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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Cyclohexene epoxidation with H 2 O 2 in the vapor and liquid phases over a vanadium-based metal–organic framework

A metal–organic framework, MIL-47(V) containing coordinatively saturated V +IV sites linked together by terephthalic linkers, was prepared by a solvothermal method and evaluated as a catalyst in the epoxidation of cyclohexene. We have compared the catalytic activity in the condensed and gas phase oxidation of cyclohexene to discuss the effect of temperature and reaction phase in cyclohexene epoxidation over MIL-47(V). The catalysts were examined for the epoxidation of cyclohexene with H 2 O 2 at 50, 65, 120, and 150 °C. Finally, we observed significant differences in product selectivity between liquid-phase and gas-phase operations and confirmed that the active sites are tightly incorporated into the MOF as node channels and thus resistant to leaching.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Magnetic and EPR Spectroscopic Studies of Thiolate Bridged Divalent Ni, Pd, and Pt Ions Capped with VO(N 2 S 2 ) Metalloligands

Reactions of the metallodithiolate complex VO(bme-dach) (hereafter abbreviated as V, where bme-dach = N,N ′-bis(2-mercaptoethyl)-1,4-diazacycloheptane) with [Pd II (CH 3 CN) 4 ](BF 4 ) 2 and [Pt II (CH 3 CN) 4 ](BF 4 ) 2 yield the V–M–V trimetallic compounds [VPdV](BF 4 ) 2 (2) and [VPtV](BF 4 ) 2 (3). Reaction of a similar metalloligand, VO(bme-daco) (hereafter abbreviated as V′ where bme-daco = N,N′-bis(2-mercaptoethyl)-1,5-diazacyclooctane) with [Ni II (CH 3 CN) 6 ](BF 4 ) 2 afforded the related salt [V′NiV′](BF 4 ) 2 (1). X-ray structural analyses revealed that cations in 1, 2, and 3 adopt a stairstep C 2h structure consisting of two terminal VO(N 2 S 2 ) moieties bridged via thiolate sulfur to the group 10 metal ions. Weak ferromagnetic superexchange coupling (J = 0.282 cm –1 for 1, 0.954 cm –1 for 2, and 1.372 cm –1 for 3) was observed between the two S = 1/2 V IV centers separated by distances in the range of 5.9–6.3 Å, with J values varying following the order Ni < Pd < Pt. Frozen-solution EPR spectra measured on the more soluble [BArF 24 ] − (BArF 24 – = tetrakis((3,5-trifluoromethyl)phenyl)borate) analogues revealed that the [VPtV] 2+ cation exhibits a 15-line hyperfine splitting of 225 MHz at g = 4 in parallel mode, confirming exchange coupling between the two 51 V, I = 7/2 nuclei. Density-functional theory (DFT) calculations indicate an S = 1 ground state for 1–3. These results demonstrate that the choice of paramagnetic metallodithiolate ligand and diamagnetic bridge in such trimetallic species influences the sign and magnitude of magnetic interactions.

anions↗
NASA NTRS1992

Newly identified main-sequence A stars with circumstellar dust

The IRAS Faint Source Survey data base and the ADDSCAN/SCANPI software are used to search for systems with circumstellar dust in two samples: all of the 62 A stars in Woolley's catalog, which lie near the main sequence and are typically within 25 pc of the sun, and all A stars in the Bright Star Catalogue with mV in the range 4-5 and v sin i not less than 100 km/s. In the first sample, 11 nearby A stars having (12)-(25) and (25)-(60) colors consistent with circumstellar dust are found. The analysis of the second sample demonstrates that the use of the FSS data base increases the likelihood of identifying A stars with circumstellar dust fainter than mV = 4. Three more new dusty systems are found in this sample. Beta Pictoris (A5 IV-V) is the only star within 25 pc of the sun that displays IR colors indicative of both warm and cool dust. It is inferred from the absence of cool dust in the vast majority of the systems that the dust disks of these stars are much less extended than that seen around Beta Pictoris.

Cheng, K.-P.↗
DOE OSTI2020

Identification and Quantification of Technetium Species in Hanford Waste Tank AN-102

Technetium-99 (Tc) generated from the fission of 235U and 239Pu in high yields is one of the most difficult contaminants to be addressed at the U.S. Department of Energy Hanford Site. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO4-) (oxidation state VII) as well as in reduced forms (oxidation state < VII) collectively known as non-pertechnetate species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non- pertechnetate species and their identification in the actual tank waste samples, which would facilitate development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(IV, VII) compounds was generated using a range of techniques and applied to the characterization of the actual tank waste supernatant collected from the tank 241-AN-102 at Hanford, WA. A sample of the 241-AN-102 tank waste supernatant was processed to adjust Na concentration to about 5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion exchange resin. Cesium-loaded sRF column was eluted with 0.5 M HNO3. As received AN-102, Cs-depleted AN-102 effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-pertechnetate Tc present in the 241-AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)3]+ and Tc(IV) compounds. This is the second experimental observation of the [fac-Tc(CO)3]+ species in the Hanford tank waste and the first demonstration of multiple forms of non-pertechnetate species existing simultaneously in the waste, cumulatively highlighting their importance for the waste processing.

Low Activity Waste (LAW), High Level Waste, nuclea↗
DOE OSTI2020

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors

We report controlling site disorder in ternary and multinary compounds enables tuning optical and electronic properties at fixed lattice constants and stoichiometries, moving beyond many of the challenges facing binary alloy systems. Here, we consider possible enhancements to energy-related applications through the integration of disorder-tunable materials in devices such as light-emitting diodes, photonics, photovoltaics, photocatalytic materials, batteries, and thermoelectrics. However, challenges remain in controlling and characterizing disorder. Focusing primarily on II–IV–V 2 materials, we identify three metrics for experimentally characterizing cation site disorder. Complementary to these experiments, we discuss simulation methods to understand disordered materials. Nonidealities, such as off-stoichiometry and oxygen incorporation, can occur while synthesizing metastable disordered materials. While nonidealities may seem undesirable, we describe how if harnessed they could provide another knob for tuning disorder and subsequently properties. To illustrate the effects of disorder on device-relevant properties, we provide case examples of disordered materials and their potential in device applications.

36 MATERIALS SCIENCE↗
NASA NTRS1997

The RS CVn Binary HD 155555: A Comparative Study of the Atmospheres for the Two Component Stars

We present GHRS/HST observations of the RS CVn binary system HD 155555. Several key UV emission lines (Fe XXI, Si IV, O V, C IV) have been analyzed to provide information about the heating rate throughout the atmosphere from the chromosphere to the corona. We show that both the G and K components reveal features of a chromosphere, transition region and corona. The emission measure distribution as a function of temperature for both components is derived and compared with the RS Cvn system, HR 1099, and the Sun. The transition region and coronal lines of both stars show nonthermal broadenings of approx. 20-30 km/s. Possible physical implications for coronal heating mechanisms are discussed.

Airapetian, V. S.↗
DOE OSTI2024

Implementation of an extensible property modeling framework in ESPEI with applications to molar volume and elastic stiffness models

Property models are becoming more widely adopted by commercial Calphad databases, but they are not nearly as common in non-commercial or traditional academic Calphad databases. A primary driver is that user-friendly Calphad modeling tools that support property models are not widely available. Here we present new property modeling capabilities that have been implemented in ESPEI (the Extensible, Self-optimizing Phase Equilibrium Infrastructure). These capabilities include both generating property model parameters from data and improvements to the algorithmic selection of the most appropriate model from a series of candidates. Additionally, two illustrative examples are given that use ESPEI to fit different property models. First, we generate molar volume model parameters for Group IV, V, and VI refractory BCC alloys based on the model by Lu et al. (2005). Second, we demonstrate the extensibility of ESPEI’s property modeling capabilities by implementing a custom PyCalphad model for BCC elastic stiffness parameters to generate and compare parameters to the ones assessed by Marker et al. (2018) using the same data. Property models generated by ESPEI can be used in PyCalphad or further optimized with uncertainty quantification using ESPEI.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Sensor Fusion: Comprehensive Real-Time, On-Line Monitoring for Process Control via Visible, Near-Infrared, and Raman Spectroscopy

On-line monitoring based on optical spectroscopy provides unprecedented insight into the chemical composition of process streams or batches. Amplifying this approach through utilizing multiple forms of optical spectroscopy in sensor fusion can greatly expand the number and type of chemical species that can be identified and quantified. This is demonstrated herein, on the analysis of used nuclear fuel recycling streams: highly complex processes with multiple target and interfering analytes. The optical techniques of visible absorbance, near infrared absorbance, and Raman spectroscopy were combined to quantify plutonium (III, IV, VI), uranium (IV, VI), neptunium (IV, V, VI), and nitric acid. Chemometric modeling was used to quantify analytes in process streams in real-time and results were successfully used to enable immediate process control and generation of a product stream at a set composition ratio. This represents a significant step forward in the ability to monitor and control complex chemical processes occurring in harsh chemical environments.

47 OTHER INSTRUMENTATION↗
DOE OSTI2022

Illuminating Ligand Field Contributions to Molecular Qubit Spin Relaxation via T 1 Anisotropy

Electron spin relaxation in paramagnetic transition metal complexes constitutes a key limitation on the growth of molecular quantum information science. However, there exist very few experimental observables for probing spin relaxation mechanisms, leading to a proliferation of inconsistent theoretical models. Here we demonstrate that spin relaxation anisotropy in pulsed electron paramagnetic resonance is a powerful spectroscopic probe for molecular spin dynamics across a library of highly coherent Cu(II) and V(IV) complexes. Here, neither the static spin Hamiltonian anisotropy nor contemporary computational models of spin relaxation are able to account for the experimental T 1 anisotropy. Through analysis of the spin-orbit coupled wavefunctions, we derive an analytical theory for the T 1 anisotropy that accurately reproduces the average experimental anisotropy of 2.5. Furthermore, compound-by-compound deviations from the average anisotropy provide a promising approach for observing specific ligand field and vibronic excited state coupling effects on spin relaxation. Finally, we present a simple density functional theory workflow for computationally predicting T 1 anisotropy. Analysis of spin relaxation anisotropy leads to deeper fundamental understanding of spin-phonon coupling and relaxation mechanisms, promising to complement temperature-dependent relaxation rates as a key metric for understanding molecular spin qubits.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The high-valent vanadium chemistry of isoindoline chelates

Isoindoline-based chelates, in particular bis(arylimino)isoindolines, have shown extensive metal binding chemistry. Although this chemistry has been explored for the middle and late transition metal ions, little work has been carried out on early transition metal complexes. In this article, we present the first examples of vanadium coordinated using four bis(arylimino)isoindolines, in which the aryl groups are pyrazole, indazole, benzimidazole, and pyridine (ligands 1–4 , respectively). We isolated five complexes using vanadyl sulfate or vanadyl acetylacetonate as the vanadium source. In all cases, the ligands bound in a meridional mode, and for four of the complexes, the vanadium ion was observed in the V(v) oxidation state. Three of the ligands ( 1–3 ) formed VO 2 complexes with vanadyl sulfate and vanadyl acetylacetonate, but the bis(pyridylimino)isoindoline (ligand 4 ) formed a V(v) oxosulfonato complex with the former starting material and a vanadyl V(iv) acetylacetonate with the latter starting material. All metal compounds were structurally elucidated by X-ray crystallographic methods, and we probed their electronic structures using DFT methods.

Bore, Joan C. [Univ. of Akron, OH (United States)]↗
DOE OSTI2022

Molecular orbital projectors in non-empirical jmDFT recover exact conditions in transition-metal chemistry

Low-cost, non-empirical corrections to semi-local density functional theory are essential for accurately modeling transition-metal chemistry. Here, we demonstrate the judiciously modified density functional theory (jmDFT) approach with non-empirical U and J parameters obtained directly from frontier orbital energetics on a series of transition-metal complexes. We curate a set of nine representative Ti(III) and V(IV) d 1 transition-metal complexes and evaluate their flat-plane errors along the fractional spin and charge lines. We demonstrate that while jmDFT improves upon both DFT+U and semi-local DFT with the standard atomic orbital projectors (AOPs), it does so inefficiently. We rationalize these inefficiencies by quantifying hybridization in the relevant frontier orbitals. To overcome these limitations, we introduce a procedure for computing a molecular orbital projector (MOP) basis for use with jmDFT. We demonstrate this single set of d 1 MOPs to be suitable for nearly eliminating all energetic delocalization and static correlation errors. In all cases, MOP jmDFT outperforms AOP jmDFT, and it eliminates most flat-plane errors at non-empirical values. Unlike DFT+U or hybrid functionals, jmDFT nearly eliminates energetic delocalization and static correlation errors within a non-empirical framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Emulation Modeling for Development of Cyber-Defense Capabilities for Satellite Systems

The objective of this project was to develop a novel capability to generate synthetic data sets for the purpose of training Machine Learning (ML) algorithms for the detection of malicious activities on satellite systems. The approach experimented with was to a) generate sparse data sets using emulation modeling and b) enlarge the sparse data using Generative Adversarial Networks (GANs). We based our emulation modeling on the Open Source NASA Operational Simulator for Small Satellites (NOS3) developed by the Katherine Johnson Independent Verification and Validation (IV&V) program in West Virginia. Significant new capabilities on NOS3 had to be developed for our data set generation needs. To expand these data sets for the purpose of training ML, we experimented with a) Extreme Learning Machines (ELMs) and b) Wasserstein-GANs (WGAN-GP).

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗
NASA NTRS1978

Ultraviolet observations of cool stars. VIII - Interstellar matter toward Procyon

The profile of the chromospheric L-alpha emission line of the F5 IV-V star Procyon (Alpha CMi, d = 3.5 pc) has been measured using the high-resolution Princeton spectrometer aboard NASA's Copernicus satellite. L-alpha absorption lines of interstellar deuterium and hydrogen are distinctly present. The average number density of interstellar hydrogen along the line of sight is found to be 0.11 + or - 0.02 per cu cm, similar to the densities that have been found in the directions of the stars Epsilon Eri, Epsilon Ind, and Alpha Cen A. These stars are all within 3.5 pc of the earth. The ratio of deuterium to hydrogen in the direction of Procyon is found to be 1.3 (+1.2, -0.5) x 10 to the -5th.

Anderson, R. C.↗
NASA NTRS1981

IUE ultraviolet observations of W UM a Stars

International Ultraviolet Explorer observations of four W UMa eclipsing binary systems (44 Boo, VW Cep, W UMa, and epsilon) are discussed. The stars generally show large surface fluxes of high temperature lines (C II, C IV, N V, Si IV) which may result from the high rotational velocities forced by synchronous rotation. High dispersion spectra of the 44 Boo system in the Mg II line enable the individual stellar components to be identified. The line widths and phase variations are consistent with the optically determined spectroscopic orbit. Circumstellar absorption of Mg II may be presented at selected phases.

Dupree, A. K.↗
NASA NTRS1981

X-ray and optical observations of HD 155638 - A remarkably active cool star

X-ray and optical observations of the 8.5-mag star HD 155638 are reported which reveal a remarkably active chromosphere and corona for the star. The object was first observed in soft X-rays with the HEAO 1 A2 low-energy detectors, and later reobserved with the HEAO 2 IPC. X-ray fluxes of about 2 x 10 to the -11th and 3 x 10 to the -12th ergs/sq cm per sec were obtained on the two occasions, indicative of source variability over the 2.5-year period between observations. SIT spectrographs taken in July-August 1980 show evidence of Ca II H and K core emission reversals and filled-in H alpha, while spectra taken in March and July 1981 show evidence of asymmetry and variability in the Ca II reversals. The spectral data are consistent with a G8 IV-V classification, from which is inferred a distance of 35-120 pc, and an X-ray luminosity from 4 x 10 to the 29th to 4 x 10 to the 31st ergs/sec. An absence of emission lines characteristic of mass transfer in binary systems indicates the X-rays to be coronal in origin. The properties of the star are noted to be similar to those of the RS CVn binaries.

Stern, R. A.↗
NASA NTRS1982

A note on the assignments of Rydberg states of COS

Assignments of the Rydberg states which converge to the respective X-tilde and B-tilde ion states of the COS(+) ion are reported. The assignments were made based on previously established orderings for the quantum defects of isoelectronic molecules. The Rydberg series I and II, which converge to the X-tilde 2 Pi state of COS(+), and the series III, IV, V, VI and VII, which converge to the B-tilde 2 Sigma + state, are assigned to molecular orbitals characterized by predominant sulfur orbitals, in contrast to those converging to the C-tilde states, which are characterized by oxygen atomic orbitals.

Wu, C. Y. R.↗
NASA NTRS1982

A spectroscopic study of LMC X-4

The orbital radial velocity semi-amplitude of the binary star system LMC X-4 primary was determined to be 37.9 + or - 2.4 km/s from measurements of the hydrogen absorption lines. The semi-amplitude of the He I and He II absorption lines are consistent with this, namely 44.9 + or - 5.0 and 37.3 + or - 5.3 km/s. The phase and shape of the radial velocity curves of the three ions are consistent with a circular orbit and an ephemeris based upon X-ray measurements of the neutron star, with the exception that the He II absorption line radial velocity curve has detectable shape distortion. Measurements of the He II LAMBOA 4686 emission line velocity are consistent with a phase shifted sine wave of semi-amplitude 535 km/s, a square wave of semi-amplitude 407 km/s, or high order harmonic fits. The spectral type was found to be 08.5 IV-V during X-ray eclipse. Variations to types as early as 07 occur, but not as a function or orbital phase. Absorption line peculiarities were noted on 6 of 58 spectra.

Petro, L. D.↗
NASA NTRS1986

Doppler tomography of the stellar wind of the Wolf-Rayet binary star V444 Cygni

High dispersion IUE observations of V444 Cyg around its orbit, emphasizing the C IV, N V, N IV, and He II profile variations are presented. The density and velocity structure of the wind, and details of the interaction between the O star and WR wind are discussed. Absorption becomes strongest and most nearly symmetric during primary eclipse, when the line of sight passes through the densest and most sluggish part of the wind. As the orbit progresses through quadrature, the terminal velocity does not change substantially, although the line of sight to the O star intersects more distant portions of the wind at lower velocity, indicating that there is still a considerable absorption in the line being seen toward the WR core. At secondary minimum, the core is partially occulted and the presence of the cavity eliminates the absorption component, while at third quadrature, a profile almost identical in appearance to that at first quadrature is observed.

Brown, Douglas N.↗