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At least 127 records · Page 7

Role of Transition Metals in Metal–Organic Frameworks as Nanoporous Ion Emitters for Thermal Ionization Mass Spectrometry

Thermal ionization mass spectroscopy (TIMS) is a powerful analytical technique that allows for precise determination of isotopic ratios. Analysis on low abundance samples, however, can be limited by the ionization efficiency. Following an investigation into a new type of metal-organic hybrid material devised to promote the emission of analyte ions (nano-PIES) and reduce traditional sample loading problems, this work probes the impact that changing the metal in the material has on the ionization of Uranium-238. Being derived from metal-organic frameworks (MOFs), nano-PIEs inherit the tunability of the parent MOFs; the MOF-74 series has been well studied for probing the impact various framework metals (i.e., Mg, Mn, Co, Ni, Cu, Zn, and Cd) have on material properties, and thus, a series of nano-PIEs with different metals were derived from an isoreticular MOF-74 series. In conclusion, trends in ionization efficiency were studied as a function of ionization potential, volatility, and work function of the framework metals as well as the mechanism of ionization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elemental Fractionation During Rapid Accretion of the Moon Triggered by a Giant Impact

Recently, Ida et al. made an N-body simulation of lunar accretion from a protolunar disk formed by a giant impact. One of their important conclusions is that the accretion time of the Moon is as short as one month. Such rapid accretion is a necessary consequence of the high surface density of a lunar mass disk accreting just beyond the Roche limit (about 3Re); the Safronov accretion time (a few days) is even shorter. The energy of accretion always exceeds the gravitational binding energy of newly arriving matter. Hence, without an energy sink, the accreting body is thermally unstable. For the Earth and other planets, radiation acts as the sink. However, in such a short accretion time, the Moon cannot radiate the accretional energy. Even radiating at a silicate cloudtop temperature of roughly 2000 K, it would take more than 100 yr to radiatively cool the Moon. The plausible alternative heat sinks are heat capacity, latent heat of vaporization, and thermal escape of the gas to space (i.e., hydrodynamic blowoff). The latter becomes plausible for the Moon because the scale height at 2000 K (about 300 km) is a significant fraction of the lunar radius. The early stages of lunar (or "lunatesimal") growth release relatively little energy and can occur simply by heating the material, especially if the accreting material is originally cold. However, the material is unlikely to be cold, because the disk itself is hot and cooling time is long, while the lunar accretion time iss very short. Therefore, the moon is likely to accrete condensed material just after it condenses. Accordingly, the newly accreted material will be on the verge of vaporization and will have very little heat capacity to spare. The immediate heat sink is the latent heat of vaporization. Most of the vapor will escape from the moon, because the thermal energy in the gas can be used to drive escape. However, vaporization is generally incomplete. the latent heat of vaporization exceeds the energy of accretion. Viewed globally, the accretional energy is about half the energy required to vaporize the entire Moon. Thus to first approximation, half of the Moon-forming material can be vaporized and lost during accretion. During this process, we would expect preferential loss of relatively volatile elements. Escape will retard the rate of accretion. To test these ideas, we computed detailed models of the thermal state of the Moon during accretion. We pay special attention to the structure of the silicate atmosphere and its loss rate by calculating the chemical species at equilibrium. We used the PHEQ program which includes 12 elements (H,O,C,Mg,Si,Fe,Ca, Al, Na,Ti, and N.) and 272 compounds (including ionic compounds). Because of the large heats of vaporization and ionization, the adiabatic atmosphere is nearly isothermal and massive escape is expected. The pressure of the atmosphere is determined by the balance between vaporization of a accreting material and escape. If the accretion time is one month, a 0.3 bar atmosphere is expected. Elemental fractionation depends strongly on the temperature of the accreting material. The initial temperature of the material can be estimated from the condition of gravitational instability in the protolunar disk. As shown by Ida et al, accretion starts when gravitational instability occurs when more than 99% of the material condenses. At this point, all of Ca, Al, Si, Mg, and Fe, and 95% of Na (probably K also), are in condensed phases. If the moon is formed from the accretion of such material, volatile elements such as Na, and K are retained by the moon only early in accretion. At later times, K and Na are lost and a fraction of the MG, Si and Fe is lost. However, refractory elements such as Ca and Al are retained and so achieve a mild degree (factor 2) of superabundance.

Abe, Y.↗

Magnesium Hall Thruster

This Phase II project is developing a magnesium (Mg) Hall effect thruster system that would open the door for in situ resource utilization (ISRU)-based solar system exploration. Magnesium is light and easy to ionize. For a Mars- Earth transfer, the propellant mass savings with respect to a xenon Hall effect thruster (HET) system are enormous. Magnesium also can be combusted in a rocket with carbon dioxide (CO2) or water (H2O), enabling a multimode propulsion system with propellant sharing and ISRU. In the near term, CO2 and H2O would be collected in situ on Mars or the moon. In the far term, Mg itself would be collected from Martian and lunar regolith. In Phase I, an integrated, medium-power (1- to 3-kW) Mg HET system was developed and tested. Controlled, steady operation at constant voltage and power was demonstrated. Preliminary measurements indicate a specific impulse (Isp) greater than 4,000 s was achieved at a discharge potential of 400 V. The feasibility of delivering fluidized Mg powder to a medium- or high-power thruster also was demonstrated. Phase II of the project evaluated the performance of an integrated, highpower Mg Hall thruster system in a relevant space environment. Researchers improved the medium power thruster system and characterized it in detail. Researchers also designed and built a high-power (8- to 20-kW) Mg HET. A fluidized powder feed system supporting the high-power thruster was built and delivered to Busek Company, Inc.

Szabo, James J.↗

Evidence Report: Risk of Radiation Carcinogenesis

As noted by Durante and Cucinotta (2008), cancer risk caused by exposure to space radiation is now generally considered a main hindrance to interplanetary travel for the following reasons: large uncertainties are associated with the projected cancer risk estimates; no simple and effective countermeasures are available, and significant uncertainties prevent scientists from determining the effectiveness of countermeasures. Optimizing operational parameters such as the length of space missions, crew selection for age and sex, or applying mitigation measures such as radiation shielding or use of biological countermeasures can be used to reduce risk, but these procedures have inherent limitations and are clouded by uncertainties. Space radiation is comprised of high energy protons, neutrons and high charge (Z) and energy (E) nuclei (HZE). The ionization patterns and resulting biological insults of these particles in molecules, cells, and tissues are distinct from typical terrestrial radiation, which is largely X-rays and gamma-rays, and generally characterized as low linear energy transfer (LET) radiation. Galactic cosmic rays (GCR) are comprised mostly of highly energetic protons with a small component of high charge and energy (HZE) nuclei. Prominent HZE nuclei include He, C, O, Ne, Mg, Si, and Fe. GCR ions have median energies near 1 GeV/n, and energies as high as 10 GeV/n make important contributions to the total exposure. Ionizing radiation is a well known carcinogen on Earth (BEIR 2006). The risks of cancer from X-rays and gamma-rays have been established at doses above 50 mSv (5 rem), although there are important uncertainties and on-going scientific debate about cancer risk at lower doses and at low dose rates (<50 mSv/h). The relationship between the early biological effects of HZE nuclei and the probability of cancer in humans is poorly understood, and it is this missing knowledge that leads to significant uncertainties in projecting cancer risks during space exploration (Cucinotta and Durante 2006; Durante and Cucinotta 2008).

Huff, Janice↗

Spectral analysis of a high-velocity meteor

A spectrogram of a fast optical meteor was reduced and analyzed, and 60 features were identified in the spectrum. Air and ionized elements in this meteor radiate throughout the spectrum from 3000 A to 6800 A. A mass of 9 mg and an effective radiation temperature of approximately 5700 K were computed for the meteor. Weight ratios of Ca:Fe, and Mg:Fe, and Na:Fe were computed. A plasma particle velocity distribution for meteors was derived, and the average collision speed obtained from this distribution was compared with the relative collision speed of a Fe-N2 gas mixture at 5700 K.

Harvey, G. A.↗

Chemically anomalous, pre-accretionally irradiated grains in interplanetary dust -- interstellar grains?

Ultrafine-grained matrix is a unique and fundamental building block of chondritic porous (CP) interplanetary dust particles. Most IDPs so far determined to be of cometary origin belong to the CP class. The matrix in CP IDPs is not homogeneous but rather a loose mixture of discrete single crystals (e.g., olivine, pyroxene, Fe sulfides) and polyphase grains. The petrographic diversity observed among the polyphase grains suggest that they were formed under variable physiochemical conditions. One particular class of polyphase grains are a dominant component in cometary IDPs. Although their occurrence is well documented, the terminology used to describe them is confused. They have been called many names. Here they are simply called GEMS (Glass with Embedded Metal and Sulfides). The bulk compositions of GEMS are within a factor of 3 chondritic (solar) for all major elements except C. Quantitative thin-film X-ray (EDS) analyses have shown that GEMS are systematically depleted in Mg and Si, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Electron energy-loss spectroscopy (EELS) suggests that the excess O is present as hydroxyl (-OH) groups. These same chemical 'anomalies' were observed in solar-wind-irradiated amorphous rims on the surfaces of IDPs, suggesting that the compositions of GEMS reflect prior exposure to ionizing radiation. In order to test this hypothesis, a sample of Allende (CV3) matrix was exposed to proton flux. Radiation-damaged amorphous rims on olivine and pyroxene crystals in the Allende sample were found to be depleted in Mg and Ca, enriched in S, Fe, and Ni, and stoichiometrically enriched in O. Thus, the compositions of GEMS are indeed consistent with exposure to ionizing radiation. This study suggests that chemical as well as isotopic anomalies may be used to identify presolar interstellar grains in primitive meteoritic materials.

Bradley, J. P.↗

Solar-metallicity gas in the extended halo of a galaxy at z ∼ 0.12

ABSTRACT We present the detection and analysis of a weak low-ionization absorber at z = 0.121 22 along the sightline of the blazar PG 1424+240, using spectroscopic data from both HST/COS and STIS. The absorber is a weak Mg ii analogue, with an incidence of weak C ii and Si ii, along with multicomponent C iv and O vi. The low ions are tracing a dense (nH ∼ 10−3 cm−3) parsec-scale cloud of solar or higher metallicity. The kinematically coincident higher ions are either from a more diffuse (nH ∼ 10−5–10−4 cm−3) photoionized phase of kiloparsec-scale dimensions or are tracing a warm (T ∼ 2 × 105 K) collisionally ionized transition temperature plasma layer. The absorber resides in a galaxy overdense region, with 18 luminous (>L*) galaxies within a projected radius of 5 Mpc and velocity of 750 km s−1. The multiphase properties, high metallicity, and proximity to a 1.4L* galaxy, at ρ ∼ 200 kpc and separation |Δv| = 11 km s−1, favour the possibility of the absorption tracing circumgalactic gas. The absorber serves as an example of weak Mg ii–O vi systems as a means to study multiphase high-velocity clouds in external galaxies.

Pradeep, Jayadev↗

Attosecond time delays at Cooper minima in valence-shell photoionization of alkali-metal and alkaline-earth-metal atoms

Ji et al. [New J. Phys. 26, 093014 (2024)] established a direct link between the photoionization cross section and the attosecond time delay near Cooper minima (CM) in the valence shells of noble-gas atoms. This link is based on the analytic properties of the ionization amplitude in the complex plane of the photoelectron energy, and is particularly sensitive to the winding number of the amplitude around the origin of the complex energy plane. Here, in this study, we demonstrate an analogous relation for photoionization of the valence 𝑛⁢𝑠 shells of alkali-metal atoms (AMA), from Na (𝑛 = 3) to Cs (𝑛 = 6), as well as alkaline-earth-metal atoms (AEMA), from Mg (𝑛 = 3) to Ba (𝑛 = 6). To this end, we employ a fully relativistic formalism that separates the two complementary 𝑛⁢𝑠 1/2 → 𝐸⁢𝑝 1/2 and 𝐸⁢𝑝 3/2 ionization channels. Each of these channels exhibits a phase variation close to 𝜋, but in opposite directions, near their respective Cooper minima. This phase variation vanishes in a nonrelativistic formulation, where the two channels become degenerate. For AMA, due to the threshold proximity of the CM, the universal Coulomb contribution to the time delay must be subtracted. The remaining component of the time delay is target-specific, angular-dependent, and accessible through comparative measurements.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Neutral calcium, strontium and barium - Determination of f values of the principal series by the hook method

The hook method is used to measure the absolute gf values of the following lines: the first 13 members of the principal series, the ground-level transition at 2275.46 A, and the intercombination line at 6572.78 A in Ca I; the first 22 members of the principal series, the ground-level transitions at 2428.1 and 2680.08 A, and the intercombination line at 6892.6 A in Sr I; and the members from principal quantum numbers 12 to 21, inclusive, as well as the ground-level transitions at 2432.5, 2444.6, and 2454.06 A in Ba I. The results are compared with those of previous measurements, and the quantum-defect method is applied to plot the oscillator strengths of the discrete transitions in the principal series of Mg I, Ca I, and Sr I in order to obtain estimates of the photoionization cross sections at the first ionization limit. The resulting cross sections are found to be about twice as large as previous values based on vapor-pressure data.

Parkinson, W. H.↗

The interstellar medium near the sun. II - The line of sight to Alpha Virginis

Measurements of the UV interstellar lines in Alpha Vir between 935 and 2960 A are reported. The derived abundances indicate significant depletion of Al, Si, Mn, Fe, and possibly Mg, whereas S, C, Ar, and O appear to be essentially undepleted. About half the gas is shown to be ionized, with a mean electron density of no more than 1 per cu cm, and the remainder is neutral, though both regions have the same velocity to within 2 km/s. A small fraction of the gas is apparently at a temperature of 400,000 K. The possibility of measuring the temperature of the H I gas is discussed, using the observed relationship between Doppler width and mass. A detailed discussion is included of the data analysis useful for comparatively simple lines of sight in terms of density, temperature, and extent of the possible physical regions, and of the relevant radiation field. An unidentified feature at 1063.2 A is reported.

York, D. G.↗

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗

A study of X-ray and infrared emissions from dusty nonradiative shock waves

We have constructed models that predict the dynamic evolution and infrared (IR) emission of grains behind nonradiative shock waves. We present a self-consistent treatment of the effect of grain destruction and heating on the ionization structure and X-ray emission of the postshock gas. Incorporating thermal sputtering, collisional heating, and deceleration of grains in the postshock flow, we predict the IR and X-ray fluxes from the dusty plasma as a function of swept-up column density. Heavy elements such as C, O, Mg, S, Si and Fe are initially depleted from the gas phase but are gradually returned as the grains are destroyed. The injected neutral atoms require some time to 'catch up' with the ionization state of the ambient gas. The nonequilibrium ionization state and gradient in elemental abundances in the postshock flow produces characteristic X-ray signatures that can be related to the age of the shock and amount of grain destruction. We study the effects of preshock density and shock velocity on the X-ray and IR emission from the shock. We show that the effects of graindestruction on the X-ray spectra of shock waves are substantial. In particular, temperatures derived from X-ray spectra of middle-aged remnants are likely to be overestimated by approximately 15% if cosmic abundances are assumed. Due to the long timescales for grain destruction in X-ray gases over a wide range of temperatures, we suggest that future X-ray spectra studies of supernova remnants be based on depleted abundances instead of cosmic abundances. Our model predictions agree reasonably well with IRAS and Einstein IPC observations of the Cygnus Loop.

Vancura, Olaf↗

Toward the Observation of Dimagnesocene

We have examined the electronic structure of C 5 H 5 MgMgC 5 H 5 , or dimagnesocene, using high-level coupled-cluster techniques. This research is suitable in light of the remarkable synthesis of the valence-isoelectronic diberyllocene by Boronski, Crumpton, Wales, and Aldridge. The Mg–Mg bond distance is predicted to be 2.758 Å, and the Mg–Mg bond dissociation energy is predicted to be 51.8 kcal/mol. Unique aspects to the present research is our characterization of the ionization energy and the electron affinity of this molecule, the energy of dissociation into two neutral cyclopentadienyl magnesium radicals, the determination of the neutral structure at the CCSD(T)/cc-pVTZ level, and the computation of the Raman intensities at the MP2/cc-pVDZ level. Apart from mass spectroscopy, the simplest means of experimental detection is gas-phase or matrix-isolated infrared spectroscopy, in which the A 2 ″ peak at 801 cm –1 should be the most prominent, with an intensity of 581 km/mol.

bond cleavage↗

Steps toward determination of the size and structure of the broad-line region in active galactic nuclei. I - An 8 month campaign of monitoring NGC 5548 with IUE

Emission-line and UV continuum observations of the type I Seyfert galaxy NGC 5548 were carried out for a period of 8 months with the IUE satellite. It was found that both the continuum shape and the line ratios of NGC 5548, while being not unusual for type I Seyfert galaxies, are strongly variable. The UV continuum flux and broad emission line fluxed went through three large maxima and three deep minima; the ratio of miximum to minimum flux was about 4.5 for the continuum at 1350 A. The N V and the He II emission lines exhibited maximum-to-minimum flux ratios as high as those of the continuum; other ionization lines (Ly-alpha, C IV, and C III) exhibited smaller amplitude fluctuations, with the smallest being recorded for the Mg II line (about 1.3). It was found that, except for Mg II, the emission-line variations correlated extremely well with those of the 1350-A continuum.

Clavel, J.↗

High redshift radio galaxies

High redshift galaxies that host powerful radio sources are examined. An overview is presented of the content of radio surveys: 3CR and 3CRR, 4C and 4C/USS, B2/1 Jy, MG, MRC/1Jy, Parkes/PSR, B3, and ESO Key-Project. Narrow-line radio galaxies in the visible and UV, the source of ionization and excitation of the emission lines, emission-line luminosities, morphology of the line-emitting gas, physical properties and energetics, kinematics of the line-emitting gas, and implications from the emission lines are discussed. The morphologies and environments of the host galaxies, the alignment effect, and spectral energy distributions and ages are also examined.

Mccarthy, Patrick J.↗

XMM-Newton Observations of Solar Wind Charge Exchange Emission

We present an XMM-Newton spectrum of diffuse X-ray emission from within the solar system. The spectrum is dominated by O VII and O VIII lines at 0.57 keV and 0.65 keV, O VIII (and possibly Fe XVII) lines at approximately 0.8 keV, Ne IX lines at approximately 0.92 keV, and Mg XI lines at approximately 1.35 keV. This spectrum is consistent with what is expected from charge exchange emission between the highly ionized solar wind and either interstellar neutrals in the heliosphere or material from Earth's exosphere. The emission is clearly seen as a low-energy ( E less than 1.5 keV) spectral enhancement in one of a series of observations of the Hubble Deep Field North. The X-ray enhancement is concurrent with an enhancement in the solar wind measured by the ACE satellite. The solar wind enhancement reaches a flux level an order of magnitude more intense than typical fluxes at 1 AU, and has ion ratios with significantly enhanced higher ionization states. Whereas observations of the solar wind plasma made at a single point reflect only local conditions which may only be representative of solar wind properties with spatial scales ranging from less than half of an Earth radii (approximately 10 s) to 100 Earth radii, X-ray observations of solar wind charge exchange are remote sensing measurements which may provide observations which are significantly more global in character. Besides being of interest in its own right for studies of the solar system, this emission can have significant consequences for observations of more cosmological objects. It can provide emission lines at zero redshift which are of particular interest (e.g., O VII and O VIII) in studies of diffuse thermal emission, and which can therefore act as contamination in objects which cover the entire detector field of view. We propose the use of solar wind monitoring data, such as from the ACE and Wind spacecraft, as a diagnostic to screen for such possibilities.

Snowden, S. L.↗

Single-Event Effect Testing of the PNI RM3100 Magnetometer for Space Applications

The results of a destructive single-event effect susceptibility radiation test of the PNI RM3100 magnetometer sensor, specifically the MagI 2 C ASIC (application-specific integrated circuit) on the sensor board are presented. The sensor is a low-resource commercial off-the-shelf (COTS) magneto-inductive magnetometer. The device was monitored for destructive events and functional interruptions during exposure to a heavy ion beam at the Lawrence Berkeley National Laboratory's 88′′ Cyclotron. The RM3100 did not experience any destructive single-event effects when irradiated to a total fluence of 1.4 × 10 7 cm −2 at an effective linear energy transfer (LET) of 76.7 MeV cm 2 mg −1 while operated at nominal voltage (3.3 V) and elevated temperature (85 ∘C). When these results are combined with previous total ionizing dose tests showing no failures up to 150 kRad (Si), we conclude that the PNI RM3100 is extremely radiation tolerant and can be used in a variety of space environments.

Mark B. Moldwin↗

Distributed polarization-doped GaN p–n diodes with near-unity ideality factor and avalanche breakdown voltage of 1.25 kV

Polarization-induced (Pi) distributed or bulk doping in GaN, with a zero dopant ionization energy, can reduce temperature or frequency dispersions in impurity-doped p–n junctions caused by the deep-acceptor-nature of Mg, thus offering GaN power devices promising prospects. Before comprehensively assessing the benefits of Pi-doping, ideal junction behaviors and high-voltage capabilities should be confirmed. In this work, we demonstrate near-ideal forward and reverse I–V characteristics in Pi-doped GaN power p–n diodes, which incorporates linearly graded, coherently strained AlGaN layers. Hall measurements show a net increase in the hole concentration of 8.9 × 1016 cm−3 in the p-layer as a result of the polarization charge. In the Pi-doped n-layer, a record-low electron concentration of 2.5 × 1016 cm−3 is realized due to the gradual grading of Al0-0.72GaN over 1 μm. The Pi-doped p–n diodes have an ideality factor as low as 1.1 and a 0.10 V higher turn-on voltage than the impurity-doped p–n diodes due to the increase in the bandgap at the junction edge. A differential specific on-resistance of 0.1 mΩ cm2 is extracted from the Pi-doped p–n diodes, similar with the impurity-doped counterpart. The Pi-doped diodes show an avalanche breakdown voltage of ∼1.25 kV, indicating a high reverse blocking capability even without an ideal edge-termination. This work confirms that distributed Pi-doping can be incorporated in high-voltage GaN power devices to increase hole concentrations while maintaining excellent junction properties.

Nomoto, Kazuki↗