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At least 361 records · Page 20

Mass spectrometer measurements of test gas composition in a shock tunnel

Shock tunnels afford a means of generating hypersonic flow at high stagnation enthalpies, but they have the disadvantage that thermochemical effects make the composition of the test flow different to that of ambient air. The composition can be predicted by numerical calculations of the nozzle flow expansion, using simplified thermochemical models and, in the absence of experimental measurements, it has been necessary to accept the results given by these calculations. This note reports measurements of test gas composition, at stagnation enthalpies up to 12.5 MJ.kg(exp -1), taken with a time-of-flight mass spectrometer. Limited results have been obtained in previous measurements. These were taken at higher stagnation enthalpies, and used a quadruple mass spectrometer. The time-of-flight method was preferred here because it enabled a number of complete mass spectra to be obtained in each test, and because it gives good mass resolution over the range of interest with air (up to 50 a.m.a.).

Skinner, K. A.↗

Search for physics beyond the standard model in multilepton final states in proton-proton collisions at $\sqrt{s} =$ 13 TeV

A search for physics beyond the standard model in events with at least three charged leptons (electrons or muons) is presented. The data sample corresponds to an integrated luminosity of 137 fb$^{−1}$ of proton-proton collisions at $ \sqrt{s} $ = 13 TeV, collected with the CMS detector at the LHC in 2016–2018. The two targeted signal processes are pair production of type-III seesaw heavy fermions and production of a light scalar or pseudoscalar boson in association with a pair of top quarks. The heavy fermions may be manifested as an excess of events with large values of leptonic transverse momenta or missing transverse momentum. The light scalars or pseudoscalars may create a localized excess in the dilepton mass spectra. The results exclude heavy fermions of the type-III seesaw model for masses below 880 GeV at 95% confidence level in the scenario of equal branching fractions to each lepton flavor. This is the most restrictive limit on the flavor-democratic scenario of the type-III seesaw model to date. Assuming a Yukawa coupling of unit strength to top quarks, branching fractions of new scalar (pseudoscalar) bosons to dielectrons or dimuons above 0.004 (0.03) and 0.04 (0.03) are excluded at 95% confidence level for masses in the range 15–75 and 108–340 GeV, respectively. These are the first limits in these channels on an extension of the standard model with scalar or pseudoscalar particles.[graphic not available: see fulltext]

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Spectroscopic Characterization of $μ$-$η$ 1 :$η$ 1 -Peroxo Ligands Formed by Reaction of Dioxygen with Electron-Rich Iridium Clusters

Although oxygen is a common ligand in supported metal catalysts, its coordination has been challenging to elucidate. Herein we characterize a diiridium complex that has been previously shown by X-ray diffraction crystallography to incorporate a μ-η 1 :η 1 -peroxo ligand. We observe markedly enhanced intensity at 788 cm -1 in the Raman spectrum of this complex, which is a consequence of bonding of the peroxo ligand but does not shift upon 18 O labeling. Electronic structure calculations at the density functional theory level suggest that this increase in Raman intensity results from bands associated with rocking of CH 2 substituents directly attached to P(Ph) 2 groups coupling with the O-O band. These results provide part of the foundation for understanding oxygen ligands on a silica-supported tetrairidium carbonyl cluster stabilized with bulky electron-donating phosphine ligands [ p-tert -butyl-calix[4]arene(OPr) 3 (OCH 2 PPh 2 ) (Ph = phenyl; Pr = propyl)]. Reaction of the cluster with O2 also led to the growing in of a Raman band at 788 cm -1 , similar to that in the diiridium complex and also assigned to the bonding of a bridging peroxo ligand. Infrared spectra recorded as the supported cluster reacted in sequential exposures to (i) H 2 , (ii) O 2 , (iii) H 2 , and (iv) CO indicate that two bridging peroxo ligands were bonded irreversibly per tetrairidium cluster, replacing bridging carbonyl ligands without altering either the cluster frame or the phosphine ligands. X-ray absorption near edge and infrared spectra include isosbestic points signifying a stoichiometrically simple reaction of the cluster with O 2 , and mass spectra of the effluent gas show that CO 2 formed by oxidation of one terminal CO ligand per cluster as H 2 (and not H 2 O) formed, evidence that hydride ligands had been present on the cluster following treatment (i). The understanding of how O 2 reacts with the metal polyhedron provides a foundation for understanding of how oxidation catalysis may proceed on the surfaces of noble metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Noble dark matter: Surprising elusiveness of dark baryons

Dark matter could be a baryonic composite of stronglyc upled constituents transforming under SU⁡(2) 𝐿 . We classify the SU⁡(2) 𝐿 representations of baryons in a class of simple confining dark sectors and find that the lightest state can be a pure singlet or a singlet that mixes with other neutral components of SU⁡(2) 𝐿 representations, which strongly suppresses the dark matter candidate’s interactions with the Standard Model. We focus on models with a confining SU⁡(𝑁 𝑐 ) and heavy dark quarks constituting vectorlike 𝑁 𝑓 -plet of SU⁢(2) 𝐿 . For benchmark 𝑁 𝑐 and 𝑁 𝑓 , we calculate baryon mass spectra, incorporating electroweak gauge boson exchange in the nonrelativistic quark model, and demonstrate that above TeV mass scales, dark matter is dominantly a singlet state. The combination of this singlet nature with the recently discovered ℋ-parity results in an inert state analogous to noble gases, hence we coin the term noble dark matter. Our results can be understood in the nonrelativistic effective theory that treats the dark baryons as elementary states, where we find singlets accompanying triplets, 5-plets, or more exotic representations. This generalization of WIMP-like theories is more difficult to find or rule out than dark matter models that include only a single SU⁡(2) 𝐿 multiplet (such as a wino), motivating new searches in colliders and a reanalysis of direct and indirect detection prospects in astrophysical observations.

dark matter direct detection↗

Ultraviolet stellar spectra obtained on Skylab

A 15-cm aperture f/3 Ritchey-Chretien telescope equipped with a 4 deg calcium fluoride prism was employed in taking objective prism spectra from 1300 to 5000 A in 188 stars, in the three Skylab missions. Spectra of 2 A resolution at 1400 A and 10 A at 2000 A, extending to B0 stars such that V equals 6.5, were taken of 400 stars in the neighborhood of 1500 A. Stellar temperature and luminosity variations are revealed in resonance lines of C IV and Si IV. Profiles of P Cygni type show up in the spectra of all stars with absolute bolometric magnitudes brighter than minus 8.4, implying appreciable outflow of mass. Spectra with emission lines shortward of 2000 A were obtained for 12 WR stars, and spectra of some companion stars dominating the UV spectra are reported.

Henize, K. G.↗

Cosmic ray mass and momentum spectra at mountain altitude

A cosmic ray mass spectrometer using a superconducting magnet, digitized wire spark chambers, and a scintillation counter time of flight system, has been operated at an altitude of 2750 meters. The apparatus is most sensitive to charged particles with momentum to mass ratios between 0.2 and 2.0. Results for the momentum spectra of protons and deuterons are presented, as well as upper limits for H-3 and He-3. The reaction nucleon + nucleon yields deuteron + pion accounts for part of the observed deuteron spectrum in the 0.9 to 3 GeV/c region.-

Barber, H. B.↗

Coupling field and laboratory measurements to estimate the emission factors of identified and unidentified trace gases for prescribed fires

Vegetative fuels commonly consumed in prescribed fires were collected from five locations in the southeastern and southwestern U.S. and burned in a series of 77 fires at the U.S. Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. An additional 152 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. As phase II of this study, we conducted airborne and ground-based sampling of the emissions from real prescribed fires mostly in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. These extensive field measurements of emission factors (EF) for temperate biomass burning are useful both for modeling and to examine the representativeness of our lab fire EF. The lab/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for “smoldering compounds” emitted by burning the semi-arid SW fuels should likely be increased by about a factor of 2.7 to better represent field fires. Based on the lab/field comparison, we present a table with emission factors for 365 pyrogenic species (including unidentified species) for 4 broad fuel types: pine understory, semi-arid shrublands, evergreen canopy, and duff. To our knowledge this is the most complete measurement of biomass burning emissions to date and it should enable improved representation of smoke in atmospheric models. The results provide important insights into the nature of smoke. For example, ~35% (range from 16-71%) of the mass of gas-phase NMOC species was attributed to the species that we could not identify. These unidentified species are likely not represented in most models, but some provision should be made for the fact that they will react in the atmosphere. In addition, the total mass of gas-phase NMOC divided by the mass of co-emitted PM2.5 averaged ~2.6 for the main fire types with a range from ~1.8-8.8. About 36-63% of the NMOC were likely semivolatile or of intermediate volatility. Thus, the gas-phase NMOC represent a large reservoir of potential precursors for secondary formation of organic aerosol. For the one fire in organic soil (Alaskan duff) about 28% of the emitted carbon was present as gas-phase NMOC in contrast to the other fuels for which NMOC accounted for only ~1-3% of emitted carbon. 71% of the mass of NMOC emitted by the smoldering duff was un-identified. The duff results highlight the need to learn more about the emissions from smoldering organic soils. The NMOC/“NOx-as-NO” ratio was consistently about ten for the main fire types when accounting for all NMOC, indicating strongly NOx-limited O3 production conditions. Finally, the fuel consumption per unit area was measured on 6 of the 14 prescribed fires and averaged 7.08 ± 2.09 (1) Mg ha-1.

Yokelson, R. J.↗

Urban influence on the concentration and composition of submicron particulate matter in central Amazonia

An understanding of how anthropogenic emissions affect the concentrations and composition of airborne particulate matter (PM) is fundamental to quantifying the influence of human activities on climate and air quality. The central Amazon Basin, especially around the city of Manaus, Brazil, has experienced rapid changes in the past decades due to ongoing urbanization. Herein, changes in the concentration and composition of submicron PM due to pollution downwind of the Manaus metropolitan region are reported as part of the GoAmazon2014/5 experiment. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a suite of other gas- and particle-phase instruments were deployed at the T3 research site, 70 km downwind of Manaus, during the wet season. At this site, organic components represented 79±7 % of the non-refractory PM 1 mass concentration on average, which was in the same range as several upwind sites. However, the organic PM 1 was considerably more oxidized at T3 compared to upwind measurements. Positive-matrix factorization (PMF) was applied to the time series of organic mass spectra collected at the T3 site, yielding three factors representing secondary processes (73±15 % of total organic mass concentration) and three factors representing primary anthropogenic emissions (27±15 %). Fuzzy c-means clustering (FCM) was applied to the afternoon time series of concentrations of NO y , ozone, total particle number, black carbon, and sulfate. Four clusters were identified and characterized by distinct air mass origins and particle compositions. Two clusters, Bkgd-1 and Bkgd-2, were associated with background conditions. Bkgd-1 appeared to represent near-field atmospheric PM production and oxidation of a day or less. Bkgd-2 appeared to represent material transported and oxidized for two or more days, often with out-of-basin contributions. Two other clusters, Pol-1 and Pol-2, represented the Manaus influence, one apparently associated with the northern region of Manaus and the other with the southern region of the city. A composite of the PMF and FCM analyses provided insights into the anthropogenic effects on PM concentration and composition. The increase in mass concentration of submicron PM ranged from 25 % to 200 % under polluted compared with background conditions, including contributions from both primary and secondary PM. Furthermore, a comparison of PMF factor loadings for different clusters suggested a shift in the pathways of PM production under polluted conditions. Nitrogen oxides may have played a critical role in these shifts. Increased concentrations of nitrogen oxides can shift pathways of PM production from HO 2 -dominant to NO-dominant as well as increase the concentrations of oxidants in the atmosphere. Consequently, the oxidation of biogenic and anthropogenic precursor gases as well as the oxidative processing of preexisting atmospheric PM can be accelerated. This combined set of results demonstrates the susceptibility of atmospheric chemistry, air quality, and associated climate forcing to anthropogenic perturbations over tropical forests.

54 ENVIRONMENTAL SCIENCES↗

Mass analysis of neutral particles and ions released during electrical breakdowns on spacecraft surfaces

Charged-particle fluxes from breakdown events were studied. Methods to measure mass spectra and total emitted flux of neutral particles were developed. The design and construction of the specialized mass spectrometer was completed. Electrical breakdowns were initiated by a movable blunt contact touching the insulating surface. The contact discharge apparatus was used for final development of two different high-speed recording systems and for measurements of the composition of the materials given off by the discharge. It was shown that intense instantaneous fluxes of neutral particles were released from the sites of electrical breakdown events. A laser micropulse mass analyzer showed that visible discoloration at breakdown sites were correllated with the presence of iron on the polymer side of the film, presumably caused by punch-through to the Inconel backing. Kapton samples irradiated by an oxygen ion beam were tested. The irradiated samples were free of surface hydrocarbon contamination but otherwise behaved in the same way as the Kapton samples tested earlier. Only the two samples exposed to oxygen ion bombardment were relatively clean. This indicates an additional variable that should be considered when testing spacecraft materials in the laboratory.

Kendall, B. R. F.↗

Evolving, dynamical models for collapsed-core globular clusters - M15 and NGC 6624

The stellar populations of the collapsed-core globular clusters M15 and NGC 6624 are investigated by fitting observed surface-brightness and projected velocity-dispersion profiles. The present evolving cluster models were generated by the direct Fokker-Planck method and incorporate realistic stellar mass spectra and energy input from binaries formed by three-body interactions. An evolved power-law mass function with nonluminous remnants of maximum mass 1.0-1.4 solar mass is adopted. M15 is found to be best fitted by postcollapse evolving models with a mass-function slope of x = 0.9 (where x = 1.35 corresponds to the Salpeter mass function) and a maximum remnant mass of 1.3 solar mass. Postcollapse core oscillations, driven by energy input from hard binaries, can produce sufficiently rapid core expansion to explain the resolution of the core of M15 by HST observations reported by Lauer et al. (1991).

Grabhorn, Robert P.↗

Measurements of the composition of aerosol component of Venusian atmosphere with Vega 1 lander, preliminary data

Preliminary investigation of mass spectra of gaseous products of pyrolyzed Venusian cloud particles collected and analyzed by the complex device of mass-spectrometer and collector pyrolyzer on board Vega 1 lander revealed the presence of heavy particles in the upper cloud layer. Based on 64 amu peak (SO2+), an estimate of the lower limit of the sulfuric acid aerosol content at the 62 to 54 km heights of approximately 2.0 mg/cu m is obtained. A chlorine line (35 and 37 amu) is also present in the mass spectrum with a lower limit of the chlorine concentration of approximately 0.3 mg/ cu m.

Surkov, Y. A.↗

Gaussian mixture model clustering algorithms for the analysis of high-precision mass measurements

The development of the phase-imaging ion-cyclotron resonance (PI-ICR) technique for use in Penning trap mass spectrometry (PTMS) increased the speed and precision with which PTMS experiments can be carried out. In PI-ICR, data sets of the locations of individual ion hits on a detector are created showing how ions cluster together into spots according to their cyclotron frequency. Ideal data sets would consist of a single, 2D-spherical spot with no other noise, but in practice data sets typically contain multiple spots, non-spherical spots, or significant noise, all of which can make determining the locations of spot centers non-trivial. A method for assigning groups of ions to their respective spots and determining the spot centers is therefore essential for further improving precision and confidence in PI-ICR experiments. Here, we present the class of Gaussian mixture model (GMM) clustering algorithms as an optimal solution. We show that on simulated PI-ICR data, several types of GMM clustering algorithms perform better than other clustering algorithms over a variety of typical scenarios encountered in PI-ICR. The mass spectra of 163Gd, 163 mGd, 162 Tb, and 162 mTb measured using PI-ICR at the Canadian Penning trap mass spectrometer were checked using GMMs, producing results that were in close agreement with the previously published values.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Supersymmetry with scalar sequestering

Supersymmetric models with a strongly interacting superconformal hidden sector (HS) may drive soft supersymmetry (SUSY) breaking scalar masses, bilinear soft term B μ and Higgs combinations m H u , d 2 + μ 2 to small values at some intermediate scale, leading to unique sparticle mass spectra along with possibly diminished fine-tuning in spite of a large superpotential μ parameter. We set up a computer code to calculate such spectra, which are then susceptible to a variety of constraints: (1) possible charge-or-color breaking (CCB) minima in the scalar potential, (2) unbounded from below (UFB) scalar potential, (3) improper electroweak symmetry breaking, (4) a charged or sneutrino lightest SUSY particle (LSP), (5) generating m h ∼ 125 GeV , (6) consistency with LHC sparticle mass limits, and (7) naturalness. We find this bevy of constraints leaves little or no viable parameter space for the case where hidden sector dynamics dominates minimal supersymmetric standard model (MSSM) running, even for the case of nonuniversal gaugino masses. For the case with moderate HS running with comparable MSSM running, and with universal gaugino masses, then the fine-tuning is ameliorated, but nonetheless remains high. Viable spectra with moderate HS running and with low fine-tuning and large μ can be found for nonuniversal gaugino masses. Published by the American Physical Society 2024

Astronomy & Astrophysics↗

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C 5 H 8 O 4 ) droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C 5 ) hydroxyl functionalization product (C 5 H 8 O 5 ) and a C 4 fragmentation product (C 4 H 6 O 3 ). These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission) of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model) coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from 0.362 to 0.424; however, the diameter of the droplets decreases by 6.1 %. This can be attributed to the formation of volatile fragmentation products that partition to the gas phase, leading to a net loss of organic species and associated particle-phase water, and thus a smaller droplet size. Overall, fragmentation and volatilization processes play a larger role than the functionalization process in determining the evolution of aerosol water content and droplet size at high-oxidation stages.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this study investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH 3 SO 4 Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85%. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO 4 - ) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH 2 O) and a sulfate radical anion (SO 4 .- ) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k , is (3.79 ± 0.19) × 10 -13 cm 3 molecule -1 s -1 with an effective OH uptake coefficient, γ eff , of 0.17 ± 0.03. While about 40% of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 10 12 molecule cm -3 s), only a 3% decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an organosulfate can lead to the formation of sulfate radical anion and produce inorganic sulfate. Fragmentation processes and sulfate radical anion chemistry play a key role in determining the compositional evolution of sodium methyl sulfate during heterogeneous OH oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The lunar terminator ionosphere

The extended ionosphere is seen by the Suprathermal Ion Detector Experiments (SIDE) near the terminator. An analysis of the energy and mass spectra of these ions accelerated by the interplanetary electric field indicates the following: (1) the principal ion species are in the mass per unit charge ranges consistent with neon and argon, (20-28 and 40-44 amu/q); (2) the lunar atmosphere in these mass ranges is distributed exponentially; (3) the terminator region surface number density for Ne-20 is of the order of 10 to the 5th/cu cm; (4) the terminator region lunar surface potential is negative from about 10 to 100 volts; and (5) this potential has a screening length of the order of a kilometer.

Benson, J.↗

Veneziano variations: how unique are string amplitudes?

String theory offers an elegant and concrete realization of how to consistently couple states of arbitrarily high spin. But how unique is this construction? In this paper we derive a novel, multi-parameter family of four-point scattering amplitudes exhibiting i) polynomially bounded high-energy behavior and ii) exchange of an infinite tower of high-spin modes, albeit with a finite number of states at each resonance. These amplitudes take an infinite-product form and, depending on parameters, exhibit mass spectra that are either unbounded or bounded, thus corresponding to generalizations of the Veneziano and Coon amplitudes, respectively. For the bounded case, masses converge to an accumulation point, a peculiar feature seen in the Coon amplitude but more recently understood to arise naturally in string theory [1]. Importantly, our amplitudes contain free parameters allowing for the customization of the slope and offset of the spin-dependence in the Regge trajectory. We compute all partial waves for this multi-parameter class of amplitudes and identify unitary regions of parameter space. For the unbounded case, we apply similar methods to derive new deformations of the Veneziano and Virasoro-Shapiro amplitudes.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗