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

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Chemically Separable Ruthenium Hydride Isomers with Distinct Hydride Transfer Properties

Transition metal hydrides are key intermediates in biological and industrial catalysis, where control over hydride donor ability (hydricity) is essential for optimizing reactivity. Herein, we report a series of isomeric ruthenium hydrides in which the ligand trans to the ruthenium hydride bond–either an N-heterocyclic carbene or pyridine–modulates the thermodynamic hydricity by up to 8 kcal mol –1 . These hydrides exhibited distinct reactivity toward CO 2 and various organic hydride acceptors, enabling detailed kinetic and mechanistic analysis. Stopped-flow experiments, isotopic labeling, and computational studies supported an outer-sphere hydride transfer mechanism. Linear free energy relationships (LFERs) and Marcus relationships were utilized to correlate the changes in thermodynamics and kinetics, revealing that ligands with strong trans effects and trans influence can disrupt conventional scaling relationships, which can be a powerful strategy for promoting new reactivity paradigms in hydride transfer reactions.

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

Unexpected Hydricity of a Bis-Carbene Iridium Complex Provides Insight into Electronic Structure Impacts on Hydride Donor Ability

The hydricity (ΔG° H– ), or hydride donor ability, of a transition metal complex is a thermodynamic parameter which can aid in the design and interpretation of various catalytic reactions that involve hydride transfer as a key step. In an attempt to generate a strong hydride donor, the bis-carbene ligand 3,3′-methylenebis(1-methyl-imidazol-2-ylidene) (“bis-mim”) was installed in an iridium hydride complex, [Cp*Ir(bis-mim)H] + . Experimental and computational studies show that [Cp*Ir(bis-mim)H] + is actually a relatively weak hydride donor, however. To understand why the complex is an unexpectedly weak hydride donor, experimental and computational studies probing the steric and electronic effects on hydricity were conducted. Steric factors had a minimal impact on thermodynamic hydricity but dampened kinetic hydricity. In conclusion, the poor thermodynamic hydride donor ability can be attributed to an electronic structure that results in relatively long Cp*−Ir bonds, an unusually high Ir–H BDFE and pK a values that have an outsized influence on thermochemical cycles for hydricity.

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

Time-reversal of an unknown quantum state

For decades, researchers have sought to understand how the irreversibility of the surrounding world emerges from the seemingly time-symmetric, fundamental laws of physics. Quantum mechanics conjectured a clue that final irreversibility is set by the measurement procedure and that the time-reversal requires complex conjugation of the wave function, which is overly complex to spontaneously appear in nature. Building on this Landau-Wigner conjecture, it became possible to demonstrate that time-reversal is exponentially improbable in a virgin nature and to design an algorithm artificially reversing a time arrow for a given quantum state on the IBM quantum computer. However, the implemented arrow-of-time reversal embraced only the known states initially disentangled from the thermodynamic reservoir. Here we develop a procedure for reversing the temporal evolution of an arbitrary unknown quantum state. This opens the route for general universal algorithms sending temporal evolution of an arbitrary system backward in time.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

A Computational Framework to Accelerate the Discovery of Perovskites for Solar Thermochemical Hydrogen Production: Identification of Gd Perovskite Oxide Redox Mediators

A high-throughput computational framework to identify novel multinary perovskite redox mediators is presented, and this framework is applied to discover the Gd-containing perovskite oxide compositions Gd 2 BB'O 6 , GdA'B 2 O 6 , and GdA'BB'O 6 that split water. The computational scheme uses a sequence of empirical approaches to evaluate the stabilities, electronic properties, and oxygen vacancy thermodynamics of these materials, including contributions to the enthalpies and entropies of reduction, ΔH TR and ΔS TR . This scheme uses the machine-learned descriptor τ to identify compositions that are likely stable as perovskites, the bond valence method to estimate the magnitude and phase of BO 6 octahedral tilting and provide accurate initial estimates of perovskite geometries, and density functional theory including magnetic- and defect-sampling to predict STCH-relevant properties. Eighty-three promising STCH candidate perovskite oxides down-selected from 4392 Gd-containing compositions are reported, three of which are referred to experimental collaborators for characterization and exhibit STCH activity. Our results demonstrate that the high-throughput computational scheme described herein—which is used to evaluate Gd-containing compositions but can be applied to any multinary perovskite oxide compositional space(s) of interest—accelerates the discovery of novel STCH active redox mediators with reasonable computational expense.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Production of Very Light Elements and Strontium in the Early Ejecta of Neutron Star Mergers

Abstract We study the production of very light elements ( Z < 20) in the dynamical and spiral-wave wind ejecta of binary neutron star mergers by combining detailed nucleosynthesis calculations with the outcome of numerical relativity merger simulations. All our models are targeted to GW170817 and include neutrino radiation. We explore different finite-temperature, composition-dependent nuclear equations of state, and binary mass ratios, and find that hydrogen and helium are the most abundant light elements. For both elements, the decay of free neutrons is the driving nuclear reaction. In particular, ∼0.5–2 × 10 −6 M ⊙ of hydrogen are produced in the fast expanding tail of the dynamical ejecta, while ∼1.5–11 × 10 −6 M ⊙ of helium are synthesized in the bulk of the dynamical ejecta, usually in association with heavy r -process elements. By computing synthetic spectra, we find that the possibility of detecting hydrogen and helium features in kilonova spectra is very unlikely for fiducial masses and luminosities, even when including nonlocal thermodynamic equilibrium effects. The latter could be crucial to observe helium lines a few days after merger for faint kilonovae or for luminous kilonovae ejecting large masses of helium. Finally, we compute the amount of strontium synthesized in the dynamical and spiral-wave wind ejecta, and find that it is consistent with (or even larger than, in the case of a long-lived remnant) the one required to explain early spectral features in the kilonova of GW170817.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Gravity effects on Hawking radiation from charged black strings in Rastall theory

Highlights: • Introductory review of charged black strings in Rastall theory. • Detailed description of Hawking temperature. • Graphically Analysis of Hawking temperature. • Discuss the stability of charged black strings. The Rastall theory of gravity is the generalized form of the Einstein theory which describes the conservation law of energy and momentum tensor. In our work, we compute the charged black strings solution in the background of Rastall theory by applying the Newman–Janis approach. After computing the charged black strings solution in the background of Rastall theory, we study the thermodynamical property (i.e., Hawking temperature) for the charged black strings. Furthermore, we investigate the graphical representation of Hawking temperature via event horizon to check the stability conditions of charged black strings under the influence of Rastall theory. Moreover, we examine the modified Hawking temperature for charged black strings in Rastall theory by taking into account the quantum gravity effects. We also discuss the physical state of charged black strings under the effects of quantum gravity and spin parameter (appears due to Rastall theory in charged black strings solution).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

An accelerated approach to inline non-LTE modeling

A goal across many physics and engineering disciplines is to use radiation-hydrodynamics codes to accurately simulate systems that are expected to deviate from local thermodynamic equilibrium (LTE), such as laser-driven hohlraums, stellar coronae, and supernova ejecta. The computational expense of traditional non-LTE (NLTE) opacity calculations can dominate the cost of simulating these systems and render NLTE physics untenable in most cases. In this paper, we present a new parallel implementation for NLTE opacity calculations that employs advanced load balancing, vectorization, and memory management to significantly reduce the computational costs of these calculations. Using the radiation-hydrodynamics code xRAGE , we demonstrate this new implementation on three test problems and present order-of-magnitude speed improvements.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Homoleptic An(IV) Dimethyl Sulfoxide Complexes of Th–Pu Enable Insight into Solution Speciation and Redox

A family of 8- and 9- coordinate homoleptic dimethyl sulfoxide An(IV) complexes is used to evaluate the solvation properties of tetravalent actinide ions in dimethyl sulfoxide (DMSO) vs aqueous media. These compounds are prepared from aqueous mixtures of DMSO and yield crystalline solids, whose solid-state electronic absorption spectra are compared to solution phase spectra, providing insight into the solution speciation. The thermodynamics of the equilibria between the 8- and 9-coordinate compounds were determined experimentally and computationally, showing a trend that correlates with ionic radius. Cyclic voltammetry data for the +IV/+III couples of Np and Pu in the DMSO electrolyte indicate that the +IV ions are significantly stabilized compared to aqueous media due to the more donating nature of DMSO compared to water. As a result, computational studies of these systems indicate that further reactivity may take place upon reduction to the +III oxidation state.

Actinides↗
DOE OSTI2021

The Energy Exascale Earth System Model Simulations With High Vertical Resolution in the Lower Troposphere

Abstract General circulation models (GCMs) are typically run with coarse vertical resolution. For example, the Energy Exascale Earth System Model (E3SM) has a vertical resolution of about 200 m in the boundary layer, which is far too coarse to resolve sharp gradients often found in the thermodynamic fields capping subtropical marine stratocumulus. In this article, we present a series of multiyear atmosphere only simulations of E3SM version 1 where we progressively increase the vertical resolution in the lower troposphere to scales approaching those often used in large eddy simulation (LES). We report marginal impacts in regards to the simulation of boundary layer clouds when vertical resolution is moderately increased, yet find significant positive impacts when the vertical resolution approaches that typically used in LES (∼10 m). In these experiments, there is a marked change in the simulated turbulence and thermodynamics which leads to more abundant marine stratocumulus. However, these simulations are burdened with excessive computational cost. They are also subject to degradations in overall climate metrics due to time step sensitivities and because some processes and parameterizations are sensitive to changes in the vertical resolution.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Probing entanglement in a 2D hard-core Bose–Hubbard lattice

Entanglement and its propagation are central to understanding many physical properties of quantum systems. Notably, within closed quantum many-body systems, entanglement is believed to yield emergent thermodynamic behaviour. However, a universal understanding remains challenging owing to the non-integrability and computational intractability of most large-scale quantum systems. Quantum hardware platforms provide a means to study the formation and scaling of entanglement in interacting many-body systems. Here we use a controllable 4 × 4 array of superconducting qubits to emulate a 2D hard-core Bose–Hubbard (HCBH) lattice. We generate superposition states by simultaneously driving all lattice sites and extract correlation lengths and entanglement entropy across its many-body energy spectrum. We observe volume-law entanglement scaling for states at the centre of the spectrum and a crossover to the onset of area-law scaling near its edges.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Interfacial water asymmetry at ideal electrochemical interfaces

Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements and the thermodynamics of the inner layer with potential of maximum entropy measurements. Relating these properties by computational modeling of the electrochemical interface has so far been challenging due to the low accuracy of classical molecular dynamics (MD) for capacitance and the limited time and length scales of ab initio MD. Here, we combine large ensembles of long-time-scale classical MD simulations with charge response from electronic density functional theory to predict the potential-dependent capacitance of a family of ideal aqueous electrochemical interfaces with different peak capacitances. We show that while the potential of maximum capacitance varies, this entire family exhibits an electrode charge of maximum capacitance (CMC) between -2.9 and -2.2 μC/cm 2 , regardless of the details in the electronic response. Simulated heating of the same interfaces reveals that the entropy peaks at a charge of maximum entropy (CME) of -5.1 ± 0.6 μC/cm 2 , in agreement with experimental findings for metallic electrodes. The CME and CMC both indicate asymmetric response of interfacial water that is stronger for negatively charged electrodes, while the difference between CME and CMC illustrates the richness in behavior of even the ideal electrochemical interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Understanding and Overcoming Water-induced Interfacial Degradation in Si Modules (Final Technical Report)

Moisture ingress is an established issue for photovoltaic module durability. Durability studies probing moisture effects typically evaluate performance losses at the module level, attributing global power losses to the overall humidity condition of the test environment while leaving local module behavior unknown. This project successfully develops an in situ short-wave infrared probe of moisture content in PV modules with demonstrated detection limits better than 100 ppm in EVA-encapsulated Al-BSF and PERC architectures (66 µg/cm3) and applicability across the range of terrestrial conditions. Combining this optical moisture quantification method (water reflectometry detection, WaRD) with peel testing of interfaces, biased photoluminescence imaging of performance, and first principles computation, we correlate module moisture content and cell performance over the course of accelerated damp heat tests. By performing multi-level humidity and thermal accelerated testing over thousands of hours (0, 65 and 85% RH and 25, 65, and 85°C), we are able to attribute effects of individual environmental stresses and the dependence on module architecture. Using first-principles computational chemistry, we find that the decomposition of EVA to acetic acid (Norrish II) is thermodynamically preferred over a pathway to acetaldehyde (Norrish I), elucidating the underlying chemistry of encapsulant degradation. We also find it is likely that water segregates to the stable interfaces of the cell, especially the SiNx/EVA interface. We find that moisture is strongly correlated with reduction in adhesion at the interfaces of the cells, particularly at Ag fingers. We show uniquely that the peel strength required to delaminate the encapsulant from the front of the cell depends not only on the exposure to a high heat and humid environment, but also to the moisture content during the mechanical testing, indicating an important interaction between when mechanical stresses are faced in terms of the moisture content of the module and its durability. We find that the background sheet resistance (that is, the sheet resistance rise not attributable to finger interruptions or cracks) is substantially higher in the backsheet mini-modules vs glass-glass packages when humidity and temperature are faced. This increase in power loss due to the background resistance increase over time in damp heat in glass-backsheet modules resulted in ~3-4% larger decrease in relative PCE compared to glass-glass modules. In glass-backsheet modules, the effect of the moisture dose alone is comparable or greater than that of the combined temperature and water term, suggesting that glass-backsheet modules are overall more susceptible to moisture induced performance loss. Finally, we show that thin film PV modules are amenable to WaRD measurement, based on the ability to detect moisture in POE encapsulants or in the cell stack itself. The ease of WaRD measurement and its few requirements on the bill of materials should enable broad applicability of this technique for studying the effects of moisture in PV.

14 SOLAR ENERGY↗
DOE OSTI2025

Understanding the Electronic Behavior of f-Element Intermetallics

Due to their partially filled f-orbitals, lanthanide and actinide intermetallic materials exhibit intriguing electronic, structural, and magnetic properties. These materials provide a unique platform to explore exotic magnetic and quantum phenomena that arise from their strongly correlated f-electrons, offering insights into f-electron behavior. Incorporating light elements such as boron and carbon can significantly impact the electronic, chemical, and physical properties of these materials, with varying influence between lanthanides and actinides due to the more localized f-electrons in lanthanides. In this work, lanthanide-based intermetallic single crystals containing light atoms were synthesized using the molten metal flux growth method. In this method, one or more low-melting metals such as aluminum, gallium, tin, and bismuth are used in excess as the reaction medium. This solution-state approach allows for lower reaction temperatures compared to solid-state reactions and enables the isolation of kinetic products rather than thermodynamically stable compounds. The synthesized crystals were analyzed using an extensive array of analytical and computational characterization techniques, including single crystal X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, magnetization measurements, and density functional theory calculations. These analyses provided detailed insights into the structural and magnetic properties of the synthesized materials.

37 - INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL C↗
DOE OSTI2024

Thermodynamics of the near-extremal Kerr spacetime

We examine the thermodynamics of a near-extremal Kerr black hole, and demonstrate that the geometry behaves as an ordinary quantum system with a vanishingly small degeneracy at low temperatures. This is in contrast with the classical analysis, which instead predicts a macroscopic entropy for the extremal Kerr black hole. Our results follow from a careful analysis of the gravitational path integral. Specifically, the low temperature canonical partition function behaves as Z ~ T$\frac{3}{2}$ e S 0 +c log S 0 , with S 0 the classical degeneracy and c a numerical coefficient we compute. This is in line with the general expectations for non-supersymmetric near-extremal black hole thermodynamics, as has been clarified in the recent past, although cases without spherical symmetry have not yet been fully analyzed until now. We also point out some curious features relating to the rotational zero modes of the near-extremal Kerr black hole background that affects the coefficient c. This raises a puzzle when considering similar black holes in string theory. Our results generalize to other rotating black holes, as we briefly exemplify.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations

Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here in this paper, electrospray ionization was used to generate gas-phase complexes [ML 3 ] 3+ , where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML 3 ] 3+ in the presence of H 2 O yielded a protonated ligand [L(H)] + and hydroxide [ML 2 (OH)] 2+ or hydrate [ML(L–H)(H 2 O)] 2+ , where (L–H) - is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am 3+ versus Ln 3+ , the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL 3 ] 3+ versus [LaL 3 ] 3+ and for both product isomers, [ML 2 (OH)] 2+ and [ML(L–H)(H 2 O)] 2+ . More facile removal of a ligand from [AmL 3 ] 3+ by CID does not necessarily contradict stronger Am 3+ –L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal–ligand bonding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Experimental and computational investigation into the hydrodynamics and chemical dynamics of laser ablation aluminum plasmas

Laser ablation plasma chemistry is governed by a complex interplay between hydrodynamic plasma-gas mixing processes, thermodynamics, and rapid high-temperature chemical reactions. Here, in this work, we investigate the gas-phase oxidation chemistry of ns-laser ablation aluminum plasmas in air using optical spectroscopy combined with advanced multi-physics modeling. Experimental measurements demonstrate the formation of AlO in the plasma plume as early as 1 μs while computational results reveal that several Al x O y species are distributed in the periphery of the plume at even earlier times (<20 ns) in the presence of large temperature gradients and strong shockwaves. Interactions with the ablation crater during rapid plume expansion are shown to initiate vortex formation, followed by mixing dynamics that work to pull AlO into the vortices to react with gas-phase Al to form Al 2 O. Oxygen and several aluminum oxides are simultaneously pulled up through the stem of the fireball, encouraging further intermixing between reacting species and enhanced molecular formation. This work concludes that chemical dynamics in laser ablation plasmas is driven by diffusion processes, concentration gradients, and plume hydrodynamics while strong shockwaves generated during laser ablation do not impede chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

High temperature stability and transport characteristics of hydrogen in alumina via multiscale computation

Here, the impact of hydrogen charge states on the stability and transport characteristics of hydrogen interstitials in alumina polymorphs is evaluated by multiscale computational methods including density functional theory (DFT), ab initio molecular dynamics (AIMD) and machine learned force fields. Thermodynamic calculations show that the protonic H i +1 interstitial is the most stable defect species for most values of the electronic bandgap in both and amorphous alumina (Al 2 O 3 ). Further, active learned Gaussian approximation potentials (GAP) were developed using AIMD data to study temperature dependent long time proton diffusion in alumina. Diffusivity calculations from GAP-MD simulations are found to be comparable with of the AIMD data, while being ~340 times faster and scalable to larger systems. Comparisons with diffusivity values for other interstitial charge states (H i 0 and H i -1 ) and published experimental literature indicate that H i +1 diffusion is the likely mechanism of hydrogen transport. A good agreement is obtained between H i +1 diffusivity calculated in α-Al 2 O 3 from DFT: 5.05 10 -3 exp(-0.81 eV/k B /T) cm 2 /s and reported experiment: 9.7X10 -4 exp(-0.83 eV/k B /T) cm 2 /s. Computationally and experimentally calculated energy barriers (0.81 and 0.83 eV respectively) only differ by 2.5%. Similarly, the pre-exponential diffusion coefficients only differ by 0.5 orders of magnitude. Moreover, the diffusivity of H i +1 in amorphous Al 2 O 3 in the 1000–2000 K range is calculated to be 2.53X10 -2 exp(-0.89 eV/k B /T), just one order of magnitude higher than the corresponding value in α-Al 2 O 3 . This suggests that local structural disorder does not significantly affect the energy landscape and diffusion behavior of H i +1 in Al 2 O 3 . Overall, these results show promise for the application of alumina polymorphs as hydrogen permeation barriers.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Computational Analysis of the Energetic Stability of High-Entropy Structures of a Prototypical Lanthanide-Based Metal–Organic Framework

High-entropy materials are characterized by their complex compositions, typically comprising five or more elements in near-equiatomic proportions. Applying this concept to metal ions in metal−organic frameworks (MOFs) has paved the way for exploring a new class of high-entropy MOFs. While the compositional strategy of high-entropy materials leverages configurational entropy to aid thermodynamic stability, it also poses significant analytical challenges due to the vast compositional landscape and diverse phases that these materials can adopt. We present a computational study of several complexities associated with selecting potential high-entropy versions of a prototype lanthanidebased MOF. We compute the energetics of metal mixing of these heterometallic MOFs using density functional theory (DFT) and machine learning interatomic potential (MLIP) methods. The use of MLIP methods allows a systematic exploration of the convex hull of thermodynamically stable MOF structures containing up to 5 distinct metals.

Chemical structure↗