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At least 55 records · Page 3

Two-particle angular correlations in e + e - collisions to hadronic final states in two reference coordinates at Belle

We present the analysis of two-particle angular correlations using coordinate systems defined with the conventional beam axis and the event thrust axis. We propose the latter as a good representation for the correlation structure interpretation in the e + e - collision system. The e + e - collisions to hadronic final states at center-of-mass energies of $\sqrt{s}$ = 10.52 GeV and 10.58 GeV are recorded by the Belle detector at KEKB. In this paper, results on the first dataset are supplementary to the previous Belle publication [1]. At the same time, the latter is the first two-particle correlation measurement at collision energy on the Υ(4S) resonance and is sensitive to its decay products. Measurements are reported as a function of the charged-particle multiplicity. Finally, a qualitative understanding of the correlation structure is discussed using a combination of Monte Carlo simulations and experimental data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds

We report structures of 388 neptunium-bearing crystal structures are sorted into an expanded structural hierarchy and examined. The majority of structures contain Np(V) (149), Np(VI) (99), or Np(IV) (91) whereas structures containing Np(II), Np(III), Np(VII), or more than one oxidation state are rare. Coordination geometry of Np(V) and Np(VI) compounds is dominated by the approximately linear neptunyl cation. Actinyl–actinyl interactions (AAIs) are most prevalent in Np(V) compounds and are observed in 48% of these extended structures. Prismatic coordination geometries are commonly observed in Np(IV) compounds. Np(III) organometallic complexes display a variety of coordination modes. Coordination chemistry of Np(VII) compounds is dominated by the tetra-oxido core. Updated average bond length values are provided for Np(IV), Np(V), Np(VI), and Np(VII) compounds and updated bond valence parameters for Np(IV) are reported. A graphical notation system for neptunyl structures coordinated by organic ligands was developed to facilitate discussion and identify similarities between neptunyl compounds coordinated by oxyanions and neptunyl compounds coordinated by organic ligands.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excited-state structural dynamics of nickel complexes probed by optical and X-ray transient absorption spectroscopies: insights and implications

Excited states of nickel complexes undergo a variety of photochemical processes, such as charge transfer, ligation/deligation, and redox reactions, relevant to solar energy conversion and photocatalysis. The efficiencies of the aforementioned processes are closely coupled to the molecular structures in the ground and excited states. The conventional optical transient absorption spectroscopy has revealed important excited-state pathways and kinetics, but information regarding the metal center, in particular transient structural and electronic properties, remains limited. These deficiencies are addressed by X-ray transient absorption (XTA) spectroscopy, a detailed probe of 3d orbital occupancy, oxidation state and coordination geometry. The examples of excited-state structural dynamics of nickel porphyrin and nickel phthalocyanine have been described from our previous studies with highlights on the unique structural information obtained by XTA spectroscopy. Furthermore, we close by surveying prospective applications of XTA spectroscopy to active areas of Ni-based photocatalysis based on the knowledge gained from our previous studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ground electronic state description of thiourea coordination in homoleptic Zn 2+ , Ni 2+ and Co 2+ complexes using sulfur K -edge X-ray absorption spectroscopy

Sulfur K-edge X-ray absorption spectroscopy (XAS) was employed to experimentally characterize the coordinative bond between the thiourea (TU) or thiocarbamide ligand and transition metal (TM) ions Zn 2+ , Co 2+ and Ni 2+ in distorted tetrahedral and octahedral homoleptic coordination environments. Comparisons of XAS spectra of the free TU ligand and [Zn(TU) 4 ] 2+ , [Co(TU) 4 ] 2+ and [Ni(TU) 6 ] 2+ complexes clearly identify spectral features unique to TM 2+ –S(TU) bonding. Quantitative analysis of pre-edge intensities describes the covalency of Ni 2+ —S(TU) and Co 2+ —S(TU) bonding to be at most 21% and 9% as expressed by the S 3p contributions per TM 3d electron hole. Using relevant Ni 2+ complexes with dithiocarbamate and thioether ligands, we evaluated the empirical S 1s → 3p transition dipole integrals developed for S-donor ligands and their dependence on heteroatom substitutions. With the aid of density functional theory-based ground electronic state calculations, we found evidence for the need of using a transition dipole that is dependent on the presence of conjugated heteroatom (N) substitution in these S-donor ligands.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Radical–Radical Reactions in Molecular Weight Growth: The Phenyl + Propargyl Reaction

The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C 6 H 5 ) with propargyl radical (H 2 CCCH) provides an important prototype for radical–radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300–1000 K and pressure range of 4–10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C 9 H 8 and C 9 H 7 + H product channels and report experimental isomer-resolved product branching fractions for the C 9 H 8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. Here, these ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical–radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C 9 H 7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C 9 H 7 ) recombination to indene and H-assisted isomerization that converts less stable C 9 H 8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic Structures of Iron in Oxide Glasses via 1s3p Resonant Inelastic X-ray Scattering

Electronic structures of iron in glasses are essential for unraveling the effect of transition metals on amorphous networks and controlling the electro-optical and transport properties of advanced glasses and amorphous energy-storing materials. The electronic configurations around iron in glasses, however, remain not well understood due to the structural disorders arising from multiple iron species with distinct valence, coordination, and spin states. Here, the first 1s3p resonant inelastic X-ray scattering (RIXS) for oxide glasses identifies hidden electronic configurations for Fe 2+ and Fe 3+ in amorphous networks. The results allow us to quantify the composition-induced evolution of oxygen ligand–field interactions of high-spin Fe 3d states with varying valence and coordination environments in complex glasses. The distinct electronic structures account for the electronic origins of iron-induced changes in the glass properties. The results offer prospects for a simultaneous probing of valence, coordination, and spin states of transition metals in diverse multicomponent oxide glasses and functional amorphous solids via 1s3p RIXS.

Kim, Yong-Hyun [Seoul National Univ. (Korea, Repub↗

Long Excited-State Lifetimes in Three-Coordinate Copper(I) Complexes via Triplet–Triplet Energy Transfer to Pyrene-Decorated Isocyanides

There has been much effort to improve excited-state lifetimes in photosensitizers based on earth-abundant first-row transition metals. Copper(I) complexes have gained significant attention in this field, and in most cases, sterically driven approaches are used to optimize their lifetimes. This study presents a series of three-coordinate copper(I) complexes (Cu1–Cu3) where the excited-state lifetime is extended by triplet–triplet energy transfer. The heteroleptic compounds feature a cyclohexyl-substituted β-diketiminate (CyNacNac Me ) paired with aryl isocyanide ligands, giving the general formula Cu(CyNacNac Me )(CN-Ar) (CN-dmp = 2,6-dimethylphenyl isocyanide for Cu1; CN-pyr = 1-pyrenyl isocyanide for Cu2; CN-dmp-pyr = 2,6-dimethyl-4-(1-pyrenyl)phenyl isocyanide for Cu3). The nature, energies, and dynamics of the low-energy triplet excited states are assessed with a combination of photoluminescence measurements at room temperature and 77 K, ultrafast transient absorption (UFTA) spectroscopy, and DFT calculations. The complexes with the pyrene-decorated isocyanides (Cu2 and Cu3) exhibit extended excited-state lifetimes resulting from triplet–triplet energy transfer (TTET) between the short-lived charge-transfer excited state ( 3 CT) and the long-lived pyrene-centered triplet state ( 3 pyr). This TTET process is irreversible in Cu3, producing exclusively the 3 pyr state, and in Cu2, the 3 CT and 3 pyr states are nearly isoenergetic, enabling reversible TTET and long-lived 3 CT luminescence. The improved photophysical properties in Cu2 and Cu3 result in improvements in activity for both photocatalytic stilbene E/Z isomerization via triplet energy transfer and photoredox transformations involving hydrodebromination and C–O bond activation. Furthermore, these results illustrate that the extended excited-state lifetimes achieved through TTET result in newly conceived photosynthetically relevant earth-abundant transition metal complexes.

14 SOLAR ENERGY↗

Hidden transformations in entropy-stabilized oxides

We report entropy-stabilized oxides (ESO) display a reversible entropy-driven phase transformation that can be leveraged to produce a continuum of metastable phase states, allowing for property optimization and novel functionalities. X-ray absorption spectroscopy reveals that entropic stabilization extends to the electronic structure (valence state and cation coordination) in sintered (Co,Cu,Mg,Ni,Zn)O, manifesting as a tunable lattice distortion in the entropy-stabilized phase. Co, Cu, and Zn ions reversibly transform from six-fold to four-fold coordinated structures and from low to high valence states due to the competition between electronic structures that are equilibrium and enthalpy-driven or metastable and entropy-driven. The segregation of a Cu-rich tenorite phase and a Co-rich spinel phase influences the electronic structure evolution. ESOs can adjust their electronic structures through heat treatment, providing a powerful tool for developing functional properties. These results indicate that the definition of entropy stabilization should include entropy-stabilized electronic structures, providing motivation to reassess previously studied HEO materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and bonding of a radium coordination compound in the solid state

The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra 2+ complex using 226 Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra 2+ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba 2+ ) yielded a 10-coordinate ‘Pac-Man’-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra 2+ and by analogy with Ba 2+ , supporting greater water lability in Ra 2+ complexes than in their Ba 2+ counterparts. In conclusion, barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra 2+ chemistry cannot always be predicted using Ba 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B 12 Coenzymes Controlled by the Axial Base

Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. Here these data provide insights into the role of the lower axial ligand in modulating the reactivity of B 12 coenzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generator coordinate method for transition-state dynamics in nuclear fission

Since its beginnings, fission theory has assumed that low-energy induced fission takes place through transition-state channels at the barrier tops. Nevertheless, up to now there is no microscopic theory applicable to those conditions. We suggest that modern reaction theory is suitable for this purpose, and propose a methodology based on a configuration-interaction framework using the generator coordinate method (GCM). Simple reaction-theoretic models are constructed with the Gaussian overlap approximation to parametrize both the dynamics within the channels and their incoherent couplings to states outside the barrier. The physical characteristics of the channels examined here are their effective bandwidths and the quality of the coupling to compound-nucleus states as measured by the transmission factor T. We also investigate the spacing of GCM states with respect to their degree of overlap. We find that a rather coarse mesh provides an acceptable accuracy for estimating the bandwidths and transmission factors. The common numerical stability problem in using the GCM is avoided due to the choice of meshes and the finite bandwidths of the channels. Here, the bandwidths of the channels are largely controlled by the zero-point energy with respect to the collective coordinate in the GCM configurations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Transformation theory and translation factors in inelastic atomic collisions

It is shown through the use of transformation theory that unique semiclassical atomic scattering states which obey the asymptotic conditions of formal scattering theory can be derived by transforming 'nontraveling' atomic states, ie., states whose coordinate variables are referred to a stationary origin, to frames at rest with respect to the incoming or outgoing particles. An overview of the problem of properly defining such scattering states is presented. The operator which carries out the necessary transformation from inertial to noninertial frames is derived and its properties are discussed. The relation of this transformation operator to the 'translation factor' discussed in the literature is presented. The application of this operator to transform the time-dependent Schroedinger equation from an inertial to a noninertial frame is presented and shown to introduce new terms in the resulting equation. The implications of these new terms to scattering problems are discussed.

Schmid, G. B.↗

Differential GPS and system integration of the Low Visibility Landing and Surface Operations (LVLASO) demonstration

The LVLASO Flight Demonstration of ASTA concepts (FDAC) integrates NASA-Langley's electronic moving map display and Transport Systems Research Vehicle (TSRV) (a modified Boeing 737 aircraft); ARINC's VHF data link, GPS ground station, and automated controller workstation; and Norden's surface radar/airport movement safety system. Aircraft location is shown on the electronic map display in the cockpit. An approved taxi route as well as other aircraft and surface traffic are also displayed. An Ashtech Z12 Global Positioning System (GPS) receiver on the TSRV estimates the aircraft's position. In Differential mode (DSPS), the Ashtech receiver accepts differential C/A code pseudorange corrections from a GPS ground station. The GPS ground station provides corrections up to ten satellites. The corrections are transmitted on a VHF data link at a 1 Hz. rate using the RTCM-104 format. DGPS position estimates will be within 5 meters of actual aircraft position. DGPS position estimates are blended with position, velocity, acceleration, and heading data from the TSRV Air Data/Inertial Reference System (ADIRS). The ADIRS data is accurate in the short-term, but drifts over time. The DGPS data is used to keep the ADIRS position accurate. Ownship position, velocity, heading, and turn rate are sent at a 20 Hz. rate to the electronic map display. Airport traffic is detected by the airport surface radar system. Aircraft and vehicles such as fuel trucks and baggage carts are detected. The traffic's location, velocity, and heading are sent to the TSRV. To prevent traffic symbology from jumping each second when a location update arrives, velocity and heading are used to predict a new traffic location for each display update. Possible runway incursions and collisions can be shown on the electronic map. Integrating the different systems used in the FDAC requires attention to the underlying coordinate systems. The airport diagram displayed on the electronic map is obtained from published navigational charts. The charts reference the North American Datum of 1927 (NAD27) or a local state-plane coordinate system. GPS uses the World Geodetic Standard of 1984 (WGS84). Both NAD27 and WGS84 model the Earth as an ellipsoid, however, they use a different origin and different size ellipsoids. Latitudes and longitudes given in these systems can be converted to a Cartesian system with the origin at the Earth's center. The surface radar detects traffic in a locally-level, rho-theta coordiante system. The electronic airport diagram is stored using a flat XY coordinate system. The map origin is at the tower and is referenced as True North up. All ownship and other traffic positions must be converted to the electronic map's frame of reference for display.

Rankin, James M.↗

Control Analysis of flexible Solar Sails

Future solar sail missions will require sails with dimensions on the order of 100 m to l km. At these sizes, given the gossamer nature of the sail supporting structures, flexible modes may be low enough to interact with the control system. This paper develops a practical analysis of the flexible interactions using state-space systems and modal data from standard finite element models of the sail sub- system. The modal data is combined with a rigid core bus to create a modal coordinate state-space plant, which can be analyzed for stability with a state-space controller. Results are presented for an 80 m sail for both collocated actuation and control by actuators mounted at the sail tips.

Thomas, Stephanie J.↗

The Importance of Semi-Major Axis Knowledge in the Determination of Near-Circular Orbits

Modem orbit determination has mostly been accomplished using Cartesian coordinates. This usage has carried over in recent years to the use of GPS for satellite orbit determination. The unprecedented positioning accuracy of GPS has tended to focus attention more on the system's capability to locate the spacecraft's location at a particular epoch than on its accuracy in determination of the orbit, per se. As is well-known, the latter depends on a coordinated knowledge of position, velocity, and the correlation between their errors. Failure to determine a properly coordinated position/velocity state vector at a given epoch can lead to an epoch state that does not propagate well, and/or may not be usable for the execution of orbit adjustment maneuvers. For the quite common case of near-circular orbits, the degree to which position and velocity estimates are properly coordinated is largely captured by the error in semi-major axis (SMA) they jointly produce. Figure 1 depicts the relationships among radius error, speed error, and their correlation which exist for a typical low altitude Earth orbit. Two familiar consequences are the relationship Figure 1 shows are the following: (1) downrange position error grows at the per orbit rate of 3(pi) times the SMA error; (2) a velocity change imparted to the orbit will have an error of (pi) divided by the orbit period times the SMA error. A less familiar consequence occurs in the problem of initializing the covariance matrix for a sequential orbit determination filter. An initial covariance consistent with orbital dynamics should be used if the covariance is to propagate well. Properly accounting for the SMA error of the initial state in the construction of the initial covariance accomplishes half of this objective, by specifying the partition of the covariance corresponding to down-track position and radial velocity errors. The remainder of the in-plane covariance partition may be specified in terms of the flight path angle error of the initial state. Figure 2 illustrates the effect of properly and not properly initializing a covariance. This figure was produced by propagating the covariance shown on the plot, without process noise, in a circular low Earth orbit whose period is 5828.5 seconds. The upper subplot, in which the proper relationships among position, velocity, and their correlation has been used, shows overall error growth, in terms of the standard deviations of the inertial position coordinates, of about half of the lower subplot, whose initial covariance was based on other considerations.

Carpenter, J. Russell↗

Oxidation states of iron and manganese in lignocellulose altered by the brown rot fungus Gloeophyllum trabeum measured in-situ using X-ray absorption near edge spectroscopy (XANES)

Brown rot fungi utilize iron as part of a chelator-mediated Fenton (CMF) reaction during wood biodegradation. Research suggests these fungi reduce Fe 3+ to promote oxygen radical generation resulting in depolymerization of the wood cell wall. High levels of Mn are also found in wood decayed by brown rot fungi. However, little is known about the oxidation states of Fe and Mn during the decay process. X-ray absorption near edge spectroscopy (XANES) can be used to examine metal oxidation states and coordination chemistry. In this work, XANES experiments were conducted on wood decayed by Gloeophyllum trabeum over 2–8 weeks with results showing that Mn 2+ and Fe 3+ predominated for metal oxidation states. However, Fe 2+ was present at sites of greater fungal growth In certain cases, the μXANES measurements showed that the fraction of Fe 2+ in the wood samples was as high as 50%. Localized areas of reduced iron corresponded with areas of greater fungal hyphal mass which is in agreement with how brown rot fungi decay wood via the CMF reaction. The limited change in oxidation state of Mn observed in wood with active fungal activity suggests that the role of manganese in CMF biodegradation chemistry should be further explored.

59 BASIC BIOLOGICAL SCIENCES↗

Narragansett Bay From Space: A Perspective for the 21st Century

In 1996, the NASA Administrator Dan Goldin and Rhode Island Congressman Patrick Kennedy challenged researchers in the Department of Geological Sciences at Brown University to developed a series of projects to apply remotely sensed data to problems of immediate concern to the State of Rhode Island. The result of that challenge was the project Narragansett Bay from Space: A Perspective for the 21st Century. The goals of the effort were to a) identify problems in coordination with state and local agencies, b) apply NASA technology to the problems and c) to involve small business that would benefit from incorporating remotely sensed data into their business operations. The overall effort was to serve two functions: help provide high quality science results based on remotely sensed data and increase the capacity of environmental managers and companies to use remotely sensed data. The effort has succeeded on both these fronts by providing new, quantitative information on the extent of environmental problems and developing a greater awareness and acceptance of remotely sensed data as a tool for monitoring and research.

Mustard, John F.↗

Theoretical Kinetics Predictions for Reactions on the NH 2 O Potential Energy Surface

Recent modeling studies of ammonia oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies among the existing literature mechanisms. In this study, high-level theoretical kinetics predictions have been obtained for reactions on the NH 2 O potential energy surface, including the NH 2 + O, HNO + H, and NH + OH reactions. These reactions have previously been highlighted as important reactions in NH 3 oxidation with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations, including large basis sets and high-level corrections to yield high-accuracy (~0.2 kcal/mol 2σ uncertainty) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature- and pressure-dependent kinetics. For radical–radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing directly evaluated multireference electronic energies. The analysis yields predictions for the total rate constants as well as the branching ratios. We find that the NO + H 2 channel contributes 10% of the total NH 2 + O flux at combustion temperatures, although this channel is not included in modern NH 3 oxidation mechanisms. Modeling is used to illustrate the ramifications of these rate predictions on the kinetics of NH 3 oxidation and NO x formation. Finally, the present results for NH 2 + O are important for predicting the chain branching and formation of NO in the oxidation of NH 3 and thermal DeNO x .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗