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At least 1,567 records · Page 87
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Kinetic Study of the OH + Ethylene Reaction using Frequency Modulated Laser Absorption Spectroscopy

The pressure dependence of the OH + C 2 H 4 addition reaction has been investigated using frequency modulated laser absorption spectroscopy to monitor OH kinetics. Bimolecular rate coefficients for the title reaction are reported in argon bath gas at room temperature and total pressures ranging from 2–361Torr. The pressure dependent rate coefficients measured here agree well with the majority of published kinetic studies under similar conditions. Previous high-level ab initio calculations have identified a pre-reaction complex on the OH + C 2 H 4 potential energy surface. In conclusion, the influence of this complex on the OH + C 2 H 4 kinetics has been investigated using one-dimensional master equation analyses of the current and previous experimental measurements

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Synthesis and Spectroscopic Properties of Carbazole-Oxadiazoles

Four new carbazole-oxadiazole derivatives (3a-b, 6a-b) were prepared from the reaction of aromatic aldehydes and carbohydrazides which were synthesized from carbazole aldehydes namely 9-hexyl-9H-carbazole-3-carbaldehyde 1 and 4-(9H-carbazole-9-yl)benzaldehyde 4 and acid hydrazides. The structures of the new derivatives were confirmed by {sup 1}H-NMR and FT-IR. The optical properties such as maximum absorption and emission wavelengths (λ; nm), molar extinction coefficients (ε; cm{sup −1} M{sup −1}), Stoke’s shifts (ΔλST; nm) and quantum yields (ϕF), of the carbazole-oxadiazole derivatives were declared in dichloromethane, toluene and tetrahydrofuran solutions.

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

Quantifying the Ligand-Induced Triplet Energy Transfer Barrier in a Quantum Dot-Based Upconversion System

During photon upconversion, quantum dots (QDs) transfer energy to molecules in solution through a long ligand shell. This insulating ligand shell imparts colloidal stability at the expense of efficient photosensitization. For the first time, we quantify the barrier these aliphatic ligands pose for triplet energy transfer in solution. Using transient absorption spectroscopy, we experimentally measure a small damping coefficient of 0.027 Å −1 for a ligand exceeding 10 carbons in length. The dynamic nature of ligands in solution lowers the barrier to charge or energy transfer compared to organic thin films. In addition, we show that surface ligands shorter than 8 carbons in length allow direct energy transfer from the QD, bypassing the need for a transmitter ligand to mediate energy transfer, leading to a 6.9% upconversion quantum yield compared with 0.01% for ligands with 18 carbons. Furthermore, this experimentally derived insight will enable the design of efficient QD-based photosensitizers for catalysis and energy conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

The Mimas ghost revisited - An analysis of the electron flux and electron microsignatures observed in the vicinity of Mimas at Saturn

An analysis of the electron-absorption signature observed by the cosmic-ray system on Voyager 2 near the orbit of Mimas is presented. It is found that these observations cannot be explained as the absorption signature of Mimas. By combining Pioneer 11 and Voyager 2 measurements of the electron flux at Mimas's orbit (L = 3.1), an electron spectrum is found in which most of the flux above about 100 keV is concentrated near 1 to 3 MeV. This spectral form is qualitatively consistent with the bandpass filter model of Van Allen et al. (1980). The expected Mimas absorption signature is calculated from this spectrum neglecting radial diffusion. Since no Mimas absorption signature was observed in the inbound Voyager 2 data, a lower limit on the diffusion coefficient for MeV electrons at L = 3.1 of D greater than 10 to the -8th sq Saturn radii/sec is obtained. With a diffusion coefficient this large, both the Voyager 2 and the Pioneer 11 small-scale electron-absorption-signature observations in Mimas's orbit are enigmatic. Thus the mechanism for producing these signatures is referred to as the Mimas ghost. A cloud of material in orbit with Mimas may account for the observed electron signature if the cloud is at least 1-percent opaque to electrons across a region extending over a few hundred kilometers.

Chenette, D. L.↗
NASA NTRS1988

Heterogeneous physicochemistry of the winter polar stratosphere

Present chemical theories of the Antarctic ozone hole assume that heterogeneous reactions involving polar stratospheric clouds (PSCs) are the precursor of springtime ozone depletions. However, none of the theories quantify the rates of proposed heterogeneous processed, and none utilize the extensive data base on PSC's. Thus, all of the theories must be considered incomplete until the heterogeneous mechanisms are properly defined. A unified treatment developed of the cloud related processes, both physical and chemical, and the importance of these processes using observation data is calibrated. The rates are compared competitive heterogeneous processes to place reasonable limits on critical mechanisms such as the denitrification and dechlorination of the polar winter stratosphere. Among the subjects addressed here are the physical/chemical properties of PSC's including their relevant microphysical, optical and compositional characteristics, mass transfer rates of gaseous constituents to cloud particles, adsorption, accommodation and sticking coefficients on cloud particles, time constants for condensation, absorption and other microphysical processes, effects of solubility and vapor pressure on cloud composition, the statistics of cloud processing of chemically active condensible species, rate limiting steps in heterogeneous chemical reactions, and the nonlinear dependence of ozone loss on physical and chemical parameters.

Turco, R. P.↗
NASA NTRS1991

High-reflective multilayers as narrowband VUV filters

A novel coating has been developed for the 120-230 nm wavelength VUV region which yields significantly higher reflectivity over selectable bandwidths and can be used to fabricate high-performance narrowband reflection filters; the spectral properties of such filters are greatly enhanced through their use in tandem. The coating uses a combination of high and low refractive index dielectric pairs. The proper choice of high-low ratio reduces the effects of VUV absorption for high refractive index films whose extinction coefficient is much higher than for a low-index material.

Zukic, Muamer↗
DOE OSTI2017

Cosmic Galaxy-IGM H i Relation at z ∼ 2–3 Probed in the COSMOS/UltraVISTA 1.6 Deg{sup 2} Field

We present spatial correlations of galaxies and IGM neutral hydrogen H i in the COSMOS/UltraVISTA 1.62 deg{sup 2} field. Our data consist of 13,415 photo-z galaxies at z ∼ 2–3 with K{sub s}<23.4 and the Lyα forest absorption lines in the background quasar spectra selected from SDSS data with no signature of damped Lyα system contamination. We estimate a galaxy overdensity δ {sub gal} in an impact parameter of 2.5 (proper) Mpc, and calculate the Lyα forest fluctuations δ{sub 〈F〉} whose negative values correspond to the strong Lyα forest absorption lines. We identify weak evidence of an anti-correlation between δ {sub gal} and δ{sub 〈F〉} with a Spearman’s rank correlation coefficient of −0.39 suggesting that the galaxy overdensities and the Lyα forest absorption lines positively correlate in space at the ∼90% confidence level. This positive correlation indicates that high-z galaxies exist around an excess of H i gas in the Lyα forest. We find four cosmic volumes, dubbed A {sub obs}, B {sub obs}, C {sub obs}, and D {sub obs}, that have extremely large (small) values of δ {sub gal} ≃ 0.8 (−1) and δ{sub 〈F〉}≃0.1(−0.4), three of which, B {sub obs}–D {sub obs}, significantly depart from the δ {sub gal}–δ{sub 〈F〉} correlation, and weaken the correlation signal. We perform cosmological hydrodynamical simulations and compare with our observational results. Our simulations reproduce the δ {sub gal}–δ{sub 〈F〉} correlation, agreeing with the observational results. Moreover, our simulations have model counterparts of A {sub obs}–D {sub obs}, and suggest that the observations pinpoint, by chance, a galaxy overdensity like a proto-cluster, gas filaments lying on the quasar sightline, a large void, and orthogonal low-density filaments. Our simulations indicate that the significant departures of B {sub obs}–D {sub obs} are produced by the filamentary large-scale structures and the observation sightline effects.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1987

Oxygen measurements in thin ribbon silicon

The oxygen content of thin silicon ribbons grown by the dendritic web technique was measured using a modification of the ASTM method based on Fourier transform infrared spectroscopy. Web silicon was found to have a high oxygen content, ranging from 13 to 19 ppma, calculated from the absorption peak associated with interstitial oxygen and using the new ASTM conversion coefficient. The oxygen concentration changed by about 10 percent along the growth direction of the ribbon. In some samples, a shoulder was detected on the absorption peak. A similar shoulder in Czochralski grown material has been variously interpreted in the literature as due to a complex of silicon, oxygen, and vacancies, or to a phase of SiO2 developed along dislocations in the material. In the case of web silicon, it is not clear which is the correct interpretation.

Hyland, S. L.↗
DOE OSTI2014

Structural characterization of Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} as a function of temperature using neutron powder diffraction and extended X-ray absorption fine structure techniques

The structure of Bi{sub 2}Te{sub 3} (Seebeck coefficient Standard Reference Material (SRM™ 3451)) and the related phase Sb{sub 2}Te{sub 3} have been characterized as a function of temperature using the neutron powder diffraction (NPD) and the extended X-ray absorption fine structure (EXAFS) techniques. The neutron structural studies were carried out from 20 K to 300 K for Bi{sub 2}Te{sub 3} and from 10 K to 298 K for Sb{sub 2}Te{sub 3}. The EXAFS technique for studying the local structure of the two compounds was conducted from 19 K to 298 K. Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} are isostructural, with a space group of R3{sup ¯}m. The structure consists of repeated quintuple layers of atoms, Te2-M-Te1-M-Te2 (where M = Bi or Sb) stacking along the c-axis of the unit cell. EXAFS was used to examine the bond distances and static and thermal disorders for the first three shells of Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3} as a function of temperature. The temperature dependencies of thermal disorders were analyzed using the Debye and Einstein models for lattice vibrations. The Debye and Einstein temperatures for the first two shells of Bi{sub 2}Te{sub 3} are similar to those of Sb{sub 2}Te{sub 3} within the uncertainty in the data. However, the Debye and Einstein temperatures for the third shell of Bi-Bi are significantly lower than those of the third shell of Sb-Sb. The Einstein temperature for the third shell is consistent with a soft phonon mode in both Bi{sub 2}Te{sub 3} and Sb{sub 2}Te{sub 3}. The lower Einstein temperature of Bi-Bi relative to Sb-Sb is consistent with the lower value of thermal conductivity of Bi{sub 2}Te{sub 3} relative to Sb{sub 2}Te{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1996

Modification of Einstein A Coefficient in Dissipative Gas Medium

Spontaneous radiation in dissipative gas medium such as plasmas is investigated by Langevin equations and the modified Weisskopf-Wigner approximation. Since the refractive index of gas medium is expected to be nearly unity, we shall first neglect the medium polarization effect. We show that absorption in plasmas may in certain case modify the Einstein A coefficient significantly and cause a pit in the A coefficient-density curves for relatively low temperature plasmas and also a pit in the A coefficient-temperature curves. In the next, the effect of medium polarization is taken into account in addition. To our surprise, its effect in certain case is quite significant. The dispersive curves show different behaviors in different region of parameters.

Cao, Chang-Qi↗
DOE OSTI2016

Localized modes in optics of photonic liquid crystals with local anisotropy of absorption

The localized optical modes in spiral photonic liquid crystals are theoretically studied for the certainty at the example of chiral liquid crystals (CLCs) for the case of CLC with an anisotropic local absorption. The model adopted here (absence of dielectric interfaces in the structures under investigation) makes it possible to get rid of mixing of polarizations on the surfaces of the CLC layer and of the defect structure and to reduce the corresponding equations to only the equations for light with polarization diffracting in the CLC. The dispersion equations determining connection of the edge mode (EM) and defect mode (DM) frequencies with the CLC layer parameters (anisotropy of local absorption, CLC order parameter) and other parameters of the DMS are obtained. Analytic expressions for the transmission and reflection coefficients of CLC layer and DMS for the case of CLC with an anisotropic local absorption are presented and analyzed. It is shown that the CLC layers with locally anisotropic absorption reduce the EM and DM lifetimes (and increase the lasing threshold) in the way different from the case of CLC with an isotropic local absorption. Due to the Borrmann effect revealing of which is different at the opposite stop-band edges in the case of CLC layers with an anisotropic local absorption the EM life-times for the EM frequencies at the opposite stop-bands edges may be significantly different. The options of experimental observations of the theoretically revealed phenomena are briefly discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1984

Explanation of the Normal Winter Anomaly from the Seasonal Variation of Short Wave Absorption

The frequency dependence of the winter anomaly (WA) of radio wave absorption indicates the altitude range where the considered seasonal variation of absorption, L, takes place: 75-95 km. In this height region considerable seasonal variations of ionic composition and effective recombination coefficient, alpha sub e, exist, which can cause seasonal variations of electron concentration, N, and absorption, L. An attempt to render a qualitative estimation of the normal WA, i.e., the increased ratio of winter over summer absorption, L sub w/L sub s, at medium latitudes 40 deg and 50 deg, for solar zenith angles CHi = 60 deg and 75 deg is made. This is compared with existing experimental data.

Velinov, P. J.↗
DOE OSTI2015

Theoretical study of the electronic spectra of neutral and cationic NpO and NpO{sub 2}

The electronic spectra of neutral NpO and NpO{sub 2} as well as of their mono- (NpO{sup +}, NpO{sub 2}{sup +}) and dications (NpO{sup 2+}, NpO{sub 2}{sup 2+}) were studied using multiconfigurational relativistic quantum chemical calculations at the complete active space self-consistent field/CASPT2 level of theory taking into account spin-orbit coupling. The active space included 16 orbitals: all the 7s, 6d, and 5f orbitals of neptunium together with selected orbitals of oxygen. The vertical excitation energies on the ground state geometries have been computed up to ca. 35 000 cm{sup −1}. The gas-phase electronic spectra were evaluated on the basis of the computed Einstein coefficients at 298 K and 3000 K. The computed vertical transition energies show good agreement with previous condensed-phase results on NpO{sub 2}{sup +} and NpO{sub 2}{sup 2+}.

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

Reference Gastrointestinal Absorption Fractions for Radionuclides Ingested in Soil

Oak Ridge National Laboratory is conducting a project for the Environmental Protection Agency (EPA) Office of Superfund Remediation and Technology Innovation involving derivation of cancer risk coefficients for ingestion of radionuclides in soil. EPA provides guidance on quantifying gastrointestinal (GI) absorption of a chemical in a given medium for use in risk evaluations including assessments for Superfund sites. Essentially, a medium-specific GI absorption fraction may be applied if and only if there is sound information to support that value. Otherwise, the applied GI absorption fraction should be the best estimate of fractional absorption of the chemical when ingested in highly soluble form. Based on our review of the literature on GI absorption of elements in soil, we have concluded that for many elements there is convincing evidence of substantially reduced absorption in ingested soil compared with ingestion in readily dissolved form. This report summarizes the reviewed information and proposes a comprehensive set of GI absorption fractions for ingestion of elements in soil. For most elements, the proposed GI absorption fractions are lower than the default absorption fractions recommended by the International Commission on Radiological Protection for radionuclides ingested in highly soluble form, even though considerable conservatism has been incorporated into the proposed soil-specific GI absorption fractions.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1983

Pioneer 11 observations of trapped particle absorption by Amalthea

The discovery of a microsignatury of trapped radiation in the Amalthea orbit as detected by Pioneer 11 in a flyby of Juptier in 1974 is reported and its implications for the radial diffusion coefficient in Jupiter's inner magnetosphere are discussed. A low energy telescope registered the absorption of low-energy protons as a function of the magnetic L shell durig inbound and outbound trajectories. Drift velocities of the 1 MeV particles were calculated. No correspondingly heightened effects were observed from high-energy electrons or heavier nuclei. Further analysis of the 0.5-8.7 MeV protons showed data to be consistent erosion of the particle drift shadows by a diffusion process. A limit was calculated for the highest diffusion coefficient value for the 1 MeV protons at the Amalthea orbit. The results indicate that the diffusion is driven by fluctuating electric or magnetic fields.

Mckibben, R. B.↗
DOE OSTI2015

Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra

Coupled cluster quantum chemical calculations of the potential energy surface and the induced dipole surface are reported for the He–Ar van der Waals collisional complex. Spectroscopic parameters are derived from global analytical fits while an accurate value for the long-range dipole coefficient D{sub 7} is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

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

The Effect of Acetylation on Iron Uptake and Diffusion in Water Saturated Wood Cell Walls and Implications for Decay

Acetylation is widely used as a wood modification process that protects wood from fungal decay. The mechanisms by which acetylation protects wood are not fully understood. With these experiments, we expand upon the literature and test whether previously observed differences in iron uptake by wood were a result of decreased iron binding capacity or slower diffusion. We measured the concentration of iron in 2 mm thick wood sections at 0, 10, and 20% acetylation as a function of time after exposure to iron solutions. The iron was introduced either strongly chelated with oxalate or weakly chelated with acetate. The concentrations of iron and oxalate in solution were chosen to be similar to those found during brown rot decay, while the concentration of iron and acetate matched previous work. The iron content of oxalate-exposed wood increased only slightly and was complete within an hour, suggesting little absorption and fast diffusion, or only slight surface adsorption. The increase in iron concentration from acetate solutions with time was consistent with Fickian diffusion, with a diffusion coefficient on the order of 10 -16 m 2 s -1 . The rather slow diffusion rate was likely due to significant binding of iron within the wood cell wall. The diffusion coefficient did not depend on the acetylation level; however, the capacity for iron absorption from acetate solution was greatly reduced in the acetylated wood, likely due to the loss of OH groups. We explored several hypotheses that might explain why the diffusion rate appears to be independent of the acetylation level and found none of them convincing. Implications for brown rot decay mechanisms and future research are discussed.

54 ENVIRONMENTAL SCIENCES↗