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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 1,387 records · Page 77
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Cryo-EM captures the coordination of asymmetric electron transfer through a di-copper site in DPOR

Enzymes that catalyze long-range electron transfer (ET) reactions often function as higher order complexes that possess two structurally symmetrical halves. The functional advantages for such an architecture remain a mystery. Using cryoelectron microscopy we capture snapshots of the nitrogenase-like dark-operative protochlorophyllide oxidoreductase (DPOR) during substrate binding and turnover. DPOR catalyzes reduction of the C17 = C18 double bond in protochlorophyllide during the dark chlorophyll biosynthetic pathway. DPOR is composed of electron donor (L-protein) and acceptor (NB-protein) component proteins that transiently form a complex in the presence of ATP to facilitate ET. NB-protein is an α 2 β 2 heterotetramer with two structurally identical halves. However, our structures reveal that NB-protein becomes functionally asymmetric upon substrate binding. Asymmetry results in allosteric inhibition of L-protein engagement and ET in one half. Residues that form a conduit for ET are aligned in one half while misaligned in the other. An ATP hydrolysis-coupled conformational switch is triggered once ET is accomplished in one half. These structural changes are then relayed to the other half through a di-nuclear copper center at the tetrameric interface of the NB-protein and leads to activation of ET and substrate reduction. These findings provide a mechanistic blueprint for regulation of long-range electron transfer reactions.

Computational biophysics↗
NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-enantiomeric excesses of chiral amino acids and sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, remains a key goal of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks on Mars [1-3], NASA’s Curiosity rover has significantly advanced our understanding of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars, if they were present, it is expected that amino acid hydrolysis and racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [4]. One of ESA’s Rosalind Franklin rover payload instruments called the Mars Organic Molecule Analyzer (MOMA) includes a wet chemistry package capable of measuring the enantiomeric ratios of any chiral amino acids present at part-per-million concentrations or higher [5]. The complexity and limited duration of spaceflight operations and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic compounds in ancient rocks make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, and isotopic studies and molecule-specific isotopic and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars comes from biotic or abiotic sources. Ultimately, sample return may be our best chance of identifying chemical biosignatures from a past or present martian biota, if one ever existed on Mars. NASA’s Perseverance rover will collect dozens of surface sample cores for possible future return to Earth by NASA and ESA. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of non-biological amino acids found in meteorites compared to terrestrial biochemistry and propose a set of measurement criteria that should be used to help establish the origin of any chiral asymmetry detected in samples from Mars [6].

Daniel P Glavin↗
DOE OSTI2022

Hydrazine Energy Storage: Displacing N 2 H 4 from the Metal Coordination Sphere

Hydrogen carriers, such as hydrazine (N 2 H 4 ), may facilitate long duration energy storage, a vital component for resilient grids by enabling more renewable energy generation. Lanthanide coordination chemistry with N 2 H 4 as well as efforts to displace N 2 H 4 from the metal coordination sphere to develop an efficient catalytic production cycle were detailed. Modeling the equilibrium of different ligand coordination, it was predicted that strong sigma donor molecules would be required to displace N 2 H 4 . Monitoring competition experiments with nuclear magnetic resonance confirmed that trimethyl phosphine oxide, dimethylformamide, and dimethyl sulfoxide displaced N 2 H 4 in large or small lanthanide complexes.

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

Spin-orbital correlations from complex orbital order in MgV 2⁢ O 4

MgV 2 ⁢O 4 is a spinel based on magnetic V 3+ ions, which host both spin (𝑆 = 1) and orbital (𝑙 eff = 1) moments. Owing to the underlying pyrochlore coordination of the magnetic sites, the spins in MgV 2 ⁢O 4 only antiferromagnetically order once the frustrating interactions imposed by the 𝐹⁡𝑑⁢$\overline{3}$⁢𝑚 lattice are broken through an orbitally-driven structural distortion at T 𝑆 ≃ ⁢60 K. Consequently, a Néel transition occurs at T 𝑁 ≃ ⁢40 K. Low-temperature spatial ordering of the electronic orbitals is fundamental to both the structural and magnetic properties; however, considerable discussion on whether it can be described by complex or real orbital ordering is ambiguous. We apply neutron spectroscopy to resolve the nature of the orbital ground state and characterize hysteretic spin-orbital correlations using x-ray and neutron diffraction. Neutron spectroscopy finds multiple excitation bands and we parametrize these in terms of a multilevel (or excitonic) theory based on the orbitally degenerate ground state. Meaningful for the orbital ground state, we report an “optical-like” mode at high energies that we attribute to a crystal-field-like excitation from the spin-orbital 𝑗 eff = 2 ground-state manifold to an excited 𝑗 eff =1 energy level. We parametrize the magnetic excitations in terms of a Hamiltonian with spin-orbit coupling and local crystalline electric field distortions resulting from deviations from perfect octahedra surrounding the V 3+ ions. We suggest that this provides compelling evidence for complex orbital order in MgV 2⁢ O 4 . We then apply the consequences of this model to understand hysteretic effects in the magnetic diffuse scattering where we propose that MgV 2⁢ O 4 displays a high-temperature orbital memory of the low-temperature spin order.

Frustrated magnetism↗
DOE OSTI2018

Encapsulation of a Cr III Single‐Ion Magnet within an Fe II Spin‐Crossover Supramolecular Host

Abstract Single functional molecules are regarded as future components of nanoscale spintronic devices. Supramolecular coordination chemistry provides unlimited resources to implement multiple functions to individual molecules. A novel coordination [Fe 2 ] helicate exhibiting spin‐crossover is demonstrated to be ideally suited to encapsulate a [Cr(ox) 3 ] 3− complex anion (ox=oxalate), unveiling for the first‐time single ion slow relaxation of the magnetization for this metal. A possibility of tuning the dynamics of this relaxation as well as the performance of the Cr III center as qubit arises from the observation that metastable high spin Fe II centers from the host can be generated by irradiation with green light at low temperature.

Darawsheh, Mohanad↗
DOE OSTI2018

Encapsulation of a Cr III Single‐Ion Magnet within an Fe II Spin‐Crossover Supramolecular Host

Abstract Single functional molecules are regarded as future components of nanoscale spintronic devices. Supramolecular coordination chemistry provides unlimited resources to implement multiple functions to individual molecules. A novel coordination [Fe 2 ] helicate exhibiting spin‐crossover is demonstrated to be ideally suited to encapsulate a [Cr(ox) 3 ] 3− complex anion (ox=oxalate), unveiling for the first‐time single ion slow relaxation of the magnetization for this metal. A possibility of tuning the dynamics of this relaxation as well as the performance of the Cr III center as qubit arises from the observation that metastable high spin Fe II centers from the host can be generated by irradiation with green light at low temperature.

Darawsheh, Mohanad↗
DOE OSTI2018

Benchmarking ADMM in Nonconvex NLPs

Here, we study connections between the alternating direction method of multipliers (ADMM), the classical method of multipliers (MM), and progressive hedging (PH). The connections are used to derive benchmark metrics and strategies to monitor and accelerate convergence and to help explain why ADMM and PH are capable of solving complex nonconvex NLPs. Specifically, we observe that ADMM is an inexact version of MM and approaches its performance when multiple coordination steps are performed. In addition, we use the observation that PH is a specialization of ADMM and borrow Lyapunov function and primal-dual feasibility metrics used in ADMM to explain why PH is capable of solving nonconvex NLPs. This analysis also highlights that specialized PH schemes can be derived to tackle a wider range of stochastic programs and even other problem classes. Our exposition is tutorial in nature and seeks to to motivate algorithmic improvements and new decomposition strategies.

42 ENGINEERING↗
DOE OSTI2023

Fast Charge Induced Phase Evolution and Element Contribution of Nickel-Rich Layered Cathode for Lithium-Ion Batteries

In nickel-rich layered cathode materials, three transition metals (TM = Ni, Co and Mn) play critical roles in Li storage performance. However, rate-dependent phase evolution and elemental contribution of nickel-rich cathode materials are not well understood, but very important for further design and development of these cathodes in high-power applications. Here, the rate-dependent phase evolution and elemental contribution of LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) cathode are investigated thoroughly by using time-resolved synchrotron-based in situ X-ray diffraction and absorption techniques. The increase of Ni content in NMC532 has been found to be the main cause of the complex structural changes, resulting in distortion of TM-O 6 octahedron and strong static vibration between TM and O coordination. It is revealed that the fast charge (10C and 30C) of NMC532 leads to intermediate Li-poor phases, shrinking of H2 phase region, and prolonged O1 phase. During high-rate charging, Co is oxidized easily in low voltage region, while Ni mainly dominates charge compensation in high voltage region. It is found that delithiation-induced local structure distortion transfers from Ni to Co sites in fast kinetic process. In conclusion, these findings provide in-depth understanding for the fast charge behavior of Ni-rich layered cathode materials and help to guide further development of advanced high-power lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2017

General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides

Despite many recent developments in designing and screening catalysts for improved performance, transition-metal oxides continue to prove to be challenging due to the myriad inherent complexities of the systems and the possible morphologies that they can exhibit. Herein we propose a structural descriptor, the adjusted coordination number (ACN), which can generalize the reactivity of the oxygen sites over the many possible surface facets and defects of a transition-metal oxide. We demonstrate the strong correlation of this geometric descriptor with the electronic and energetic properties of the active sites on five facets of four transition-metal oxides. We then use the structural descriptor to predict C–H activation energies to show the great potential of using ACN for the prediction of catalytic performance. This study presents a first look into quantifying the relation between active site structure and reactivity of transition-metal-oxide catalysts.

Fung, Victor↗
DOE OSTI2019

Direct, One-Pot Syntheses of MOFs Decorated with Low-Valent Metal-Phosphine Complexes

In this paper, we demonstrate a simple and generalizable method for the one pot, in situ formation of bimetallic metal–organic framework (MOF) materials decorated with crystallographically defined, low-valent metal sites. Solvothermal reactions between poly(carboxylated) aryl(phosphine) ligands and mixtures of higher- and lower-valent metal precursors achieves concomitant P–M complexation and MOF formation via metal–carboxylate network bonding. This method is demonstrated in the preparation of two new phosphine coordination materials, PCM-107 and PCM-74, which feature Ar 3 P–AuX (X = Cl, Br) and chelated $\widehat{PN}$–Cu 2 I 2 –$\widehat{PN}$ units as the MOF building blocks, respectively. PCM-107 is an active catalyst for alkyne hydroaddition, while PCM-74 shows promise for the crystallization of MOFs bearing kinetically favored isomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Solvate Ionic Liquids at Electrified Interfaces

Solvate ionic liquids (SILs) are a promising electrolyte for Li-ion batteries; thus, their behavior at electrified interfaces is crucial for the operation of these batteries. We report molecular dynamics simulation results for a prototypical SIL of lithium triglyme bis(trifluoro-methanesulfonyl)imide ([Li(G3)][TFSI]) sandwiched between electrified surfaces. At negatively charged as well as neutral electrodes, the electrolyte largely maintains the characteristics of SILs, e.g., a majority of the interfacial Li + ions remains coordinated by the similar number of oxygen atoms on G3 ligands as the bulk Li + ions. The persistence of the complex ions is attributed to the 1:1 Li-G3 ratio in bulk SILs and the fact that G3 molecules readily adapt to the interfacial environment, e.g., by aligning themselves with the surface to ensure good solvation of the interfacial Li + ions. Nevertheless, the interfacial Li + ions also display changes of solvation from that in bulk SIL by deviating from the molecular plane formed by the oxygen atoms on G3 ligands as electrodes become more negatively charged. Using density functional theory along with natural bond orbital calculations, we examine the effects of such structural distortion on the properties of the complex cation. Both the frontier orbital energies of the complex cation and the donor-acceptor interactions between Li + ions and G3 ligands are found to be dependent on the deviation of Li + ions from the molecular plane of the G3 ligands, which suggest that the reduction of Li + ions should be facilitated by the structural distortion. These results bear important implications for the nanostructures and properties of SILs near electrified interfaces during actual operations of Li-ion batteries and serve to provide guidance toward the rational design of new SILs electrolytes.

25 ENERGY STORAGE↗
DOE OSTI2026

Domain Knowledge Guided Bayesian Optimization For Autonomous Alignment Of Complex Scientific Instruments

Bayesian Optimization (BO) is a powerful tool for optimizing complex non-linear systems. However, its performance degrades in high-dimensional problems with tightly coupled parameters and highly asymmetric objective landscapes, where rewards are sparse. In such needle-in-a-haystack scenarios, even advanced methods like trust-region BO (TurBO) often lead to unsatisfactory results. We propose a domain knowledge guided Bayesian Optimization approach, which leverages physical insight to fundamentally simplify the search problem by transforming coordinates to decouple input features and align the active subspaces with the primary search axes. We demonstrate this approach's efficacy on a challenging 12-dimensional, 6-crystal Split-and-Delay optical system, where conventional approaches, including standard BO, TuRBO and multi-objective BO, consistently led to unsatisfactory results. When combined with an reverse annealing exploration strategy, this approach reliably converges to the global optimum. The coordinate transformation itself is the key to this success, significantly accelerating the search by aligning input co-ordinate axes with the problem's active subspaces. As increasingly complex scientific instruments, from large telescopes to new spectrometers at X-ray Free Electron Lasers are deployed, the demand for robust high-dimensional optimization grows. Our results demonstrate a generalizable paradigm: leveraging physical insight to transform high-dimensional, coupled optimization problems into simpler representations can enable rapid and robust automated tuning for consistent high performance while still retaining current optimization algorithms.

FOS: Computer and information sciences↗
NASA NTRS1978

Technical assessment of PSSC-supported experiments and demonstrations

A description of CTS and ATS short-term and long-term satellite demonstration supported through usage of a satellite communication ground station complex is presented. User assessments about the programmatic impact of their demonstrations and experiments were summarized. The technical planning and coordination process involved in satellite utilization is also presented.

Source record↗
NASA NTRS1980

Forebody and base region real-gas flow in severe planetary entry by a factored implicit numerical method. I - Computational fluid dynamics

A new code for the simulation of full (forebody and base region) flowfields about bluff bodies in the hypersonic regime of severe planetary entry is described. The present 'maximally conservative, maximally differenced' formulation of the unsteady compressible Navier-Stokes equations for 2-D axisymmetric 3-D flow is contrasted for stability with previous formulations of Viviand, Kutler, et al, and Thomas and Lombard. Discrete metric relations peculiar to the axisymmetric finite volume formulation are presented along with a general discussion of their relations to and consequences of failure to close computational cells. A computational mesh of curvilinear coordinate topology singular in the flow regime is presented that permits aligned capturing of the major physical features of the complex flowfield.

Lombard, C. K.↗
NASA NTRS1984

Finite difference solutions of heat conduction problems in multi-layered bodies with complex geometries

A numerical procedure is presented for analyzing a wide variety of heat conduction problems in multilayered bodies having complex geometry. The method is based on a finite difference solution of the heat conduction equation using a body fitted coordinate system transformation. Solution techniques are described for steady and transient problems with and without internal energy generation. Results are found to compare favorably with several well known solutions.

Masiulaniec, K. C.↗
NASA NTRS1990

A patched-grid algorithm for complex aircraft configurations

A patched-grid algorithm for the analysis of complex configurations with an implicit, upwind-biased Navier-Stokes solver is presented. Through the use of a generalized coordinate transformation at the zonal interface between two or more blocks, the algorithm can be applied to highly stretched viscous grids and to arbitrarily-shaped patch boundaries. Applications are made to the SR71 reconnaissance aircraft in a high-altitude environment at a supersonic speed and to the F/A-18 forebody-strake configuration at subsonic, high-alpha conditions, in support of the NASA High-Alpha Research Program.

Walters, Robert W.↗
NASA NTRS1991

A hierarchical-multiobjective framework for risk management

A broad hierarchical-multiobjective framework is established and utilized to methodologically address the management of risk. United into the framework are the hierarchical character of decision-making, the multiple decision-makers at separate levels within the hierarchy, the multiobjective character of large-scale systems, the quantitative/empirical aspects, and the qualitative/normative/judgmental aspects. The methodological components essentially consist of hierarchical-multiobjective coordination, risk of extreme events, and impact analysis. Examples of applications of the framework are presented. It is concluded that complex and interrelated forces require an analysis of trade-offs between engineering analysis and societal preferences, as in the hierarchical-multiobjective framework, to successfully address inherent risk.

Haimes, Yacov Y.↗