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At least 253 records · Page 14

Heterometallic Ce IV / V V Oxo Clusters with Adjustable Catalytic Reactivities

Heterometallic Ce IV /M oxo clusters are underexplored yet and can benefit from synergistic properties from combining cerium and other metal cations to produce efficient redox catalysts. Herein, we designed and synthesized a series of new Ce 12 V 6 oxo clusters with different capping ligands: Ce 12 V 6 -SO 4 , Ce 12 V 6 -OTs (OTs: toluenesulfonic acid), and Ce 12 V 6 -NBSA (NBSA: nitrobenzenesulfonic acid). Single crystal X-ray diffraction (SCXRD) for all three structures reveals a Ce 12 V 6 cubane core formulated [Ce 12 (VO) 6 O 24 ] 18+ with cerium on the edges of the cube, vanadyl capping the faces, and sulfate on the corners. While infrared spectroscopy (IR), ultraviolet–visible spectroscopy (UV–vis), electrospray ionization mass spectrometry (ESI-MS), and proton nuclear magnetic resonance ( 1 H NMR) proved the successful coordination of the organic ligands to the Ce 12 V 6 core, liquid phase 51 V NMR and small-angle X-ray scattering (SAXS) confirmed the integrity of the clusters in the organic solutions. Furthermore, functionalization of the Ce 12 V 6 core with organic ligands both provides increased solubility in term of homogeneous application and introduces porosity to the assemblies of Ce 12 V 6 -OTs and Ce 12 V 6 -NBSA in term of heterogeneous application, thus allowing more catalytic sites to be accessible and improving reactivity as compared to the nonporous and less soluble Ce 12 V 6 -SO 4 . Meanwhile, the coordinated ligands also influenced the electronic environment of the catalytic sites, in turn affecting the reactivity of the cluster, which we probed by the selective oxidation of 2-chloroethyl ethyl sulfide (CEES). Furthermore, this work provides a strategy to make full use of the catalytic sites within a class of inorganic sulfate capped clusters via organic ligand introduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mass spectrometry

A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

Burlingame, A. L.↗

Scaling-law equilibria for calcium in canopy-type models of the solar chromosphere

Scaling laws for resonance line formation are used to obtain approximate excitation and ionization equilibria for a three-level model of singly ionized calcium. The method has been developed for and is applied to the study of magnetograph response in the 8542 A infrared triplet line to magnetostatic canopies which schematically model diffuse, nearly horizontal fields in the low solar chromosphere. For this application, the method is shown to be efficient and semi-quantitative, and the results indicate the type and range of effects on calcium-line radiation which result from reduced gas pressure inside the magnetic regions.

Jones, H. P.↗

Changes of LISM Characteristics in the Heliospheric Interface

The LISM properties can be deduced from observations of interstellar neutral gases in the inner solar system. Parameters accessible by this method are the interstellar wind vector and the densities and temperatures of hydrogen and helium, implying also the deduction of the relative abundance ratios and the degree of ionization in the LISM. Direct inference from observations, for example resonance luminescence measurements of Ly-alpha and He-58.4 nm radiation, yields values appropriate only for the inner solar system, i.e. for the regions within the heliopause dominated by the solar wind plasma. Particularly the subsonic LISM plasma interface ahead of the heliopause causes profound changes in the properties of the neutral LISM gas traversing this region. Mainly p-H charge exchange processes ive rise to the destruction of primary hydrogen and the production of secondary hydrogen atoms, the net effect being a depletion of the neutral hydrogen component of the LISM by about 50%. Details on the depletion mechanisms, the hydrogen and oxygen extinctions, and the consequences for the Ly-alpha resonance luminescence intensity interpretations are presented.

Ripken, H. W.↗

Nonlocal thermal transport in solar flares. II - Spectroscopic diagnostics

Physical parameters obtained for a flaring solar atmosphere in an earlier paper are used here to predict time-dependent emission-line profiles and integrated intensities as a function of position for two spectral lines commonly observed during solar flares: the X-ray resonance lines of Ca XIX and Mg XI. Considerations of ionization nonequilibrium during the rise phase of the flare are addressed, and the effects on the predicted spectral-line characteristics are discussed. It is concluded that some spectroscopic diagnostics favor the nonlocal model, but other long-standing discrepancies between the numerical models and the observations remain unresolved.

Karpen, Judith T.↗

Evidence for a cool wind from the K2 dwarf in the detached binary V471 Tauri

Evidence for mass loss from the K2 dwarf in V471 Tauri is found in the form of discrete absorption features in lines of various elements (Mg, Fe, Cr, Mn) and ionization stages (Mg I, Mg II, Fe I, Fe II). Resonant Mg II absorption indicates a mass loss rate of at least 10 to the -11th solar masses per year. The wind appears to be cool (no more than a few times 10,000 K).

Mullan, D. J.↗

Prospects for detecting UF6 hydrolysis intermediates by mass spectrometry, resonance Raman, and NQR spectroscopy

Simulations are performed to consider several spectrometric and spectroscopic candidates for elucidating the mechanism of the hydrolysis of uranium hexafluoride (UF6). This study is among the first to benchmark the def-mTZVP basis sets for actinide-containing molecules, and it is shown to be a suitable basis set for surveying geometrical structures and vibrational spectra when used in conjunction with density functional theory. An experiment is proposed coupling mass spectrometric ion selection with vibrational spectroscopy, and supporting infrared and Raman spectral simulations demonstrate that ionization blue-shifts bands and can change their qualitative features. Ultraviolet resonance Raman is shown to have good prospects for discriminating U–O–U bridged intermediates, evidence for which was observed recently [L. E. McNamara et al., J. Phys. Chem. A 130, 775–786 (2026)]. As a more speculative approach, we also consider the prospect of addressing 233U or 235U nuclei by quadrupole resonance (NQR) spectroscopy for assigning early stage intermediate complexes. In doing so, we provide a first order-of-magnitude estimate for the collision-induced NQR signal for the UF6 dimer, which is of interest for the interpretation of a fast decoherence time observed in liquid-phase nuclear magnetic resonance. Having provided critical insights into the formation and stability of UF6 hydrolysis intermediates in previous studies, this computational spectroscopy survey is expected to help guide and expedite future laboratory campaigns.

Lutz, Jesse J. [Center for Computing Research, San↗

Study of vacuum ultraviolet emission in helium and helium/nitrogen mixtures

Helium is frequently used as a working medium for the generation of plasmas and is capable of energetic photon emissions. These energetic photon emissions are often attributed to the formation of helium excimer and subsequent photon emission. When the plasma device is exposed to another gas, such as nitrogen, this energetic photon emission can cause photoionization and further ionization wave penetration into the additional gas. Often ignored are the helium resonance emissions that are assumed to be radiation trapped and therefore not pertinent to photoionization. Here, experimental evidence for the presence of helium atomic emission in a pulsed discharge at ten’s of Torr is shown. Simulations of a discharge in similar conditions agree with the experimental measurements. In this context, the role of atomic and molecular helium light emission on photoionization of molecular nitrogen in an ionization wave is studied using a kinetic modeling approach that accounts for radiation dynamics in a developing low-temperature plasma. Three different mixtures of helium at a total pressure of 250 Torr are studied in simulation. Photoionization of the nitrogen molecule by vacuum ultraviolet helium emission is used as the only seed source ahead of the ionization front. It is found that even though radiation trapped, the atomic helium emission lines are the significant source of photoionization of nitrogen. The significant effect of radiation trapped photon emission on ionization wave dynamics demonstrates the need to consider these radiation dynamics in plasma reactors where self-absorbed radiation is ignored.

42 ENGINEERING↗

Investigation of a Light Gas Helicon Plasma Source for the VASIMR Space Propulsion System

An efficient plasma source producing a high-density (approx.10(exp 19/cu m) light gas (e.g. H, D, or He) flowing plasma with a high degree of ionization is a critical component of the Variable Specific Impulse Magnetoplasma Rocket (VASIMR) concept. We are developing an antenna to apply ICRF power near the fundamental ion cyclotron resonance to further accelerate the plasma ions to velocities appropriate for space propulsion applications. The high degree of ionization and a low vacuum background pressure are important to eliminate the problem of radial losses due to charge exchange. We have performed parametric (e.g. gas flow, power (0.5 - 3 kW), magnetic field , frequency (25 and 50 MHz)) studies of a helicon operating with gas (H2 D2, He, N2 and Ar) injected at one end with a high magnetic mirror downstream of the antenna. We have explored operation with a cusp and a mirror field upstream. Plasma flows into a low background vacuum (<10(exp -4) torr) at velocities higher than the ion sound speed. High densities (approx. 10(exp 19/cu m) have been achieved at the location where ICRF will be applied, just downstream of the magnetic mirror.

Squire, J. P.↗

Fundamental data for modeling electron-induced processes in plasma remediation of perfluoroalkyl substances

Plasma treatment of per- and polyfluoroalkyl substances (PFAS) contaminated water is a potentially energy efficient remediation method. In this treatment, an atmospheric pressure plasma interacts with surface-resident PFAS molecules. Developing a reaction mechanism and modeling of plasma–PFAS interactions requires fundamental data for electron–molecule reactions. In this paper, we present results of electron scattering calculations, potential energy landscapes and their implications for plasma modelling of a dielectric barrier discharge in PFAS contaminated gases, a first step towards modelling of plasma–water–PFAS intereactions. It is found that the plasma degradation of PFAS is dominated by dissociative electron attachment with the importance of other contributing processes varying depending on the molecule. All molecules posses a large number of shape resonances – transient negative ion states – from near-threshold up to ionization threshold. These states lie in the region of the most probable electron energies in the plasma (4–5 eV) and consequently are expected to further enhance the fragmentation dynamics in both dissociative attachment and dissociative excitation.

54 ENVIRONMENTAL SCIENCES↗

Resonant control of photoelectron directionality by interfering one- and two-photon pathways

Coherent control of interfering one- and two-photon processes has for decades been the subject of research to achieve the redirection of photocurrent. The present study develops two-pathway coherent control of ground-state helium atom above-threshold photoionization for energies up to the N = 2 threshold, based on a multichannel quantum defect and R-matrix calculation. Three parameters are controlled in our treatment: the optical interference phase ΔΦ, the reduced electric field strength χ = $\mathscr{E}^2_ω$$\mathscr{E}_{2ω}$, and the final state energy ε. A small energy change near a resonance is shown to flip the emission direction of photoelectrons with high efficiency, through an example where 90% of photoelectrons whose energy is near the 2p 2 1 S e resonance flip their emission direction. However, the large fraction of photoelectrons ionized at the intermediate state energy, which are not influenced by the optical control, make this control scheme challenging to realize experimentally.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The L-alpha/H-alpha intensity ratio in PKS 0237-23

The ratio I(L-alpha)/I(H-alpha) has been measured to be 1.7 plus or minus 0.6 in the quasar PKS 0237-23. The measured ratio is similar to that measured in 3C 273 by Davidsen et al. and to that inferred by Baldwin from a study of a large number of quasars; it is a factor of 5 to 14 smaller than expected from recombination theory. If the L-alpha radiation is resonantly scattered and there are modest amounts of dust within the ionized region, the measured ratio may be interpreted in terms of recombination theory, with L-alpha being depleted by absorption by the dust.

Hyland, A. R.↗

Experimental and theoretical investigation for the suppression of the plasma arc drop in the thermionic converter

Ion generation and recombination mechanisms in the cesium plasma as they pertain to the advanced mode thermionic energy converter were studied. The decay of highly ionized cesium plasma was studied in the near afterglow to examine the recombination processes. Very low recombination in such a plasma may prove to be of considerable importance in practical converters. The approaches of external cesium generation were vibrationally excited nitrogen as an energy source of ionization of cesium ion, and microwave power as a means of resonant sustenance of the cesium plasma. Experimental data obtained so far show that all three techniques - i.e., the non-LTE high-voltage pulsing, the energy transfer from vibrationally excited diatomic gases, and the external pumping with a microwave resonant cavity - can produce plasmas with their densities significantly higher than the Richardson density. The implication of these findings as related to Lam's theory is discussed.

Shaw, D. T.↗

Ultraviolet high-resolution spectroscopy of the X-ray binary Sk 160/SMC X-1

High-resolution IUE spectra of Sk 160, the optical counterpart of the X-ray source SMC X-1, show substantial variations with orbital phase of the resonance P Cygni profiles. These variations are ascribed to the changing ionization state in the stellar wind caused by the X-rays emitted by the companion, as suggested by Hatchett and McCray and first established for the galactic X-ray binary Vela X-1. Furthermore, the profile observed during X-ray eclipse differs significantly from profiles of similar stars in the absence of X-ray ionization.

Hammerschlag-Hensberge, G.↗

Analysis of glow discharges for understanding the process of film formation

The physical and chemical processes which occur during the formation of different types of films in a variety of glow discharge plasmas are discussed. Emphasis is placed on plasma diagnostic experiments using spectroscopic methods, probe analysis, mass spectrometric sampling and magnetic resonance techniques which are well suited to investigate the neutral and ionized gas phase species as well as some aspects of plasma surface interactions. The results on metallic, semi-conducting and insulating films are reviewed in conjunction with proposed models and the problem encountered under film deposition conditions. It is concluded that the understanding of film deposition process requires additional experimental information on plasma surface interactions of free radicals and the synergetic effects where photon, electron and ion bombardment change the reactivity of the incident radical with the surface.

Venugopalan, M.↗

Measurement of polycyclic aromatic hydrocarbon (PAHs) in interplanetary dust particles

We report here the first definitive measurements of specific organic molecules (polycyclic aromatic hydrocarbons (PAH's)) in interplanetary dust particles (IDP's). An improved version of the microbeam-two-step laser mass spectrometer was used for the analysis. Two IDP's gave similar mass spectra showing an abundance of PAH's. Control samples, including particles of probable terrestrial origin from the same stratospheric collector, gave either null results or quite different spectra. We conclude that the PAH's are probably indigenous to the IDP's and are not terrestrial contaminants. The instrument used to study the particles is a two-step laser mass spectrometer. Constituent neutral molecules of the sample are first desorbed with a pulsed infrared laser beam focussed to 40 micrometers. In the second step, PAH's in the desorbed plume are preferentially ionized by a pulsed UV laser beam. Resulting ions produced by resonant absorption are extracted into a reflectron time-of-flight mass spectrometer. This instrument has high spatial resolution, high ion transmission, unlimited mass range, and multichannel detection of all ion masses from a single laser shot.

Clemett, S. J.↗