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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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Pressure Effects on the 4 f Electronic Structure of Light Lanthanides

Adopting the satellite structure of the $\mathcal{Lγ_1}$ line in nonresonant x-ray emission spectra, we probe the high-pressure evolution of the bare 4f signature of the early light lanthanides at ambient temperature. For Ce and Pr the satellite peak experiences a sudden reduction concurrent with their respective volume collapse (VC) transitions. These new experimental results are supported by calculations using state-of-the-art extended atomic structure codes for Ce and Pr, and also for Nd, which does not exhibit a VC. Here, our work suggests that changes to the 4f occupation are more consistently associated with evolution of the satellite than is the reduction of the 4f moment. Indeed, we show that in the case of Ce, mixing of a higher atomic angular momentum state, driven by the increased hybridization, acts to obscure the expected satellite reduction. These measurements emphasize the importance of a unified study of a full set of microscopic observables to obtain the most discerning test of the underlying, fundamental f-electron phenomena at high pressures.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Two-dimensional polythiophene homopolymer as promising hole transport material for high-performance perovskite solar cells

A polythiophene homopolymer with conjugated side chains (2D-PT) was applied as a hole transport material (HTM) of perovskite solar cells (PSCs). The all-conjugated two-dimensional structure effectively increases the ionization potential, realizing a high open-circuit voltage near 1 V for the 2D-PT-based PSC. Very interestingly, the two-dimensional wide-angle X-ray scattering measurements show that the 2D-PT molecules are self-assembled into ordered structure with a face-on dominant orientation and exhibit a hole mobility, which is ~1.6 times faster than that of poly(3-hexylthiophene) (P3HT). Consequently, the power conversion efficiency of PSC is noticeably increased by ~30% as 2D-PT replaces P3HT as HTM. Moreover, the densely packed 2D-PT slows down the moisture induced degradation of perovskite crystals, leading to a better environmental stability. As a result, this work demonstrates that two-dimensional non-donor-acceptor structural conjugated polymers can be utilized as promising HTM of PSCs.

36 MATERIALS SCIENCE↗
NASA NTRS1992

Compressibility effects on large structures in free shear flows

Space-time correlations were used to study compressibility effects on large structures in mixing layers. Two high-Reynolds number mixing layers with M(c) = 0.51 (case 1) and 0.86 (case 2) were studied. The results indicate that the structures in case 1 are similar to those in the incompressible case, but less organized. The structures in case 2 are highly three-dimensional, with a good spatial but a poor temporal orgnization. The streamwise correlations showed a decay rate four to five times greater for case 2 relative to case 1. While the spanwise correlations for case 1 showed trends similar to incompressible mixing layers, the behavior of case 2 was very different. The pressure fluctuations in the fully developed region of case 2 displayed significant rms variation in the spanwise direction with a well-defined pattern. Based on these measurements, the structures in case 2 seem to be of a horseshoe type, transversely spanning the mixing layer with the head in the low-speed side and the legs inclined in both the x-y and the x-z planes.

Samimy, M.↗
NASA NTRS1996

Planning an Effective Speakers Outreach Program

The National Aeronautics and Space Administration (NASA) and, in particular, the Marshall Space Flight Center (MSFC) have played pivotal roles in the advancement of space exploration and space-related science and discovery since the early 1960's. Many of the extraordinary accomplishments and advancements of NASA and MSFC have gone largely unheralded to the general public, though they often border on the miraculous. This lack of suitable and deserved announcement of these "miracles" seems to have occurred because NASA engineers and scientists are inclined to regard extraordinary accomplishment as a normal course of events. The goal in this project has been to determine an effective structure and mechanism for communicating to the general public the extent to which our investment in our US civilian space program, NASA, is, in fact, a very wise investment. The project has involved discerning important messages of truth which beg to be conveyed to the public. It also sought to identify MSFC personnel who are particularly effective as messengers or communicators. A third aspect of the project was to identify particular target audiences who would appreciate knowing the facts about their NASA investment. The intent is to incorporate the results into the formation of an effective, proactive MSFC speakers bureau. A corollary accomplishment for the summer was participation in the formation of an educational outreach program known as Nasa Ambassadors. Nasa Ambassadors are chosen from the participants in the various MSFC summer programs including: Summer Faculty Fellowship Program (SFFP), Science Teacher Enrichment Program (STEP), Community College Enrichment Program (CCEP), Joint Venture (JOVE) program, and the NASA Academy program. NASA Ambassadors agree to make pre-packaged NASA-related presentations to non-academic audiences in their home communities. The packaged presentations were created by a small cadre of participants from the 1996 MSFC summer programs, volunteering their time beyond their normal NASA summer research commitment. A total of eight presentations were created and made available for use by NASA Ambassadors. A major segment of the research effort during the summer has been devoted to verifying and documenting certain "spinoff' contributions of NASA technology and in determining their relevance and impact to our society and our nation's economy. The purpose behind the verification/documentation research has been to shed light on the question of whether or not our NASA investment is a wise investment. It has revealed that NASA is a wise investment.

McDonald, Malcolm W.↗
DOE OSTI2018

Linear and Nonlinear Optical Properties of Metal Nanocomposite Materials

The scientific theme of this award stated in its title is “Linear and Nonlinear Optical Properties of Metal Nanoparticle Composites.” The motivation for the proposal was based on prior work that highlighted unusual third-order nonlinear optical response of metal-nanoparticle composites created by Vanderbilt researchers at the Oak Ridge National Laboratory (ORNL) by implanting metal ions into fused-silica and sapphire substrates and annealing them under appropriate conditions to produce a solid solution comprising noble-metal nanoparticles embedded in an insulating matrix. For example, the well-known localized surface plasmon resonance (LSPR) of gold and silver nanoclusters and nanoparticles was known to yield enhanced effects on the nonlinear absorption and nonlinear refractive index of these materials. The project soon expanded to embrace a wider range of materials and nanostructures, including particularly vanadium dioxide with its insulator-to-metal transition, a wide variety of substrate hosts, and zinc oxide with its multi-faceted band-edge exciton that can be coupled to plasmonic degrees of freedom in silver and aluminum. We employed second- and third-order nonlinear optical spectroscopies and confocal microscopy to quantify the coupling between nanoparticles and adsorbates across interfaces. Because ORNL closed the ion-beam surface-modification facility in 2004, we then developed a nanofabrication technique combining focused ion-beam lithography and pulsed laser deposition to create ordered arrays of metal and oxide nanoparticles in various planar geometries and heterostructures. By 2008, aided by finite-difference time-domain and finite-element calculations, we began to design and fabricate plasmonic “workbenches” on which we could excite quasiparticles (e.g., excitons, phonons, plasmons) using optical signals and electrical impulses, and map the material response down to femtosecond time and nanometer length scales. We developed additional nanofabrication capabilities (e.g., dual-layer electron-beam lithography, quantum-well fabrication and multilayer magnetron sputtering and electron-beam deposition) to create a variety of novel heterostructures as model nanocomposite systems. This led to several new opportunities to study the optical properties of these composites informed by views of potential device configurations. Among the scientific themes that emerged in published papers based on new materials and nanostructures were the following: ultrafast electron dynamics in metamaterials, including ultrafast THz microscopy of the insulator-to-metal transition in VO 2 nanoparticles; plasmon-driven electron injection to promote phase transitions in VO 2 ; and second-harmonic generation in nanostructures without inversion symmetry, in particular, the Archimedean spiral with overall sub-wavelength dimensions. We also explored dimensional and structural effects in plasmonic coupling, including exciton-plasmon coupling in ZnO nanowires; exciton-plasmon coupling in structures incorporating two-dimensional dichalcogenides; and tunable plasmon-induced transparency in plasmonic heterostructures incorporating phase-changing VO 2 . Finally, it should be noted that the work on Archimedean nanospirals and plasmon-exciton coupling led directly into a current quantum-optics research project on photon correlations in diamond nanoparticles, exemplified by the first publication from that effort [Ref. [47] in the bibliography]. A more detailed account setting in the appropriate scientific context all forty-eight papers supported by this award follows.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Amino Acid Residues Controlling Domain Interaction and Interdomain Electron Transfer in Cellobiose Dehydrogenase

The function of cellobiose dehydrogenase (CDH) in biosensors, biofuel cells, and as a physiological redox partner of lytic polysaccharide monooxygenase (LPMO) is based on its role as an electron donor. Before donating electrons to LPMO or electrodes, an interdomain electron transfer from the catalytic FAD-containing dehydrogenase domain to the electron shuttling cytochrome domain of CDH is required. This study investigates the role of two crucial amino acids located at the dehydrogenase domain on domain interaction and interdomain electron transfer by structure-based engineering. The electron transfer kinetics of wild-type Myriococcum thermophilum CDH and its variants M309A, R698S, and M309A/R698S were analyzed by stopped-flow spectrophotometry and structural effects were studied by small-angle X-ray scattering. The data show that R698 is essential to pull the cytochrome domain close to the dehydrogenase domain and orient the heme propionate group towards the FAD, while M309 is an integral part of the electron transfer pathway – its mutation reducing the interdomain electron transfer 10-fold. Structural models and molecular dynamics simulations pinpoint the action of these two residues on the domain interaction and interdomain electron transfer.

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

Text Mining for Process–Structure–Properties Relationships in Metals

With the advent of large language models (LLMs), the vast unstructured text within millions of academic papers is increasingly accessible for materials discovery—although significant challenges remain. While LLMs offer promising few- and zero-shot learning capabilities, particularly valuable in the materials domain where expert annotations are scarce, general-purpose LLMs often fail to address key materials-specific queries without further adaptation. To bridge this gap, fine-tuning LLMs on human-labeled data is essential for effective structured knowledge extraction (Liu in The Importance of Human-Labeled Data in the Era of LLMs, 2023). Here, in this study, we introduce a novel annotation schema designed to extract generic process–structure–properties relationships from scientific literature. We demonstrate the utility of this approach using a dataset of 128 abstracts, with annotations drawn from two distinct domains: high-temperature materials (Domain I) and uncertainty quantification in simulating materials microstructure (Domain II). Initially, we developed a conditional random field (CRF) model based on MatBERT—a domain-specific BERT variant—and evaluated its performance on Domain I. Subsequently, we compared this model with a fine-tuned LLM (GPT-4o from OpenAI) under identical conditions. Our results indicate that fine-tuning LLMs can significantly improve entity extraction performance over the BERT-CRF baseline on Domain I. However, when additional examples from Domain II were incorporated, the performance of the BERT-CRF model became comparable to that of the GPT-4o model. These findings underscore the potential of our schema for structured knowledge extraction and highlight the complementary strengths of both modeling approaches.

Materials science↗
DOE OSTI2025

Allosteric prediction via convolutional neural networks and protein structural and dynamical features

Allostery is the phenomenon whereby a binding event or covalent modification at one site in a protein modulates function at a distal site, thus changing a protein’s functional state. As such, it is a ubiquitous aspect of protein functional regulation. Computationally predicting allosteric states is important as part of the broader challenge of functional annotation, but it also has practical implications for drug development, as targeting an allosteric site often affords greater specificity compared with targeting an orthosteric site. This study introduces a machine learning approach to predict the allosteric functional state using the small G-protein KRas as the model system, due to its implication in many types of cancer and being well studied as a result with many x-ray crystallographic structures of KRas available with different mutations and ligands bound. Using structural and dynamical features that can be cast as images, namely interatomic distances, contact maps, covariance, and mutual information, supervised learning was performed using convolutional neural networks. Two pretrained convolutional neural network architectures, GoogLeNet and ResNet18, were fine-tuned to classify KRas into active or inactive states based on these features. Across training regimes, atomic contact maps emerged as the most effective structural feature, whereas linearized mutual information outperformed covariance in capturing dynamical correlations relevant to allostery. Models achieved significant validation accuracy, with atomic contact maps yielding up to 90% accuracy. In conclusion, the findings suggest that integrating global structural rearrangements and correlated motion patterns with deep learning can reliably predict protein allosteric states, offering a promising framework for understanding allosteric regulation and developing targeted therapeutics.

Rajeshwar T., Rajitha [Oak Ridge National Laborato↗
DOE OSTI2023

Controlling the toxicity of biomass-derived difunctional molecules as potential pharmaceutical ingredients for specific activity toward microorganisms and mammalian cells

A biomass-derived difuran compound, denoted as HAH (HMF–acetone–HMF), synthesized by aldol-condensation of 5-hydroxyfurfural (HMF) and acetone, can be partially hydrogenated to provide an electron-rich difuran compound (PHAH) for Diels–Alder reactions with maleimide derivatives. The nitrogen (N) site in the maleimide can be substituted by imidation with amine-containing compounds to control the hydrophobicity of the maleimide moiety in adducts of furans and maleimide by Diels–Alder reaction, denoted as norcantharimides (Diels–Alder adducts). The structural effects on the toxicity of various biomass-derived small molecules synthesized in this manner to regulate biological processes, defined as low molecular weight (≤1000 g mol -1 ) organic compounds, were investigated against diverse microbial and mammalian cell types. The biological toxicity increased when hydrophobic N-substitutions and C[double bond, length as m-dash]C bonds were introduced into the molecular structure. Among the synthesized norcantharamide derivatives, some compounds demonstrated pH-dependent toxicities against specific cell types. Reaction kinetics analyses of the norcantharimides in biological conditions suggest that this pH-dependent toxicity of norcantharimides could arise from retro Diels–Alder reactions in the presence of a Brønsted acid that catalyzes the release of an N-substituted maleimide, which has higher toxicity against fungal cells than the toxicity of the Diels–Alder adduct. These synthetic approaches can be used to design biologically-active small molecules that exhibit selective toxicity against various cell types (e.g., fungal, cancer cells) and provide a sustainable platform for production of prodrugs that could actively or passively affect the viability of infectious cells.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1996

Performance of Integrated Fiber Optic, Piezoelectric, and Shape Memory Alloy Actuators/Sensors in Thermoset Composites

Recently, scientists and engineers have investigated the advantages of smart materials and structures by including actuators in material systems for controlling and altering the response of structural environments. Applications of these materials systems include vibration suppression/isolation, precision positioning, damage detection and tunable devices. Some of the embedded materials being investigated for accomplishing these tasks include piezoelectric ceramics, shape memory alloys, and fiber optics. These materials have some benefits and some shortcomings; each is being studied for use in active material design in the SPICES (Synthesis and Processing of Intelligent Cost Effective Structures) Consortium. The focus of this paper concerns the manufacturing aspects of smart structures by incorporating piezoelectric ceramics, shape memory alloys and fiber optics in a reinforced thermoset matrix via resin transfer molding (RTM).

Trottier, C. Michael↗
NASA NTRS2000

A Theoretical Investigation of the Infrared Spectroscopic Properties of Closed-Shell Polycyclic Aromatic Hydrocarbon Cations

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

Hudgins, Douglas M.↗
NASA NTRS2013

Hyperspectral Remote Sensing of Foliar Nitrogen Content

A strong positive correlation between vegetation canopy bidirectional reflectance factor (BRF) in the near infrared (NIR) spectral region and foliar mass-based nitrogen concentration (%N) has been reported in some temperate and boreal forests. This relationship, if true, would indicate an additional role for nitrogen in the climate system via its influence on surface albedo and may offer a simple approach for monitoring foliar nitrogen using satellite data. We report, however, that the previously reported correlation is an artifact - it is a consequence of variations in canopy structure, rather than of %N. The data underlying this relationship were collected at sites with varying proportions of foliar nitrogen-poor needleleaf and nitrogen-rich broadleaf species, whose canopy structure differs considerably. When the BRF data are corrected for canopy-structure effects, the residual reflectance variations are negatively related to %N at all wavelengths in the interval 423-855 nm. This suggests that the observed positive correlation between BRF and %N conveys no information about %N. We find that to infer leaf biochemical constituents, e.g., N content, from remotely sensed data, BRF spectra in the interval 710-790 nm provide critical information for correction of structural influences. Our analysis also suggests that surface characteristics of leaves impact remote sensing of its internal constituents. This further decreases the ability to remotely sense canopy foliar nitrogen. Finally, the analysis presented here is generic to the problem of remote sensing of leaf-tissue constituents and is therefore not a specific critique of articles espousing remote sensing of foliar %N.

Knyazikhin, Yuri↗
NASA NTRS2021

Assessing impacts of canopy 3D structure on chlorophyll fluorescence radiance and radiative budget of deciduous forest stands using DART

Although remote sensing (RS) of solar-induced chlorophyll fluorescence (SIF) is increasingly used as a valuable source of information about vegetation photosynthetic activity, the RS SIF observations are significantly influenced by canopy-specific structural features (i.e., canopy architecture including leaf area index and presence of woody components), atmospheric conditions during their acquisition (e.g., proportion of direct and diffuse irradiance) and observational geometric configurations (e.g., sun and viewing directions). Radiative transfer (RT) models have the potential to provide a better understanding of the canopy structural effects on the SIF emission and RS signals. Here, we used the DART model to assess the daily influence, from morning to evening, of forest 3D architecture on SIF nadir radiance, emission, escape factor and nadir yield of eight 100 m × 100 m forest study plots established in a temperate deciduous forest of the Smithsonian Environmental Research Center (Edgewater, MD, USA). The 3D architecture of each plot was derived from airborne LiDAR. DART simulations of these 3D forest plots and their 1D (i.e., vertical profile of sun-adapted and shade-adapted leaves) and 0D (i.e., homogeneous layer of sun-adapted leaves above an homogeneous layer of shade-adapted leaves) abstractions were compared to assess the relative errors (ε1D−3D and ε0D−3D) associated with horizontal and vertical structural heterogeneity, respectively. Forest 3D structure, especially horizontal heterogeneity, had a great influence on forest nadir SIF radiance, resulting in ε1D−3D up to 55% at 8:00 and 18:00 (i.e., for oblique sun directions). The key indicators of this impact, in the descending order of importance, were the SIF escape factor (ε1D−3D up to 40%), the attenuation of incident photosynthetically active radiation (ε1D−3D less than 5%), and the SIF emission yield (ε1D−3D less than 2%). The influence of forest architecture on the nadir SIF escape factor and SIF yield (ε1D−3D up to 40%) varied over time, with differences in forest stand structure, and per spectral domain, being always larger between 640 and 700 nm than between 700 and 850 nm. In addition, woody elements demonstrated a large influence on forest SIF radiance due to their “shading” effect (ε up to 17%) and their “blocking” effect (ε ≈ 10%), both of them higher for far-red than for red SIF. These results underline the importance of 3D forest canopy architecture, especially 2D heterogeneity, and inclusion of woody elements in RT modeling used for interpretation of the RS SIF signal, and subsequently for the estimation of gross primary production and detection of vegetation stress.

Omar Regaieg↗
NASA NTRS2001

Closed-Shell Polycyclic Aromatic Hydrocarbon Cations: A New Category of Interstellar Polycyclic Aromatic Hydrocarbons

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of polycyclic aromatic hydrocarbon (PAH) cations that explore both size and electronic structure effects of the infrared spectroscopic properties of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms (C(sub odd) PAHs); and (2) protonated PAH cations (HPAH+). Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18 in both neutral and (radical) cationic form are also reported and compared with those of the other species. Overall, the C(sub odd) PAHs spectra are dominated by strong CC stretching modes near 1600 cm(exp -1) and display spectra that are remarkably insensitive to molecular size. The HPAH+ species evince a more complex spectrum consistent with the added contributions of aliphatic modes and their generally lower symmetry. Finally, for both classes of closed-shell cations, the intensity of the aromatic CH stretching modes is found to increase with molecular size far out of proportion with the number of CH groups, approaching a value more typical of neutral PAHs for the largest species studied.

Hudgins, Douglas M.↗
NASA NTRS1993

Viewpoint 9--molecular structure of aqueous interfaces

In this review we summarize recent progress in our understanding of the structure of aqueous interfaces emerging from molecular level computer simulations. It is emphasized that the presence of the interface induces specific structural effects which, in turn, influence a wide variety of phenomena occurring near the phase boundaries. At the liquid-vapor interface, the most probable orientations of a water molecule is such that its dipole moment lies parallel to the interface, one O-H bond points toward the vapor and the other O-H bond is directed toward the liquid. The orientational distributions are broad and slightly asymmetric, resulting in an excess dipole moment pointing toward the liquid. These structural preferences persist at interfaces between water and nonpolar liquids, indicating that the interactions between the two liquids in contact are weak. It was found that liquid-liquid interfaces are locally sharp but broadened by capillary waves. One consequence of anisotropic orientations of interfacial water molecules is asymmetric interactions, with respect to the sign of the charge, of ions with the water surface. It was found that even very close to the surface ions retain their hydration shells. New features of aqueous interfaces have been revealed in studies of water-membrane and water-monolayer systems. In particular, water molecules are strongly oriented by the polar head groups of the amphiphilic phase, and they penetrate the hydrophilic head-group region, but not the hydrophobic core. At infinite dilution near interfaces, amphiphilic molecules exhibit behavior different from that in the gas phase or in bulk water. This result sheds new light on the nature of hydrophobic effect in the interfacial regions. The presence of interfaces was also shown to affect both equilibrium and dynamic components of rates of chemical reactions. Applications of continuum models to interfacial problems have been, so far, unsuccessful. This, again, underscores the importance of molecular-level information about interfaces.

Review, Tutorial↗