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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies

Here, the combination of two different β-diketone ligands facilitates the size-controlled assembly of pure heterometallic [LnLn'Ln] linear compounds thanks to two different coordination sites present in the molecular scaffold. [HoCeHo], [ErCeEr], and [YbCeYb] analogues are presented here and are characterized both in the solid state and in solution, demonstrating the selectivity of this unique method to produce heterometallic 4f molecular entities.

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

Diffusion Monte Carlo Study of the Structure and Spectroscopy of H 3 O –

A potential energy surface for H 3 O – has been developed based on the NN+(MOB-ML) approach we developed for studies of complexes of OH – with two or three water molecules. Unlike those systems, H 3 O – has two low-energy isomers, H – ·H 2 O and OH – ·H 2 , which differ in energy by less than 2.5 kcal mol –1 , and which are separated by a barrier of roughly 4.5 kcal mol –1 . We find that by training the NN+(MOB-ML) model using structures based on diffusion Monte Carlo (DMC) simulations initiated in the two potential minima, we are able to obtain a potential surface that describes both isomers. Using these potentials, the structure and spectra of H 3 O – and its deuterated analogues are investigated using DMC. These calculations show that the ground state wave function for H 3 O – is mainly localized in the H – ·H 2 O minimum in the potential, with a small amount of the probability amplitude (<5%) in the region of the OH – ·H 2 minimum. The delocalization of the wave function into the secondary minimum is lowered by deuteration of the water molecule, while replacing H – with D – increases the isomerization due to the shortening of the average distance between the hydride ion and the hydrogen atom in water to which it is bound. Introducing one quantum of excitation in the H – ···H 2 O stretching vibration increases the amount of isomerization, while the isomerization decreases with additional excitation of this mode. Excitation of the free OH stretch in the water molecule also increases the amount of isomerization, while excitation of the out-of-plane bending vibration suppresses the isomerization. Furthermore, the effects of partial deuteration on the frequencies for these vibrations are also explored.

Chemical structure↗
DOE OSTI2024

Iron( IV ) alkyl complexes: electronic structure contributions to Fe–C bond homolysis and migration reactions that form N–C bonds from N 2

High-valent iron alkyl complexes are rare, as they are prone to Fe–C bond homolysis. Here, we describe an unusual way to access formally iron(IV) alkyl complexes through double silylation of iron(I) alkyl dinitrogen complexes to form an NNSi 2 group. Spectroscopically validated computations show that the disilylehydrazido(2−) ligand stabilizes the formal iron(IV) oxidation state through a strongly covalent Fe–N π-interaction, in which one π-bond fits an “inverted field” description. This means that the two bonding electrons are localized more on the metal than the ligand, and thus an iron(II) resonance structure is a significant contributor, similar to the previously-reported phenyl analogue. However, in contrast to the phenyl complex which has an S = 1 ground state, the ground state of the alkyl complex is S = 2, which places one electron in the π* orbital, leading to longer and weaker Fe–N bonds. The reactivity of these hydrazido(2−) complexes is dependent on the steric and electronic properties of the specific alkyl group. When the alkyl group is the bulky trimethylsilylmethyl, the formally iron(IV) species is stable at room temperature and no migration of the alkyl ligand is observed. However, the analogous complex with the smaller methyl ligand does indeed undergo migration of the carbon-based ligand to the NNSi 2 group to form a new N–C bond. This migration is followed by isomerization of the hydrazido ligand, and the product exists as two isomers that have distinct η 1 and η 2 binding of the hydrazido group. Lastly, when the alkyl group is benzyl, the Fe–C bond homolyzes to give a three-coordinate hydrazido(2−) complex which is likely due to the greater stability of a benzyl radical compared to that for methyl or trimethylsilylmethyl. These studies demonstrate the availability of a hydrocarbyl migration pathway at formally iron(IV) centers to form new N–C bonds directly to N 2 , though product selectivity is highly dependent on the identity of the migrating group.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Valley-dependent exciton fine structure and Autler–Townes doublets from Berry phases in monolayer MoSe 2

The Berry phase of Bloch states can have profound effects on electron dynamics and lead to novel transport phenomena, such as the anomalous Hall effect and the valley Hall effect. Recently, it was predicted that the Berry phase effect can also modify the exciton states in transition metal dichalcogenide monolayers, and lift the energy degeneracy of exciton states with opposite angular momentum through an effective valley-orbital coupling. Here, we report the observation and control of the Berry phase-induced splitting of the 2p exciton states in monolayer molybdenum diselenide (MoSe 2 ) using the intraexciton optical Stark spectroscopy. We observe the time-reversal-symmetric analogue of the orbital Zeeman effect resulting from the valley-dependent Berry phase, which leads to energy difference of +14 (-14) meV between the 2p+ and 2p- exciton states in the K (K') valley, consistent with the ordering from our ab initio GW-Bethe–Salpeter equation results. In addition, we show that the light–matter coupling between intraexciton states is remarkably strong, leading to a prominent valley-dependent Autler–Townes doublet under resonant driving. Finally, our study opens up pathways to coherently manipulate the quantum states and excitonic excitation with infrared radiation in two-dimensional semiconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Investigations into the assembly behaviour of a ‘rigidified’ p -carboxylatocalix[4]arene

The p-carboxylatocalix[4]arenes have been shown to be versatile supramolecular building blocks capable of forming a range of bi-layers, capsules and nanoscale tubules in the solid state. In this work, we report the synthesis of a new ‘rigidified’ analogue, as well as investigations into its self-assembly and related coordination chemistry. These behaviours are reminiscent of other p-carboxylatocalix[4]arenes despite the presence of rigidifying groups at the lower-rim, suggesting that this building block may be further exploited in the assembly of a range of new metal–organic cages and coordination polymers.

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

An integer- N frequency synthesizer for flexible on-chip clock generation

A low-power integer-N frequency synthesizer for flexible on-chip clock generation has been designed in a 65 nm CMOS process. The circuit can be programmed to generate two independent low-jitter clocks between 30 MHz and 3 GHz that are locked to a 10–50 MHz reference input. The design uses a phase-locked loop (PLL) with a dual-tuned LC voltage-controlled oscillator (VCO), programmable feedback divider, and dual output dividers. The total power consumption from 1.2 V and 0.8 V supplies is 4.0 mW. In conclusion, experimental results confirm the functionality of the proposed synthesizer over a wide range of output frequencies.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Quantum Solver of Contracted Eigenvalue Equations for Scalable Molecular Simulations on Quantum Computing Devices

The accurate computation of ground and excited states of many-fermion quantum systems is one of the most consequential, contemporary challenges in the physical and computational sciences whose solution stands to benefit significantly from the advent of quantum computing devices. Existing methodologies using phase estimation or variational algorithms have potential drawbacks such as deep circuits requiring substantial error correction or non-trivial high-dimensional classical optimization. In this work, we introduce a quantum solver of contracted eigenvalue equations, the quantum analogue of classical methods for the energies and reduced density matrices of ground and excited states. The solver does not require deep circuits or difficult classical optimization and achieves an exponential speed-up over its classical counterpart. We demonstrate the algorithm though computations on both a quantum simulator and two IBM quantum processing units.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Q-balls meet fuzzballs: non-BPS microstate geometries

We construct a three-parameter family of non-extremal microstate geometries, or “microstrata”, that are dual to states and deformations of the D1-D5 CFT. These families are non-extremal analogues of superstrata. We find these microstrata by using a Q-ball-inspired Ansatz that reduces the equations of motion to solving for eleven functions of one variable. We then solve this system both perturbatively and numerically and the results match extremely well. We find that the solutions have normal mode frequencies that depend upon the amplitudes of the excitations. We also show that, at higher order in perturbations, some of the solutions, having started with normalizable modes, develop a “non-normalizable” part, suggesting that the microstrata represent states in a perturbed form of the D1-D5 CFT. This paper is intended as a “Proof of Concept” for the Q-ball-inspired approach, and we will describe how it opens the way to many interesting follow-up calculations both in supergravity and in the dual holographic field theory.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Fyn–Saracatinib Complex Structure Reveals an Active State-like Conformation

Fyn is a Src-family tyrosine kinase implicated in synaptic dysfunction and neuroinflammation across multiple neurodegenerative disorders, including Alzheimer’s disease (AD) and Parkinson’s disease (PD). Saracatinib (AZD0530) is a potent Src-family inhibitor that has been explored as a repurposed therapeutic; however, its clinical utility is limited by poor kinase selectivity caused by high sequence conservation within Src-family ATP-binding sites. Here, we combine surface plasmon resonance (SPR) and X-ray crystallography to define saracatinib recognition by the Fyn kinase domain (KD). SPR single-cycle kinetics shows that saracatinib binds the isolated Fyn KD and full-length Fyn with low-nanomolar affinity, whereas dasatinib binds with subnanomolar affinity and markedly slower dissociation. We determined the crystal structure of the Fyn KD-saracatinib complex at 2.22 Å resolution. The kinase adopts an active-like conformation with the DFG motif and αC-helix in the ‘in’ state and a conserved β3 αC Lys-Glu salt bridge. Saracatinib occupies the adenine and ribose pockets, and engages the hinge through direct and water-mediated hydrogen bonding while complementing a hydrophobic back pocket by van der Waals contacts. Comparison with reported saracatinib-bound structures of other kinases suggests that the active-state geometry observed for Fyn creates a pocket not observed in inactive-like complexes, providing a structural handle for designing Fyn-selective inhibitors. Comparison with all saracatinib-bound kinase co-structures currently available in the PDB (ALK2 and PKMYT1) indicates a conserved monodentate hinge binding mode but kinase-dependent αC-helix conformations, providing a structural rationale for designing Fyn-selective analogues.

AZD0530↗
DOE OSTI2021

Thermodynamic Implementations of Quantum Processes

Abstract Recent understanding of the thermodynamics of small-scale systems have enabled the characterization of the thermodynamic requirements of implementing quantum processes for fixed input states. Here, we extend these results to construct optimal universal implementations of a given process, that is, implementations that are accurate for any possible input state even after many independent and identically distributed (i.i.d.) repetitions of the process. We find that the optimal work cost rate of such an implementation is given by the thermodynamic capacity of the process, which is a single-letter and additive quantity defined as the maximal difference in relative entropy to the thermal state between the input and the output of the channel. Beyond being a thermodynamic analogue of the reverse Shannon theorem for quantum channels, our results introduce a new notion of quantum typicality and present a thermodynamic application of convex-split methods.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

The Impact of Ethylenediaminetetraacetic Acid (EDTA) on the Sorption of Nd(III), Th{sup (IV)}, and U(VI) onto Dolomite in WIPP-Relevant Brines, GWB and ERDA-6 - 20356

Storage of legacy, transuranic waste at the Waste Isolation Pilot Plant (WIPP) requires accurate risk models for performance assessments. These models must predict the long-term fate and transport of contaminants in the WIPP and surrounding environment. Laboratory support is necessary for the development of an accurate model through better understanding of contaminant behavior in the WIPP. The WIPP is a deep geologic repository that is characterized by high ionic strength due to evaporite deposits in the Salado formation (porewaters up to 7.4 M). High concentrations of sodium chloride (NaCl), calcium chloride (CaCl{sub 2}), and magnesium chloride (MgCl{sub 2}) are particularly of concern due to their potential impact on solubility and ultimately transport of contaminants of concern. Additionally, ligands capable of forming strong complexes with metals are found in significant concentrations in the WIPP environment due to their disposal from waste processing and formation during degradation of repository components (e.g. cellulose degradation by calcium hydroxide in cement). Consequently, there is a need to investigate the fate and transport of contaminants in the WIPP environment with a focus on the effects of high ionic strength and strongly coordinating ligands. Contaminants of high concern include the actinides (U(VI), Pu(IV), and Am(III)). Laboratory support of the WIPP modeling efforts was provided by this research. A series of batch experiments were utilized to study the impact of ionic strength, contaminant concentration, and the presence of ethylenediaminetetraacetic acid (EDTA) on the sorption of Nd(III), Th(IV), and U(VI) onto dolomite, a carbonate mineral found within the Culebra formation. The Culebra formation is the most transmissive layer above the WIPP, making transport of contaminants the most likely route in previous risk assessments. Two brines specifically designed to imitate conditions within the WIPP environment were used in these experiments. The U.S. Energy Research and Development Administration Well 6 (ERDA-6, 95%) brine simulates a low Mg environment, while the generic weep brine (GWB, 95%) simulates the WIPP environment with a high Mg concentration. Mg is added to the repository in the form of MgO as an engineered barrier and is naturally present in some formations. It is expected to scavenge carbonate from solutions decreasing formation of the highly soluble and competitive uranium-carbonate complexes. EDTA is used during manipulations of nuclear materials due to its ability to form strong, stable complexes with the actinides and may be found in high concentrations (up to 0.08 mM) within the WIPP as waste canisters degrade. Further, it may provide additional avenues for unwanted transport of contaminants. Nd(III) and Th(IV) were used as stable analogues of Am(III) and Pu(IV), respectively, to represent the most common oxidation states of actinides in the WIPP environment in addition to U(VI). The potential for colloid formation was also investigated with low and high concentrations of contaminants (10 and 1000 μg/L) using three size-dependent particle separation steps. The results of this research provide a better understanding of potential behavior of actinides in the presence of EDTA and within WIPP-relevant brines. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Thienopyrroledione-Based Photosensitizers as Strong Photoinduced Oxidants: Oxidation of Fe(bpy) 3 2+ in a >1.3 V Dye-Sensitized Solar Cell

The creation of visible light absorbing organic dyes as strong photoinduced oxidants is needed for many potential applications in energy production and storage. In order to access more positive potentials, the electron deficient thienopyrroledione building block is promising as a π-bridge combined with weak aryl-ether donor groups and the phenyl-cyanoacetic acid acceptor group. The thienopyrroledione (TPD) building block is compared to the ubiquitous benzothiadiazole (BTD) building block which was recently used in a dye-sensitized solar cell (DSC) device with >1.4 V photovoltage output. The variation in dye donor group is studied through UV-Vis absorption spectroscopy and electrochemical methods both in solution and on TiO2 films. The TPD building block resulted in a more positive ground state and excited state oxidation potential, a higher photocurrent (up to 3.5 mA/cm 2 ), and a higher power conversion efficiency (up to 2.9%) than a BTD analogue while retaining comparable photovoltages (~1.3 V versus ~1.4 V). Computational analysis was used to better understand the optical properties of the thienopyrroledione-based dyes showing overlap of orbitals at the TPD bridge in the S 0 and S 1 states. The dyes were analyzed in high voltage-DSC devices with a challenging to oxidize redox shuttle, [Fe(bpy) 3 ] 2+ , at 1.37 V versus NHE.

25 ENERGY STORAGE↗
DOE OSTI2024

The damage Mechanics challenge Results: Participant predictions compared with experiment

In this article, We present results from a recent exercise where participating organizations were asked to provide model-based blind predictions of damage evolution in 3D-printed geomaterial analogue test articles. Participants were provided with a range of data characterizing both the undamaged state (e.g., ultrasonic measurements) and damage evolution (e.g., 3-point bending, unconfined compression, and Brazilian testing) of the material. In this paper, we focus on comparisons between the participants’ predictions and the previously secret challenge problem experimental observations. We present valuable lessons learned for the application of numerical methods to deformation and failure in brittle-ductile materials. The exercise also enables us to identify which specific types of calibration data were of most utility to the participants in developing their predictions. Further, we identify additional data that would have been useful for participants to improve the confidence of their predictions. Consequently, this work improves our understanding of how to better characterize a material to enable more accurate prediction of damage and failure propagation in natural and engineered brittle-ductile materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effects of the Inverse Trans-Influence in a Berkelium(III) Phosphine Oxide Complex

An example of a 249 Bk 3+ phosphine oxide complex has been prepared to examine and quantify the effects of the inverse trans-influence (ITI) on a late actinide complex. This has been accomplished through a comparison of cis and trans Bk-ligand bonds in the meridional berkelium(III) complex, BkBr 3 (OPCy 3 ) 3 (OPCy 3 = tricyclohexylphosphine oxide). A detailed bond metric analysis was completed that includes the shortest published distance for a Bk 3+ −O bond, attributed to the smaller coordination number of Bk 3+ of six in mer-BkBr 3 (OPCy 3 ) 3 . ITI calculations of the trans Bk 3+ −O bond provide an ITI value (98.5(2)%) comparable to that of mer-AmBr 3 (OPCy 3 ) 3 (98.2(2)%) and indicate a small 5f orbital contribution to bonding. This effect is discussed in the context of the isomorphous lanthanide(III) series where the ITI is calculated to be higher for mer-BkBr 3 (OPCy 3 ) 3 than in most Ln 3+ analogues.

Actinides↗
DOE OSTI2019

Transition form factors: γ * + p → Δ ( 1232 ) , Δ ( 1600 )

We report that electroproduction form factors describing the γ * p → Δ + ( 1232 ) , Δ + ( 1600 ) transitions are computed using a fully dynamical diquark-quark approximation to the Poincaré-covariant three-body bound-state problem in relativistic quantum field theory. In this approach, the Δ ( 1600 ) is an analogue of the Roper resonance in the nucleon sector, appearing as the simplest radial excitation of the Δ ( 1232 ) . Precise measurements of the γ * p → Δ + ( 1232 ) transition already exist on 0 ≤ Q 2 ≲ 8 GeV 2 , and the calculated results compare favorably with the data outside the meson-cloud domain. The predictions for the γ * p → Δ + ( 1600 ) magnetic dipole and electric quadrupole transition form factors are consistent with the empirical values at the real photon point, and extend to Q 2 ≈ 6 m p 2 , enabling a meaningful direct comparison with experiment once analysis of existing data is completed. In both cases, the electric quadrupole form factor is particularly sensitive to deformation of the Δ -baryons. Interestingly, while the γ * p → Δ + ( 1232 ) transition form factors are larger in magnitude than those for γ * p → Δ + ( 1600 ) in some neighborhood of the real photon point, this ordering is reversed on Q 2 ≳ 2 m p 2 , suggesting that the γ * p → Δ + ( 1600 ) transition is more localized in configuration space.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Interwoven magnetic kagome metal overcomes geometric frustration

Magnetic kagome materials provide a platform for exploring magneto-transport phenomena, symmetry breaking and charge ordering driven by the intricate interplay among electronic structure, topology and magnetism. Yet geometric frustration in conventional kagome magnets limits their tunability. Here we propose a design strategy for interweaving quasi-one-dimensional magnetic Tb zigzag chains with non-magnetic Ti-based kagome bilayers in TbTi 3 Bi 4 . Comprehensive spectroscopic analyses reveal coexisting elliptical-spiral magnetic and spin-density-wave orders accompanied by a large ~90 meV band-folding gap. The combined magnetic and electronic state leads to a giant anomalous Hall conductivity of 10 5 Ω −1 cm −1 , which exceeds that observed in frustrated kagome analogues. These results establish TbTi 3 Bi 4 as a model system of magnetic kagome metals with strong electron–magnetism interactions and underscore the necessity of interweaving designed magnetic and charge layers separately to achieve tunable transport properties. This design strategy will enable the discovery of emergent quantum states and next-generation electronic materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗