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At least 991 records · Page 55
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Lone Pairs of Carbogenic Center Enable Thermally Activated Delayed Fluorescence from Carbon to Ligand Charge Transfer Excited States

Carbogenic compounds of the type L→C(0)←L, where L represents various ligands such as phosphines or carbenes, and C(0) denotes zerovalent carbon with two orthogonal lone pairs, are widely utilized in organic and coordination chemistry; however, in-depth photophysical and optical properties remain largely unknown. In the following work, we report detailed luminescent properties of one of the most prominent examples of carbogenic compounds, hexaphenylcarbodiphosphorane (CDP). Combined spectroscopic/TD-DFT studies demonstrate that both lone pairs of CDP participate in the observed visible light absorption and emission, which are associated with carbon lone pairs π*(PPh3) carbon to ligand charge transfer states (CLCTs). The CLCT exhibits a considerably decoupled electron-hole pair, resulting in a small S1-T1 gap and thermally assisted delayed fluorescence (TADF). Moreover, two lone pairs teamed up around C(0) provide numerous close-lying σ- and π-CLCT singlet and triplet states, which allow, for organic TADF emitters, extremely fast rates of exergonic intersystem crossing up to 1.27×109 s-1, competitive with some 3d and 4d metal-based TADF luminophores. These results open fresh directions for innovative design of novel luminescent materials for high-end photonic applications, utilizing lone pairs of carbogenic centers as donors of electron density in the excited states.

Mrózek, Ondřej [University of Southern California]↗
DOE OSTI2021

Efimov-like states and quantum funneling effects on synthetic hyperbolic surfaces

Engineering lattice models with tailored inter-site tunnelings and onsite energies could synthesize essentially arbitrary Riemannian surfaces with highly tunable local curvatures. Here, we point out that discrete synthetic Poincaré half-planes and Poincaré disks, which are created by lattices in flat planes, support infinitely degenerate eigenstates for any nonzero eigenenergies. Such Efimov-like states exhibit a discrete scaling symmetry and imply an unprecedented apparatus for studying quantum anomaly using hyperbolic surfaces. Furthermore, all eigenstates are exponentially localized in the hyperbolic coordinates, signifying the first example of quantum funneling effects in Hermitian systems. As such, any initial wave packet travels towards the edge of the Poincaré half-plane or its equivalent on the Poincaré disk, delivering an efficient scheme to harvest light and atoms in two dimensions. Furthermore, our findings unfold the intriguing properties of hyperbolic spaces and suggest that Efimov states may be regarded as a projection from a curved space with an extra dimension.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Copper-dependent halogenase catalyses unactivated C−H bond functionalization

Carbon–hydrogen (C–H) bonds are the foundation of essentially every organic molecule, making them an ideal place to do chemical synthesis. The key challenge is achieving selectivity for one particular C(sp 3 )−H bond. In recent years, metalloenzymes have been found to perform C(sp 3 )−H bond functionalization. Despite substantial progresses in the past two decades, enzymatic halogenation and pseudohalogenation of unactivated C(sp 3 )−H—providing a functional handle for further modification—have been achieved with only non-haem iron/α-ketoglutarate-dependent halogenases, and are therefore limited by the chemistry possible with these enzymes. Here, in this work, we report the discovery and characterization of a previously unknown halogenase ApnU, part of a protein family containing domain of unknown function 3328 (DUF3328). ApnU uses copper in its active site to catalyse iterative chlorinations on multiple unactivated C(sp 3 )−H bonds. By taking advantage of the softer copper centre, we demonstrate that ApnU can catalyse unprecedented enzymatic C(sp 3 )−H bond functionalization such as iodination and thiocyanation. Using biochemical characterization and proteomics analysis, we identified the functional oligomeric state of ApnU as a covalently linked homodimer, which contains three essential pairs—one interchain and two intrachain—of disulfide bonds. The metal-coordination active site in ApnU consists of binuclear type II copper centres, as revealed by electron paramagnetic resonance spectroscopy. This discovery expands the enzymatic capability of C(sp 3 )−H halogenases and provides a foundational understanding of this family of binuclear copper-dependent oxidative enzymes.

biocatalysis↗
DOE OSTI2025

Investigating Np(VI) Nitrate Speciation Control through Temperature and Optical Spectroscopy

Numerous areas of nuclear processing, such as radioisotope production, nuclear waste remediation, and separations, depend upon the speciation of f-elements in the solution state. However, fundamental knowledge of the actinides─particularly Np─lags behind most of the elements on the periodic table. Despite the importance of Np(VI) chemistry in separations and nuclear processing, its speciation in HNO 3 remains uncertain. This work addresses some of these gaps by investigating the effect of HNO 3 concentration and temperature on the spectra and speciation of the Np(VI) nitrate system. Six samples of Np in 1 to 10 M HNO 3 were prepared and treated with (NH 4 ) 2 [Ce(NO 3 ) 6 ] to stabilize the hexavalent oxidation state. The absorbance spectrum of the 10 M HNO 3 is drastically different from the spectra of the other samples; the 10 M spectrum indicates coordination of nitrate ligands to the Np(VI)O 2 2+ ion to form a complex with high symmetry. Additionally, absorbance spectra were recorded over the temperature range of 15 to 40 °C, and systematic increases and decreases in certain spectral features of the ultraviolet–visible (UV–vis)–near-infrared (NIR) spectra are present in the spectra. The difference in spectral features suggests that Np(VI) nitrate speciation depends on temperature. Dilution studies of this sample were monitored with UV–vis–NIR and Raman spectroscopies. Spectral data indicate the presence of multiple complexes with different symmetries, including a high-symmetry complex with an inversion center. As samples are diluted and aquo ligands replace nitrate ligands bound to the Np(VI) neptunyl cation, changes in spectroscopic signals indicate a decrease in the high-symmetry nitrate complex and an increase in the lower-symmetry aquo complex. Additionally, the Raman band associated with the Np(VI)O 2 2+ symmetric stretch broadens with dilution and is fitted with two peaks. These peaks are assigned to Np(VI) aquo and nitrato complexes, indicating that this vibrational mode is sensitive to the coordination environment of the Np(VI) neptunyl cation and that contributions from these two Np(VI) complexes can be distinguished. This unique experimental data could be used to advance computational models describing the electronic transitions of complex actinyl ions.

Absorption↗
DOE OSTI2023

Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO 4 and Th–ReO 4 Frameworks and Solutions

Technetium-99, a β-emitter produced from 235 U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO 4 – ) with the actinides (An) during nuclear fuel reprocessing. Previous studies suggested that direct coordination of pertechnetate with An plays an important role in the coextraction process. However, few studies have provided direct evidence for An–TcO 4 – bonding in the solid state, and even fewer in solution. The present study describes synthesis and structural elucidation of a family of thorium(IV)-pertechnetate/perrhenate (ReO 4 – , nonradioactive surrogate) compounds, which is obtained by dissolution of thorium oxyhydroxide in perrhenic/pertechnic acid followed by crystallization, with or without heating. For reaction ratios of 3:1, 4:1, and 6:1 MO 4 – /Th(IV) (M = Tc, Re), the crystallized compounds reflect the same ratio, suggesting facile and flexible coordination. Furthermore, nine structures reveal 1-dimensional and 2-dimensional frameworks with varying topologies. While a multitude of compounds isolated from 4:1 (and 6:1) reaction solutions feature Th monomers linked by MO 4 – , the 3:1 reaction solution yielded the well-known dihydroxide-bridged thorium dimer, linked, and capped by MO 4 – . Density functional theory calculations on ReO 4 – /TcO 4 – isomorphs suggest similar bonding characteristics in the solid state, but experimental solution characterization noted differences. Specifically, small-angle X-ray scattering studies suggest the bonding of Th–TcO 4 – persists in solution, while Th–ReO 4 – bonding is less apparent.

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

Static and dynamic properties of atomic nuclei with high-resolution potentials

Here, we compute ground-state and dynamical properties of 4 He and 16 O nuclei using as input high-resolution, phenomenological nucleon-nucleon and three-nucleon forces that are local in coordinate space. The nuclear Schrodinger equation for both nuclei is accurately solved employing the auxiliary-field diffusion Monte Carlo approach. For the 4 He nucleus, detailed benchmarks are carried out with the hyperspherical harmonics method. In addition to presenting results for the binding energies and radii, we also analyze the momentum distributions of these nuclei and their Euclidean response function corresponding to the isoscalar density transition. The latter quantity is particularly relevant for lepton-nucleus scattering experiments, as it paves the way to quantum Monte Carlo calculations of electroweak response functions of 16 O.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
NASA NTRS1974

Robot arm dynamics and control

Variations in total inertia and gravity loads at the joint outputs are treated along with the relative importance of gravity and acceleration-generated reaction torques or forces versus inertia torques or forces. The relation between the dynamical state equations in explicit terms and servoing the manipulator is briefly discussed in the framework of state variable feedback control which also forms the basis of adaptive manipulator control. Exact state equations were determined for total inertia and gravity loads at the joint outputs as a function of joint variables, using the constant inertial and geometric parameters of the individual links defined in the respective link coordinate frames. The range of maximum variations in total inertia and gravity loads at the joint outputs was calculated for both no load and load in the hand. The main result is the construction of a set of greatly simplified state equations which describe the total inertia and gravity load variations at the output of the six joints with an average error of less than 5%.

Bejczy, A. K.↗
NASA NTRS1994

Gasdynamic models of the solar wind/interstellar medium interaction

The interaction between the solar wind and the interstellar medium is modeled self-consistently using numerical solutions of the time-dependent gasdynamic equations in spherical and cylindrical coordinates. For the results presented here it is assumed that the solar system moves through the surrounding medium with a supersonic velocity. After an initial (nonequilibrium) state has been specified, the numerical solution follows the evolution in time until the interaction relaxes to a dynamic equilibrium. As would be expected, the solutions show the formation of a bow shock upstream of the traveling solar system to deflect the interstellar plasma around the cavity created by the solar wind. A terminiation shock also forms to slow and compress the solar wind plasma. For the simulation in spherical coordinates, the downstream portion of the termination shock reaches equilibrium more than three times further from the Sun than the equilibrium distance to the termination shock on the upstream side.

Steinolfson, R. S.↗
DOE OSTI2020

Record-high stability and compactness of multiply-charged clusters aided by selected terminal groups

Multiply-charged clusters with compact sizes that are stable in the gas phase are important due to their potential applications as weakly-coordinating ions and building blocks of bulk materials. However, the number of these clusters, especially those with high charge states beyond two, is limited. In this work, we show that gas-phase di- and tri-anions with record-high stability and compactness can be developed by utilizing a series of stable mono-anions with linear configurations as ligands. A stable di-anion with a record-high second electron binding energy of 6.26 eV and the smallest tri-anion with a record-low radius of 4.85 Å have been identified. This study demonstrates that multiply-charged clusters with highly charged state and compact sizes can be stabilized solely by selected terminal groups in the structure. This finding significantly enriches the database of stable multiply-charged gas-phase clusters and provides a path towards rational design of further multiply-charged species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Structure, bonding and electronic characteristics of amorphous Se

Ovonic threshold switching (OTS) selector can effectively improve the storage density and suppress the leakage current of advanced phase-change memory. As a prototypical OTS material, amorphous GeSe is widely investigated. But the attentions paid to amorphous Se (i.e., the functional constituent in amorphous GeSe) is very limited up to now. Here, in this work, we have explored the structure, bonding and electronic characteristics of amorphous Se using ab initio molecular dynamics simulations. The results reveal that the Se atoms in amorphous Se tend to form the 2-coordinated configurations, and they connect with each other to form the long chains. The fraction of vibrational density of state located in high frequency range is relatively large, and the formation energy of Se-Se bond is as large as 4.44 eV, hinting that the Se-Se bonds in chains possess a high stability. In addition, the mid-gap state related to the OTS behavior is also found in the amorphous Se despite of the small proportion. Our findings enrich the knowledge of the amorphous Se, which contributes to the applications of Se-based OTS selectors.

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

Assessing the Level of Inter-Sectoral Policy Integration for Governance in the Water–Energy Nexus: A Comparative Study of Los Angeles and Beijing

As concerns around water scarcity and energy security increase, so too has interest in the connections between these resources, through a concept called the water–energy nexus. Efforts to improve the integration of water and energy management and to understand their cross-sector relevance are growing. In particular, this paper develops a better empirical understanding on the extent to which governance settings hinder and/or enable policy coherence between the water and energy sectors through a comparative analysis of two case studies, namely, Los Angeles County, California, the United States, and the city of Beijing, China. This paper examines the extent to which the institutional context enables policy coordination within (vertically) and between (horizontally) the water and energy sectors in Beijing and Los Angeles. To do so, we propose a framework for analyzing policy integration for the water energy nexus based on environmental policy integration (EPI). The results highlight the multiple and flexible approaches of EPI in nexus governance, not least with regards to horizontal and vertical policy integration, but also in terms of explicit (i.e., intended) and implicit (i.e., unintended) coordination. The level of nexus-focused policy integration is highly dependent on the motivation at the local context and the criteria to evaluate policy success in each sector.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
NASA NTRS1982

Merging LANDSAT Derived Land Covers into Quad-referenced Geographic Information Systems

An approach for merging multiscene LANDSAT data bases into existing geographic information systems having 5-second or smaller cells is described. The approach uses the output from the State of Maryland's UNIVAC 1180-based LANDSAT classification program ASTEP (Algorithm Simulation Test and Evaluation) developed by NASA. The structure of the technique was designed to address the problems that emerged as part of the LANDSAT classification of the 64,000 square mile Chesapeake water shed involving twelve scenes. The removal of overlap among adjacent scenes, the crossreferencing of ground control points, and the isolation of the appropriate pixels from the LANDSAT data base for subsequent positioning into a file containing ancillary data referenced to a specific USGS 7 1/2 minute quadrangle sheet are described. Examples illustrate the clustering of classified LANDSAT pixels to define the dominant land use for each of 8,100 cells within a series of quadrangle sheets distributed over the State of Maryland. The approach uses a hard copy terminal tied to an ASTEP algorithm through telephone lines. A coordinate digitizing board for inputing the position of ground control points is also valuable, although manual measurements are possible. The approach is quite efficient and should be especially attractive for use on regional scale studies.

White, J. M.↗
NASA NTRS1984

Numerical simulation of the viscous flow fields over three-dimensional complicated geometries

A 'thin-layer' Navier-Stokes code capable of predicting steady state viscous flows is applied to complicated three-dimensional flow fields. The code is written in a generalized coordinate system, and a recently developed grid generation procedure is used for the flow-field discretization. Application is made to the vortical flow over a delta wing at high angle of attack, and the computed results are compared with experimental results. The results indicate that the present method can capture the physical phenomenon well. It is observed that a leading-edge separation vortex is formed over the wing, as is a secondary separation vortex near the leading edge. The flow field behind the trailing edge is also well described. Application is also made to the transonic flow over the Shuttle configuration. The result appears to be reasonable even though no experimental data are available for comparison. These results indicate that the present approach is capable of computing complicated three-dimensional flow fields.

Fujii, K.↗
NASA NTRS1984

A numerical analysis of transient planetary waves and the vertical structure in a meso-strato-troposphere model, part 1.4A

The structure of unstable planetary waves is computed by a quasi-geostrophic model extending from the surface up to 80 km by means of eigenvalue-eigenfunction techniques in spherical coordinates. Three kinds of unstable modes of distinct phase speeds and vertical structures are identified in the winter climate state: (1) the deep Green mode with its maximum amplitude in the stratosphere; (2) the deep Charney mode with its maximum amplitude in the troposphere: and (3) the shallow Charney mode which is largely confined to the troposphere. Both the Green mode and the deep Charney mode are characterized by very slow phase speeds. They are mainly supported by upward wave energy fluxes, but the local baroclinic energy conversion within the stratosphere also contributes in supporting these deep modes. The mesosphere and the troposphere are dynamically independent in the summer season decoupled by the deep stratospheric easterly. The summer mesosphere supports the easterly unstable waves 1-4. Waves 3 and 4 are identified with the observed mesospheric 2-day wave and 1.7-day wave, respectively.

Zhang, K. S.↗
NASA NTRS1990

Preconditioned upwind methods to solve 3-D incompressible Navier-Stokes equations for viscous flows

A computational method for calculating low-speed viscous flowfields is developed. The method uses the implicit upwind-relaxation finite-difference algorithm with a nonsingular eigensystem to solve the preconditioned, three-dimensional, incompressible Navier-Stokes equations in curvilinear coordinates. The technique of local time stepping is incorporated to accelerate the rate of convergence to a steady-state solution. An extensive study of optimizing the preconditioned system is carried out for two viscous flow problems. Computed results are compared with analytical solutions and experimental data.

Hsu, C.-H.↗
NASA NTRS1992

Orbit determination by solving for gravity parameters with multiple arc data

The orbit of a satellite that repeats in the earth fixed coordinates is determined by combining GPS tracking data from multiple arcs. The satellite dynamics are modeled with the epoch state and a set of parameters, called the bin parameters, that account for the effect of the local gravitational field on the satellite current state. The epoch state is specific to each arc, and the bin parameters are common to all repeat arcs. The estimation algorithm is based on the Square Root Information Filter. It involves partitioning of the measurement matrix and use of the Householder transformation to combine multiple arc data and solve for the epoch states and the bin parameters. The bin parameters can then be converted into the earth's gravitational field with a modest amount of computation.

Wu, Jiun-Tsong↗
NASA NTRS2004

Reconditioning of Batteries on the International Space Station

Primary source of electric power for the International Space Station (ISS) is the photovoltaic module (PVM). At assembly complete stage, the ISS will be served by 4 PVMs. Each PVM contains two independent power channels such that one failure will result in loss of only one power channel. During early stages of assembly, the ISS is served by only one PVM designated as P6. Solar arrays are used to convert solar flux into electrical power. Nickel hydrogen batteries are used to store electrical power for use during periods when the solar input is not adequate to support channel loads. Batteries are operated per established procedures that ensure that they are maintained within specified temperature limits, charge current is controlled to conform to a specified charge profile, and battery voltages are maintained within specified limits. Both power channels on the PVM P6 have been operating flawlessly since December 2000 with 100 percent power availability. All components, including batteries, are monitored regularly to ensure that they are operating within specified limits and to trend their wear out and age effects. The paper briefly describes the battery trend data. Batteries have started to show some effects of aging and a battery reconditioning procedure is being evaluated at this time. Reconditioning is expected to reduce cell voltage divergence and provide data that can be used to update the state of charge (SOC) computation in the software to account for battery age. During reconditioning, each battery, one at a time, will be discharged per a specified procedure and then returned to a full state of charge. The paper describes the reconditioning procedure and the expected benefits. The reconditioning procedures have been thoroughly coordinated by all affected technical teams and approved by all required boards. The reconditioning is tentatively scheduled for September 2004.

Hajela, Gyan↗
NASA NTRS2005

Investigation of Integrated Vehicle Health Management Approaches

This report is to present the work that was performed during the summer in the Advance Computing Application office. The NFFP (NASA Faculty Fellow Program) had ten summer faculty members working on IVHM (Integrated Vehicle Health Management) technologies. The objective of this project was two-fold: 1) to become familiar with IVHM concepts and key demonstrated IVHM technologies; and 2) to integrate the research that has been performed by IVHM faculty members into the MASTLAB (Marshall Avionic Software Test Lab). IVHM is a NASA-wide effort to coordinate, integrate and apply advanced software, sensors and design technologies to increase the level of intelligence, autonomy, and health state of future vehicles. IVHM is an important concept because it is consistent with the current plan for NASA to go to the moon, mars, and beyond. In order for NASA to become more involved in deep exploration, avionic systems will need to be highly adaptable and autonomous.

Paris, Deidre↗