-oxygen bond in the bulk oxide and employ a simple normalization scheme to obtain a strong correlation with adsorption energetics. By combining our ICOHP descriptor with non DFT features in a Gaussian Process regression (GPR) model, we achieve high model accuracy with mean absolute errors of 0.166 and 0.219 eV for OH and O adsorption, respectively. By targeting the O-OH adsorption energy difference with our GPR model, we predict the the oxygen evolution reaction (OER) activity from bulk descriptors only. Furthermore, we utilize the strong correlation between the COHP and metal oxygen bond lengths to rapidly predict adsorption energetics and catalytic activity from the optimized bulk geometry. Our approach can enable an efficient search for active catalysts by eliminating the need for surface calculations in the initial screening phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Dirac Fermions and Flat Bands in Phosphorus Carbide Nanotubes: Structural and Quantum Phase Transitions in a Quasi-One-Dimensional Material

Chemically realistic quasi-one-dimensional (1D) materials in which Dirac Fermions and highly degenerate flat bands coexist intrinsically at the Fermi level are exceedingly rare, while representing a highly desirable platform for correlated and topological quantum phenomena. Here, in this work, using specialized symmetry-adapted first-principles calculations we predict a new class of nanomaterials─phosphorus carbide nanotubes (P 2 C 3 NTs)─obtained by rolling monolayer P 2 C 3 , a two-dimensional material shown in a previous letter to host “double Kagome bands”. Both armchair and zigzag P 2 C 3 NTs are stable at room temperature and feature the rare coexistence of Dirac crossings and multiple flat bands at the Fermi level inherited from the underlying honeycomb–Kagome lattice, with the flat bands resilient to elastic deformations. Under large strain, the structure transforms from honeycomb–Kagome to “brick-wall”, accompanied by multiple coupled structural and quantum phase transitions. We also uncover localized edge states, spin splitting from vacancies and dopants, and strain-tunable magnetism. Together, these results establish P 2 C 3 NTs as a chemically specific and mechanically tunable 1D material platform with potential applications in quantum hardware and spintronics.

carbon nanotubes↗

NASA NTRS1994

On the use of controls for subsonic transport performance improvement: Overview and future directions

Increasing competition among airline manufacturers and operators has highlighted the issue of aircraft efficiency. Fewer aircraft orders have led to an all-out efficiency improvement effort among the manufacturers to maintain if not increase their share of the shrinking number of aircraft sales. Aircraft efficiency is important in airline profitability and is key if fuel prices increase from their current low. In a continuing effort to improve aircraft efficiency and develop an optimal performance technology base, NASA Dryden Flight Research Center developed and flight tested an adaptive performance seeking control system to optimize the quasi-steady-state performance of the F-15 aircraft. The demonstrated technology is equally applicable to transport aircraft although with less improvement. NASA Dryden, in transitioning this technology to transport aircraft, is specifically exploring the feasibility of applying adaptive optimal control techniques to performance optimization of redundant control effectors. A simulation evaluation of a preliminary control law optimizes wing-aileron camber for minimum net aircraft drag. Two submodes are evaluated: one to minimize fuel and the other to maximize velocity. This paper covers the status of performance optimization of the current fleet of subsonic transports. Available integrated controls technologies are reviewed to define approaches using active controls. A candidate control law for adaptive performance optimization is presented along with examples of algorithm operation.

Gilyard, Glenn↗