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At least 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Comparison of the photochemical properties of phthalocyanine and hemiporphyrazine Zn(II) complexes

In DMF (dimethylformamide) solutions containing concentrations of (NEt 4 )Br (Et = ethyl) between 0.001 and 0.05 M both zinc phthalocyanine (Pc) and hemiporphyrazine (Hp) complexes are dissolved and form species [Zn(Hp)(Br)] – , and [Zn(Pc)(Br)] – . The increase in formation of the hemiporphyrazine bromide adduct is revealed by a linear dependence of the UV–Vis absorption spectrum on the Br – concentration whereas, over the same concentration range, absorption measurements indicate the formation of the phthalocyanine bromide adduct in solution. The x-ray and molecular structure of [NEt 4 ][Zn(Pc)(Br)](H 2 O) 0.33 has been determined showing the coordination of the Br – to the metal center. Photo-induced processes of the Zn complexes were investigated with deaerated solutions in a time scale t ≥10 ns. The 355 nm flash irradiation of [Zn(Hp)(Br)] – produced transient spectra which showed a bathochromic shift of the absorption maximum from 460 nm to 440 nm and an increase of the spectrum rate of decay with increasing Br – concentrations. The initial spectrum is attributed to the (nπ*–LLCT Br→Hp )[Zn(Hp)(Br)] – excited state which reacts with H-atom donors forming a radical [Zn(Hp-H)(Br)] •– . On the other hand, a transient spectrum, λ max ~600 nm, grows in a time t ≤0.6 µs when [Zn(Pc)(Br)] – is flash irradiated at 355 nm. The photoreactions of these complexes with SCN – and 2-propanol (IPA) were studied. Despite of the apparent similarity between both complexes, IPA was photo-oxidized by both complexes although by different mechanisms, an electron transfer with [Zn(Pc)(Br)] – and an H atom abstraction with [Zn(Hp)(Br)] – . Finally, the photo-oxidation of SCN– by [Zn(Pc)(Br)] – but not by [Zn(Hp)(Br)] – makes a remarkable difference between the photochemistries of these complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Source of Bright Near-Infrared Luminescence in Gold Nanoclusters

Gold nanoclusters with near-infrared (NIR) photoluminescence (PL) have great potential as sensing and imaging materials in biomedical and bioimaging applications. In this work, Au 21 (S-Adm) 15 and Au 38 S 2 (S-Adm) 20 are used to unravel the underlying mechanisms for the improved quantum yields (QY), large Stokes shifts and long PL lifetimes in gold nanoclusters. Both nanoclusters show decent PL QY. In particular, the Au 38 S 2 (S-Adm) 20 nanocluster shows a bright NIR PL at 900 nm with QY up to 15% in normal solvents (such as toluene) at ambient conditions. The relatively lower QY for Au 21 (S-Adm) 15 (4%) compared to Au 38 S 2 (S-Adm) 20 is attributed to the lowest-lying excited state being symmetry-disallowed, as evidenced by the pressure-dependent anti-spectral shift of the absorption spectra compared to PL. Yet, Au 21 (S-Adm) 15 maintains some emissive properties due to a nearby symmetry-allowed excited state. Furthermore, our results show that suppression of non-radiative decay due to the surface “lock rings” which encircle the Au kernel and the surface “lock atoms” which bridge the fundamental Au-kernel units (e.g., tetrahedra, icosahedra, etc.) is the key to obtain high QYs in gold nanoclusters. Here, the complicated excited-state processes and the small absorption coefficient of the band-edge transition lead to the large Stokes shifts and the long PL lifetimes that are widely observed in gold nanoclusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1975

Empirical relation between interstellar X-ray absorption and optical extinction

An empirical relation between interstellar X-ray absorption and optical extinction is derived from the correlation of measurements made on objects of large intrinsic diameter. The result is Av = 4.5 times 10 to the -22nd power N(H) mag, with the principal error being largely systematic in origin, where N(H) represents the column density of interstellar matter in the Brown and Gould model for the X-ray absorption coefficient. Applying this ratio to optically identified compact sources, it is concluded that sources in binary systems showing pronounced X-ray occultations have an intrinsic absorption equivalent to about 10 to the 22-nd power atoms per sq cm of interstellar matter and that there are a few compact sources where the absorption seems to be primarily interstellar in origin. The interstellar absorption expected in Cyg X-1 from the extinction of its optical counterpart is much greater than that suggested by X-ray spectra, which may be due to a soft X-ray component greater than that predicted by the power law fitted to higher energy data.

Gorenstein, P.↗
NASA NTRS1995

Stellar coronal abundances. 3: The solar first ionization potential effect determined from full-disk observation

In this paper we reanalayze the full-disk quiet-sun spectrum of Mallinovsky & Heroux (1973) with modern atomic data. The purposes of this are to check our atomic data and methods in other investigations using data from nearby stars obtained with the NASA Extreme Ultraviolet Explorer (EUVE) satellite, and to confirm that the solar first ionization potential (FIP) effect investigated by previous authors studying discrete solar regions is the same as that found in full-disk spectra. We recover the usual solar FIP effect of a coronal abundance enhancement of elements with a low FIP of a factor approximately 3-4 for lines formed at temperatures greater than approximately 10(exp 6) K. For lower temperatures, the FIP effect seems to be substantially smaller, in qualitative agreement with other data. Comparing our full-disk result with those from discrete solar structures suggest that the FIP effect is a function of altitude, with the lower temperature full-disk emission being dominated by the super-granulation network. We also compare the recent ionization balance of Arnaud & Raymond (1992) with that of Arnaud & Rothenflug (1985).

Laming, J. Martin↗
NASA NTRS2001

Spectroscopy of Cosmic Carbon Analogs in Inert-Gas Matrices and in the Gas-Phase: Comparative Results and Perspectives for Astrophysics

Recent studies of the spectroscopy of large (up to approx. 50 carbon atoms) neutral and Ionized polycyclic aromatic hydrocarbons (PAHs) and Fullerenes isolated in inert gas matrices will be presented. The advantages and the limitations of matrix isolation spectroscopy for the study of the molecular spectroscopy of interstellar dust analogs will be discussed. The laboratory data will be compared to the astronomical spectra (the interstellar extinction, the diffuse interstellar bands). Finally, the spectra of PAH ions isolated in neon/argon matrices will be compared to the spectra obtained for PAH ion seeded in a supersonic expansion. The astrophysical implications and future perspectives will be discussed.

Salama, Farid↗
NASA NTRS2016

The Effects of High Density on the X-ray Spectrum Reflected from Accretion Discs Around Black Holes

Current models of the spectrum of X-rays reflected from accretion discs around black holes and other compact objects are commonly calculated assuming that the density of the disc atmosphere is constant within several Thomson depths from the irradiated surface. An important simplifying assumption of these models is that the ionization structure of the gas is completely specified by a single, fixed value of the ionization parameter (xi), which is the ratio of the incident flux to the gas density. The density is typically fixed at n(sub e) = 10(exp 15) per cu cm. Motivated by observations, we consider higher densities in the calculation of the reflected spectrum. We show by computing model spectra for n(sub e) approximately greater than 10(exp 17) per cu cm that high-density effects significantly modify reflection spectra. The main effect is to boost the thermal continuum at energies 2 approximately less than keV. We discuss the implications of these results for interpreting observations of both active galactic nuclei and black hole binaries. We also discuss the limitations of our models imposed by the quality of the atomic data currently available.

accretion↗
DOE OSTI2023

Helical Organic and Inorganic Polymers

Despite being a staple of synthetic plastics and biomolecules, helical polymers are scarcely studied with Gaussian-basis-set ab initio electron-correlated methods on an equal footing with molecules. This article introduces an ab initio second-order many-body Green’s-function [MBGF(2)] method with nondiagonal, frequency-dependent Dyson self-energy for infinite helical polymers using screw-axis-symmetry-adapted Gaussian-spherical-harmonics basis functions. Together with the Gaussian-basis-set density-functional theory for energies, analytical atomic forces, translational-period force, and helical-angle force, it can compute correlated energy, quasiparticle energy bands, structures, and vibrational frequencies of an infinite helical polymer, which smoothly converge at the corresponding oligomer results. These methods can handle incommensurable structures, which have an infinite translational period and are hard to characterize by any other method, just as efficiently as commensurable structures. We apply them to polyethylene (2/1 helix), polyacetylene (Peierls’ system), and polytetrafluoroethylene (13/6 helix) to establish the quantitative accuracy of MBGF(2)/cc-pVDZ in simulating their (angle-resolved) ultraviolet photoelectron spectra, and of B3LYP/cc-pVDZ or 6-31G** in reproducing their structures, infrared and Raman band positions, phonon dispersions, and (coherent and incoherent) inelastic neutron scattering spectra. We then predict the same properties for infinitely catenated chains of nitrogen or oxygen and discuss their possible metastable existence under ambient conditions. They include planar zigzag polyazene (N2)x (Peierls’ system), 11/3-helical isotactic polyazane (NH)x, 9/4-helical isotactic polyfluoroazane (NF)x, and 7/2-helical polyoxane (O)x as potential high-energy-density materials.

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

Sulfur-Ligated [2Fe-2C] Clusters as Synthetic Model Systems for Nitrogenase

Metal clusters featuring carbon and sulfur donors have coordination environments comparable to the active site of nitrogenase enzymes. Here, we report a series of di-iron clusters supported by the dianionic yldiide ligands, in which the Fe sites are bridged by two μ 2 -C atoms and four pendant S donors. The [L 2 Fe 2 ] (L = {[Ph 2 P(S)] 2 C} 2– ) cluster is isolable in two oxidation levels, all-ferrous Fe 2 II and mixed-valence Fe II Fe III . The mixed-valence cluster displays two peaks in the Mössbauer spectra, indicating slow electron transfer between the two sites. The addition of the Lewis base 4-dimethylaminopyridine to the Fe2 II cluster results in coordination with only one of the two Fe sites, even in the presence of an excess base. Conversely, the cluster reacts with 8 equiv of isocyanide t BuNC to give a monometallic complex featuring a new C–C bond between the ligand backbone and the isocyanide. The electronic structure descriptions of these complexes are further supported by X-ray absorption and resonant X-ray emission spectroscopies.

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

Characterization of Two Positional Isomers of the Cs + Gly Complex Using Two-Color, IR–IR Photobleaching of the Cryogenically Cooled Ions

Metal ion binding to amino acid residues is an important interaction motif that controls the tertiary structures of oligopeptides. Analyses of the vibrational band patterns displayed by the amino acid scaffolds are commonly used to characterize the local docking motifs. Here we carry out two-color, IR-IR photobleaching measurements to obtain isomer-selective vibrational spectra of the Cs + Gly ion-molecule complex isolated in a cryogenically cooled, radiofrequency ion trap. The distinct band patterns of two non-interconverting isomers are observed and traced to different bidentate binding motifs between Cs + and the glycine scaffold. In one isomer, the ion attaches to the oxygen atoms of the carboxyl group whereas in the other it docks to the amino nitrogen and the carbonyl oxygen. Attachment to the acid head group yields a very diffuse absorption associated the OH group engaged in a strong intramolecular H-bond that closes a 5 membered ring. Furthermore, the band assignments, rearrangement pathways and electrostatic distortion of the electron density distributions in the glycine scaffold by the proximal ion are explored with electronic structure calculations and anharmonic theory.

Infrared spectroscopy↗
DOE OSTI2021

Influence of diluent concentration in localized high concentration electrolytes: elucidation of hidden diluent-Li + interactions and Li + transport mechanism

Localized high concentration electrolytes (LHCE) offer a viable dilution strategy for high concentration electrolytes (HCE) as the dilution process barely impacts the enhanced reductive/oxidative behavior of the HCE formulation but significantly lowers the overall viscosity and, in most cases, increases the ionic conductivity. On the other hand, experimental studies indicate that fluorinated ether electrolytes such as 1,1,2,2-tetrafluoroethylene 2,2,3,3-tetrafluoropropyl ether (TTE) help grow enhanced passivation layers on Ni-rich NMC cathodes. In this work, we study LHCE formulations based on lithium bis(fluorosulfonyl)imide (LiFSI), dimethyl carbonate (DMC), and TTE as the diluent. Here we use molecular dynamics methodologies, and Raman spectra measurements, to address to what extent the diluent content impacts the coordination behavior of the aggregated structures in the electrolyte and to evaluate the Li + transport properties under the influence of an external electric field. In contrast to other fluorinated ethers, we find that TTE interacts with Li + via fluorine atoms, partially limiting the DMC–Li + interactions hence altering the Li + solvation coordination. This competitive interaction with Li+ between the organic solvent and the TTE diluent influences the electrolyte's reductive/oxidative behavior. Nevertheless, the bonding strength of the Li + –F TTE is much weaker than those of the Li + –O DMC and Li + –OFSI – . Therefore, the existence of Li + –F TTE is in a transient state rather than in a steady state. These results provide plausible guiding rules for future dilution strategies of HCE electrolytes. We also demonstrate that Li + ions drift under the electric field's influence via repeated ion dissociation/association processes following a hopping conduction mechanism. Li + ions jump between aggregated networks where Li–O interactions dominate via diluent-enriched phases, a process in which the solvation shells temporarily mutate to a Li–F dominated coordination structure. We expect our results to contribute an improved atomic-level understanding of the solvation structure and dynamics of LHCE electrolytes.

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

Changes in polarization dictate necessary approximations for modeling electronic deexcitation intensity: Application to x-ray emission

Accurate simulation of electronic excitations and deexcitations are critical for complementing complex spectroscopic experiments and can provide validation to theoretical approaches. Here, using a generalized framework, we contrast the accuracy and validity of orbital-constrained and linear-response approaches that build upon Kohn-Sham density functional theory (DFT) to simulate emission spectra of electronic origin and propose an efficient approximation, named many-body x-ray emission spectroscopy or MBXES, for simulating such processes. We show analytically as well as with computed examples that for electronic (de)excitation leading to an appreciable change in polarization (i.e., density rearrangement), the adiabatic approximation in a response-based formalism will be inadequate for the calculation of oscillator strength. Thus, such a change (e.g., in the net electrostatic dipole moment of a finite system) can be used as a metric for evaluating the applicability of the adiabatic response-based approach and can be particularly valuable in x-ray emission spectroscopy. On the other hand, MBXES, the flexible method introduced in this paper, can compute oscillator strengths accurately at a much lower computational expense on the basis of two DFT-based self-consistent field calculations. Using illustrative examples of emission spectra, the efficacy of the MBXES method is demonstrated by comparison with its parent theory, orbital-optimized DFT, and with experiments.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Validation of NEAMS Tools Using MSRE Data

This report documents the benchmarks developed and performed for the tools and codes developed under the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program utilizing the MSRE experiment data. There are three focus areas explored in this work: fuel evolution, CFD, and system transient analyses. Fuel depletion is important for MSR reactor physics and fuel cycle analysis. Fuel depletion capability is currently being developed in the Griffin reactor physics code. To support this, a benchmark problem is developed using the MSRE data and an existing depletion code with flowing fuel analysis functionality (ADDER) to validate this new capability in Griffin. The ADDER calculation is compared with the TRITON-MSR results as well as the MSRE experimental data. This benchmark can be directly used to verify and validate the Griffin fuel depletion capability in future years. For CFD simulation, the MSRE CAD model is obtained from the Copenhagen Atomics and a mesh is generated for the MSRE inlet plenum. The Nek5000 code will be employed to find the flow distribution in the MSRE inlet plenum based on the mesh generated. For system analysis, a simple benchmark problem for three types of MSR system transients is developed. The SAM and SPECTRA codes are used to solve the simple problem, and the results from the two codes agree well. The SAM code is also employed to obtain the frequency response of the MSRE system at the 5 and 8 MWt power levels. The results agree well with the experiment measurements. These verification and validation efforts gives SAM users more confidence in MSR system transient simulations using SAM. Lastly, the SAM-Griffin Multiphysics coupling work is initiated. A simple one-way coupling of evaluating the precursor drift effect on the MSRE k-eff is demonstrated. This preliminary coupling work serves as the basis for future more complex Multiphysics simulation and modelling.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Hydrogen Line Shape Uncertainties in White Dwarf Model Atmospheres

For isolated white dwarf (WD) stars, fits to their observed spectra provide the most precise estimates of their effective temperatures and surface gravities. Even so, recent studies have shown that systematic offsets exist between such spectroscopic parameter determinations and those based on broadband photometry. These large discrepancies (10% in T eff , 0.1 M ⊙ in mass) provide scientific motivation for reconsidering the atomic physics employed in the model atmospheres of these stars. Recent simulation work of ours suggests that the most important remaining uncertainties in simulation-based calculations of line shapes are the treatment of 1) the electric field distribution and 2) the occupation probability (OP) prescription. We review the work that has been done in these areas and outline possible avenues for progress.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1984

NGC 7213 - A key to the nature of liners?

New optical spectra of the nearby S0 galaxy NGC 7213 are analyzed. The observations are described and a brief overview of the spectrum is given. The subtraction of the stellar component is presented, and the measurement of various emission lines is discussed in detail. Important physical parameters are derived, including those pertaining to atomic data, line widths, physical conditions, geometry and kinematics, the Balmer decrement, and ultraviolet emission lines. The Seyfert characteristics of NGC 7213 are reviewed, and the galaxy's shock features are reconciled with photoionization models. The presented arguments may apply to classical liners as well. Theoretical models that can help explain the relationships discovered among the emission lines are examined.

Filippenko, A. V.↗
NASA NTRS1984

Soft X-ray opacity in hot and photoionized gases

New calculations are presented of the soft X-ray opacity of gas having cosmic elemental abundances, but in a variety of ionization states. Coronal ionization equilibrium is considered over the range of temperatures 10 to the 4th to 3 x 10 to the 8th K and photoionization equilibrium with power-law and thermal bremsstrahlung spectra over a wide range of ionization parameters. The results are displayed in illustrative figures. For temperatures and ionization parameters commonly found in astrophysical plasmas, the opacity (particularly to photons of equal to or less than 1 keV) can be diminished by substantial factors relative to the state in which all atoms are neutral. As the dominant ionization stages change, the positions and contrasts of prominent K-edges also change.

Krolik, J. H.↗
NASA NTRS1985

Ultraviolet observations of low-excitation Herbig-Haro objects

The Herbig-Haro (HH) objects rank among the faintest objects (v approx. 17) observed with the I.U.E. Expectations that the low-excitation shock-excited HHs should be dominated by H two-photon (2q) UV emission were borne out in the first observation of HH 43 and 47 obtained in 1982. The UV continuous energy distributions in the SWP spectra of these objects were found to peak near 1500 Angstroms as predicted by the 2q hypothesis. In addition, emission lines in the Lyman band of H sub 2, excited by Lyman alpha fluorescence, were detected in HH 43. It is not clear if the molecular gas is coextensive with the atomic gas responsible for the optical emission, or if the molecular gas is immediately adjacent to the region of optical emission. The two-photon energy distribution and H sub 2 fluorescent emission were previously discussed.

Schwartz, R. D.↗
NASA NTRS1995

Effects of low earth orbit on the optical performance of multi-layer enhanced high reflectance mirrors

Two mirror designs developed for space applications were flown along with a standard mid-infrared design on the leading and trailing edges of the Long Duration Exposure Facility (LDEF). Preliminary observations of induced changes in optical performance of ZnS-coated mirrors and impact-related microstructural and microchemical effects are described in the proceedings of the First LDEF Post-Retrieval Symposium. In this paper, effects of the induced environment and meteoroid/debris impacts on mirror performance are described in more detail. Also, an analysis of reflectance spectra using the results of Auger and secondary ion mass spectroscopy (SIMS) profiling measurements are used to identify an optical-degradation mechanism for the ZnS-coated mirrors. Structural damage associated with a high-velocity impact on a (Si/Al2O3)-coated mirror was imaged optically and with scanning electron and atomic force microscopy (SEM and AFM). Scanning Auger and SIMS analysis provided chemical mapping of selected impact sites. The impact data suggest design and fabrication modifications for obtaining improved mechanical performance using a design variation identified in preflight laboratory simulations. Auger surface profile and SIMS imaging data verified the conclusion that secondary impacts are the source of contamination associated with the dendrites grown on the leading-edge ZnS-coated test samples. It was also found that dendrites can be grown in the laboratory by irradiating contaminated sites on a trailing-edge ZnS-coated sample with a rastered electron beam. These results suggest a mechanism for dendrite growth.

Donovan, Terence↗
DOE OSTI2021

Molecular structure retrieval directly from laboratory-frame photoelectron spectra in laser-induced electron diffraction

Ubiquitous to most molecular scattering methods is the challenge to retrieve bond distance and angle from the scattering signals since this requires convergence of pattern matching algorithms or fitting methods. This problem is typically exacerbated when imaging larger molecules or for dynamic systems with little a priori knowledge. Here, we employ laser-induced electron diffraction (LIED) which is a powerful means to determine the precise atomic configuration of an isolated gas-phase molecule with picometre spatial and attosecond temporal precision. We introduce a simple molecular retrieval method, which is based only on the identification of critical points in the oscillating molecular interference scattering signal that is extracted directly from the laboratory-frame photoelectron spectrum. The method is compared with a Fourier-based retrieval method, and we show that both methods correctly retrieve the asymmetrically stretched and bent field-dressed configuration of the asymmetric top molecule carbonyl sulfide (OCS), which is confirmed by our quantum-classical calculations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗