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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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At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Linear Dichroism of the Optical Properties of SnS and SnSe Van der Waals Crystals

Abstract Tin monochalcogenides SnS and SnSe, belonging to a family of Van der Waals crystals isoelectronic to black phosphorus, are known as environmentally friendly materials promising for thermoelectric conversion applications. However, they exhibit other desired functionalities, such as intrinsic linear dichroism of the optical and electronic properties originating from strongly anisotropic orthorhombic crystal structures. This property makes them perfect candidates for polarization‐sensitive photodetectors working in near‐infrared spectral range. A comprehensive study of the SnS and SnSe crystals is presented, performed by means of optical spectroscopy and photoemission spectroscopy, supported by ab initio calculations. The studies reveal the high sensitivity of the optical response of both materials to the incident light polarization, which is interpreted in terms of the electronic band dispersion and orbital composition of the electronic bands, dictating the selection rules. From the photoemission investigation the ionization potential, electron affinity and work function are determined, which are parameters crucial for the design of devices based on semiconductor heterostructures.

Chemistry↗
DOE OSTI2025

Nanofilm Composite Membranes of Bottlebrush Poly(1,3‐Dioxolane) Plasticized by Poly(Ethylene Glycol) for CO 2 /N 2 Separation

Abstract Poly(1,3‐dioxolane) has emerged as a leading membrane material for post‐combustion CO 2 capture due to its high ether oxygen content and strong affinity toward CO 2 . However, they are often cross‐linked to inhibit crystallization, which makes them impossible to fabricate into industrial thin‐film composite membranes. Herein, soluble and high molecular weight bottlebrush polymers ( b PDXLA) are synthesized using reversible addition‐fragmentation chain transfer polymerization and demonstrate the feasibility of fabricating nanofilm (≈100 nm) composite membranes (NCMs). Furthermore, b PDXLA can be plasticized using a miscible additive of poly(ethylene glycol) dimethyl ether (PEGDME) to improve CO 2 permeability while retaining good CO 2 /N 2 selectivity. For example, adding 20 mass% PEGDME improves CO 2 permeance from 930 to 1300 GPU and decreases CO 2 /N 2 selectivity from 74 to 53 at 25 °C; the membrane exhibits stable separation performance competitive with state‐of‐the‐art commercial membranes. This work unveils a practical approach to designing uncross‐linked, highly polar polymers for practical membrane gas separation and highlights a facile way to enhance performance by incorporating miscible plasticizers using industrial manufacturing processes.

Zhang, Gengyi [Department of Chemical and Biologic↗
DOE OSTI2023

Ag Alloying in Cu 2– y Ag y Ba(Ge,Sn)Se 4 Films and Photovoltaic Devices

Trigonal Cu 2 BaGe 1–x Sn x Se 4 (CBGTSe) has recently gained interest as a potential photovoltaic absorber to target mitigation of antisite defect formation in Cu 2 ZnSn(S,Se) 4 . This study examines partial substitution of Cu by Ag as a potential approach to tune the properties of Ag-incorporated CBGTSe in the following aspects: 1) phase stability and crystal structure as a function of Ag content; 2) film morphology and grain structure; 3) charge carrier properties; 4) band positions; and 5) charge carrier kinetics and recombination. Up to 20% of Cu can be substituted by Ag in CBGTSe, while above 20% a phase mixture appears. Increasing Ag content induces larger average grain size and reduced hole carrier densities. In contrast, photoelectron spectroscopy and photoluminescence measurements reveal negligible impact of Ag substitution on ionization potential (≈5.4 eV) and electron affinity (≈3.7 eV). Also, Ag content offers negligible impact on carrier lifetimes (few ns). Consistent with these fundamental properties, solar cells based on two different Ag/(Ag + Cu) ratios (≈0% and ≈20%) show comparable power conversion efficiencies (≈2.7–2.8%). Finally, these results indicate that CBGTSe films and solar cells may be less sensitive to Ag substitution compared to Cu 2 ZnSn(S,Se) 4 , at least at the current level of absorber and device optimization.

14 SOLAR ENERGY↗
DOE OSTI2022

On the S-matrix of Ising field theory in two dimensions

We explore the analytic structure of the non-perturbative S-matrix in arguably the simplest family of massive non-integrable quantum field theories: the Ising field theory (IFT) in two dimensions, which may be viewed as the Ising CFT deformed by its two relevant operators, or equivalently, the scaling limit of the Ising model in a magnetic field. Our strategy is that of collider physics: we employ Hamiltonian truncation method (TFFSA) to extract the scattering phase of the lightest particles in the elastic regime, and combine it with S-matrix bootstrap methods based on unitarity and analyticity assumptions to determine the analytic continuation of the 2 → 2 S-matrix element to the complex s-plane. Focusing primarily on the “high temperature” regime in which the IFT interpolates between that of a weakly coupled massive fermion and the E 8 affine Toda theory, we will numerically determine 3-particle amplitudes, follow the evolution of poles and certain resonances of the S-matrix, and exclude the possibility of unknown wide resonances up to reasonably high energies.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Effective field theories as Lagrange spaces

We present a formulation of scalar effective field theories in terms of the geometry of Lagrange spaces. The horizontal geometry of the Lagrange space generalizes the Riemannian geometry on the scalar field manifold, inducing a broad class of affine connections that can be used to covariantly express and simplify tree-level scattering amplitudes. Meanwhile, the vertical geometry of the Lagrange space characterizes the physical validity of the effective field theory, as a torsion component comprises strictly higher-point Wilson coefficients. Imposing analyticity, unitarity, and symmetry on the theory then constrains the signs and sizes of derivatives of the torsion component, implying that physical theories correspond to a special class of vertical geometry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Geometry, spin coupling, and dielectric control of redox potentials in [4Fe–4S] Clusters

Iron–sulfur (Fe–S) clusters are common biological cofactors that facilitate vital redox reactions. Despite extensive research, the molecular basis of redox potential tuning in ferredoxin-like proteins remains an active area of debate. In this study, we combine statistical analysis of over one thousand [4Fe–4S]-containing protein structures from the Protein Data Bank (PDB) with broken-symmetry and extended broken-symmetry density functional theory to examine how cysteine ligand orientations and environmental screening affect redox properties of the clusters. We identified five main ligand configurations, three of which are predominant in natural structures. Among these, the adiabatic electron affinity differs by less than 0.1 V, indicating that, while geometry plays a secondary role, it allows localized fine-tuning of redox properties. In contrast, electrostatic and solvation effects primarily determine the overall potential range.

Computational Chemistry↗
DOE OSTI2023

Integrated data-driven and experimental approaches to accelerate lead optimization targeting SARS-CoV- 2 main protease

Identification of potential therapeutic candidates can be expedited by integrating computational modeling with domain aware machine learning (ML) approaches followed by experimental validation. Generative deep learning models have been recently developed that can generate thousands of new candidates, but their physiochemical properties are typically not optimized. Using our deep learning models and a scaffold as a starting point, we generated tens of thousands of compounds for SARS-CoV-2 M pro that preserve the core scaffold. Here we utilized and implemented several computational tools such as structural alert and toxicity analysis, high throughput virtual screening, ML-based 3D quantitative structure–activity relationships, multi-parameter optimization, and graph neural networks on libraries of generated candidates to predict biological activity and binding affinity a priori. From these collective computational results, eight promising candidates were identified and tested experimentally using Native Mass Spectrometry (MS) and FRET-based functional assays. Two compounds, with quinazoline-2-thiol and acetylpiperidine core moiety showed IC 50 values in the low micromolar range: 2.95±0.0017 µM and 3.41±0.0015 µM, respectively. The molecular dynamics simulations further highlight that binding of these compounds results in allosteric modulations in the chain B and the interface domains of the M pro . The key fragments from these top hits can be used as input for closed loop lead optimization in the integrated pipeline.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2021

Extraction of radium and actinium with Pb resin and Rose Bengal

The extraction of radium and actinium with Eichrom Pb resin and Rose Bengal has been studied. Radium and actinium both show a strong affinity (k’ > 10,000) for the resin at intermediate pHs (~ 5–7) from solutions with Rose Bengal. The pH range and magnitude of uptake for both radium and actinium is significantly increased by the presence of Rose Bengal compared to basic solutions without this counter ion. Additionally, radium uptake is extremely fast from basic solutions with and without Rose Bengal; actinium uptake is slower, particularly in solutions without Rose Bengal. Column studies show that despite the similar behavior of actinium and radium in this system, separations of these two elements with Pb resin and Rose Bengal solutions are possible with reasonable yields due to the differences in uptake kinetics.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2021

Separation of zirconium and hafnium from early actinides and rare earth elements with eichrom’s pb resin in HCl

The separation of zirconium and hafnium isotopes from the early actinides and rare earth elements (REE) with Eichrom’s Pb resin has been studied. Batch studies were performed to characterize the behavior of actinium, thorium, zirconium, hafnium, lutetium, and yttrium on Pb resin from HCl solutions (0.001 M to 11 M). The early actinides and REE had no affinity for the resin at any concentration of HCl, but zirconium and hafnium showed a moderate uptake at high concentrations of HCl with a maximum extraction at 11 M HCl. Several column separations were tested, including with only tracer isotopes and with mass. Rapid, simple separations of zirconium from actinium, thorium, protactinium, and the REE with high yields and low elution volumes are presented with applications for tracer isotope production and fission product separations. Furthermore, the resin is less suitable for hafnium separations as hafnium tends to bleed off the resin even at high concentrations of HCl.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Environmental controls on the kinetics of iron-sulfur cluster nucleation and nanoparticle formation

Anoxic, sulfidic conditions have been prevalent since the early Proterozoic and favor aqueous iron-sulfur (FeS aq ) clusters as a major fraction of the soluble, reduced iron and sulfur pool. FeS aq cluster formation and nucleation is driven by the high affinity between ferrous iron (Fe(II)) and sulfide (HS − ), ultimately yielding particles that precipitate as iron sulfide minerals. FeS aq clusters were recently shown to be bioavailable sources of iron and sulfur for a variety of anaerobes, yet little is known of the factors that influence the kinetics of their formation and nucleation. Here we apply computational and spectroscopic approaches to investigate the dynamics of FeS aq nucleation, cluster growth, precipitation, and redissolution as a function of Fe(II)/HS − concentration, temperature, and pH. Experiments were conducted under excess HS − to mimic euxinic conditions common to contemporary anaerobic aquatic ecosystems and those of the Proterozoic. Density functional theory calculations reveal the key role of water oxygen-iron interactions in stabilizing small FeS aq clusters and promoting solubility. Dynamic light scattering revealed a concentration-dependent increase in the kinetics of FeS aq nucleation and cluster aggregation. Increasing temperature promoted FeS aq cluster nucleation and aggregation while also enhancing dissolution. Alkaline pH also promoted FeS aq nucleation and cluster aggregation. At 25 °C, pH 7.0, and at reactant concentrations of 30 µM, FeS aq clusters < 10 nm in diameter remained in solution for > 2 h. These results underscore the importance of temperature, pH, and reactant concentration in the kinetics of FeS aq nucleation and cluster growth that, in turn, influence their bioavailability in anaerobic ecosystems.

Aquatic ecosystems↗
DOE OSTI2021

Ca2+ Effects on Fe(II) Interactions with Mn-Binding Sites in Mn-Depleted Oxygen-Evolving Complexes of Photosystem II and on Fe Replacement of Mn in Mn-Containing, Ca-Depleted Complexes

Fe(II) cations bind with high efficiency and specificity at the high-affinity (HA), Mn-binding site (termed the “blocking effect” since Fe blocks further electron donation to the site) of the oxygen-evolving complex (OEC) in Mn-depleted, photosystem II (PSII) membrane fragments (Semin et al. in Biochemistry 41:5854, 2002). Furthermore, Fe(II) cations can substitute for 1 or 2Mn cations (pH dependent) in Ca-depleted PSII membranes (Semin et al. in Journal of Bioenergetics and Biomembranes 48:227, 2016; Semin et al. in Journal of Photochemistry and Photobiology B 178:192, 2018). In the current study, we examined the effect of Ca2+ cations on the interaction of Fe(II) ions with Mn-depleted [PSII(-Mn)] and Ca-depleted [PSII(-Ca)] photosystem II membranes. We found that Ca2+ cations (about 50 mM) inhibit the light-dependent oxidation of Fe(II) (5 µM) by about 25% in PSII(-Mn) membranes, whereas inhibition of the blocking process is greater at about 40%. Blocking of the HA site by Fe cations also decreases the rate of charge recombination between QA- and YZ•+ from t1/2?=?30 ms to 46 ms. However, Ca2+ does not affect the rate during the blocking process. An Fe(II) cation (20 µM) replaces 1Mn cation in the Mn4CaO5 catalytic cluster of PSII(-Ca) membranes at pH 5.7 but 2 Mn cations at pH 6.5. In the presence of Ca2+ (10 mM) during the substitution process, Fe(II) is not able to extract Mn at pH 5.7 and extracts only 1Mn at pH 6.5 (instead of two without Ca2+). Measurements of fluorescence induction kinetics support these observations. Inhibition of Mn substitution with Fe(II) cations in the OEC only occurs with Ca2+ and Sr2+ cations, which are also able to restore oxygen evolution in PSII(-Ca) samples. Nonactive cations like La3+, Ni2+, Cd2+, and Mg2+ have no influence on the replacement of Mn with Fe. These results show that the location and/or ligand composition of one Mn cation in the Mn4CaO5 cluster is strongly affected by calcium depletion or rebinding and that bound calcium affects the redox potential of the extractable Mn4 cation in the OEC, making it resistant to reduction.

calcium↗
DOE OSTI2021

Chloride facilitates Mn(III) formation during photoassembly of the Photosystem II oxygen-evolving complex

The Mn 4 Ca oxygen-evolving complex (OEC) in Photosystem II (PSII) is assembled in situ from free Mn 2+ , Ca 2+ , and water. In an early light-driven step, Mn 2+ in a protein high-affinity site is oxidized to Mn 3+ . Using dual-mode electron paramagnetic resonance spectroscopy, we observed that Mn 3+ accumulation increases as chloride concentration increases in spinach PSII membranes depleted of all extrinsic subunits. At physiologically relevant pH values, this effect requires the presence of calcium. Here, when combined with pH studies, we conclude that the first Mn 2+ oxidation event in OEC assembly requires a deprotonation that is facilitated by chloride.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

The carbon-concentrating mechanism of the extremophilic red microalga Cyanidioschyzon merolae

Abstract Cyanidioschyzon merolae is an extremophilic red microalga which grows in low-pH, high-temperature environments. The basis of C. merolae ’s environmental resilience is not fully characterized, including whether this alga uses a carbon-concentrating mechanism (CCM). To determine if C. merolae uses a CCM, we measured CO 2 uptake parameters using an open-path infra-red gas analyzer and compared them to values expected in the absence of a CCM. These measurements and analysis indicated that C. merolae had the gas-exchange characteristics of a CCM-operating organism: low CO 2 compensation point, high affinity for external CO 2 , and minimized rubisco oxygenation. The biomass δ 13 C of C. merolae was also consistent with a CCM. The apparent presence of a CCM in C. merolae suggests the use of an unusual mechanism for carbon concentration, as C. merolae is thought to lack a pyrenoid and gas-exchange measurements indicated that C. merolae primarily takes up inorganic carbon as carbon dioxide, rather than bicarbonate. We use homology to known CCM components to propose a model of a pH-gradient-based CCM, and we discuss how this CCM can be further investigated.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Simulations of Tidal Disruption Events

Numerical simulations have historically played a major role in understanding the hydrodynamics of the tidal disruption process. Given the complexity of the geometry of the system, the challenges posed by the problem have indeed stimulated much work on the numerical side. Smoothed Particles Hydrodynamics methods, for example, have seen their very first applications in the context of tidal disruption and still play a major role to this day. Likewise, initial attempts at simulating the evolution of the disrupted star with the so-called affine method have been historically very useful. Here, we provide an overview of the numerical techniques used in the field and of their limitations, and summarize the work that has been done to simulate numerically the tidal disruption process.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Oxygen Effects and Selective Oxidation of Group IV Alloying Additions in Group V-Based Refractory Multi-principal Element Alloys

Refractory multi-principal element alloys (RMPEAs) hold significant potential for advancing ultra-high-temperature technologies due to their remarkable strength retention under these conditions. However, the beneficial effects of alloying on microstructural evolution and mechanical properties are often obscured by the presence of interstitial alloying elements. The intricate interactions between substitutional alloying elements of Groups IV, V, and VI and interstitial content, whether intentional or incidental, remain poorly understood. In this study, we investigate the impact of dissolved oxygen on the microstructural evolution and stability of RMPEAs primarily composed of Group V elements, Nb and V, along with Group IV elements Ti, Zr, and Hf. We show that the strong affinity of oxygen for Group IV elements Zr and Hf leads to the internal precipitation of oxides during heat treatment, which competes with the homogenization of the as-cast dendritic microstructure. Here, we demonstrate that careful control and design of oxygen content and Group IV alloying additions are essential to minimize micro-segregation and prevent the detrimental precipitation of internal oxides. To address these challenges, we propose employing non-equilibrium solidification calculations to predict and optimize as-cast solidification structures, thereby reducing the reliance on homogenization processes.

Alloy design↗
DOE OSTI2024

Data-Driven Insights into the Structural Essence of Plasticity in High-Entropy Alloys

The heterogeneous mechanical response of a crystalline alloy with multiple principal elements was investigated using molecular dynamics simulations. The local configuration of the alloy in its quiescent state was characterized by the variables derived from the gyration tensor and the atomic electronegativity. A multivariate analysis identified the geometric and chemical factors that influenced the atomic packing variations. Further, upon straining, the non-affine displacement exhibited spatial heterogeneity. A statistical correlation was established between the local yield events and the specific features of the local configuration. Our findings, validated by the performance metrics analysis, provided a structural criterion for the instability mechanisms in high-entropy alloys (HEAs) and enhanced the understanding of their plasticity.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Effect of directed energy deposition process parameter on build quality of tantalum

Tantalum is a refractory metal used in a variety of harsh environment applications. Additive manufacturing of tantalum is limited based on its high melting point and affinity for oxygen. Directed Energy Deposition is an additive manufacturing technique with rapid deposition time and compositional flexibility within builds. Additively manufactured tantalum is susceptible to a variety of material and process-based defects. Various lack-of-fusion defects were identified resulting from excessive powder feed rates or insufficient laser power. Oxygen impurities in some samples caused cracking and increased material hardness. Precipitates were identified in the highly oxidized samples which were printed immediately after the build chamber was opened. High-density, low-defect parts were successfully produced. The effects of scan speed, laser power, and powder feed rate on density and defects were analyzed. A processing window was identified for producing high-quality parts which requires adequately high laser power and lower powder feed rate.

DED↗
DOE OSTI2020

Protein kinase A in the neutron beam: Insights for catalysis from directly observing protons

Protein kinases transmit chemical signals by phosphorylating substrate proteins, thus regulating a multitude of cellular processes. cAMP-dependent protein kinase (PKA), a prototypical enzyme for the whole kinase family, has been the focus of research for several decades, however, the details of the chemical mechanism of phosphoryl group transfer have remained unknown. We used neutron crystallography to map key proton sites and hydrogen bonding interactions in the PKA catalytic subunit (PKAc) in a product complex containing adenosine diphosphate (ADP) and the phosphorylated high affinity protein kinase substrate (pPKS) peptide. To improve neutron diffraction, we deuterated PKAc allowing us to use very small crystals. In the product complex, the phosphoryl group of pPKS is protonated whereas the catalytic Asp166 is not. H/D exchange analysis of the main-chain amides and comparison with the NMR analysis of PKAc with inhibitor peptide complex revealed exchangeable amides that may distinguish the catalytic and inhibited states.

59 BASIC BIOLOGICAL SCIENCES↗