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At least 1,549 records · Page 86

Development of a Platform for High-Resolution Ion Mobility Separations Coupled with Messenger Tagging Infrared Spectroscopy for High-Precision Structural Characterizations

The ability to uniquely identify a compound requires highly precise and orthogonal measurements. Here we describe a newly developed analytical platform that integrates high resolution ion mobility and cryogenic vibrational ion spectroscopy for high-precision structural characterizations. This platform allows for the temporal separation of isomeric/isobaric ions and provides a highly sensitive description of the ion’s adopted geometry in the gas phase. The combination of these orthogonal structural measurements yields precise descriptors that can be used to resolve between and confidently identify highly similar ions. The unique benefits of our instrument, which integrates a structures for lossless ion manipulations ion mobility (SLIM IM) device with messenger tagging infrared spectroscopy, include the ability to perform high-resolution ion mobility separations and to record the IR spectra of all ions simultaneously. The SLIM IM device, with its 13 m separation path length, allows for multipass experiments to be performed for increased resolution as needed. It is integrated with an Agilent qTOF MS where the collision cell was replaced with a cryogenically held (30 K) TW-SLIM module. The cryo-SLIM is operated in a novel manner that allows ions to be streamed through the device and collisionally cooled to a temperature where they can form noncovalently bound N 2 complexes that are maintained as they exit the device and are detected by the TOF mass analyzer. The instrument can be operated in two modes: IMS+IR where the IR spectra for mobility-selected ions can be recorded and IR-only mode where the IR spectra for all mass-resolved ions can be recorded. In IR-only mode, IR spectra (400 cm –1 spectral range) can be recorded in as short as 2 s for high throughput measurements. Further, this work details the construction of the instrument and modes of operation. It provides initial benchmarking of CCS and IR measurements to demonstrate the utility of this instrument for targeted and untargeted approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-iridium stabilized ruthenium oxide anode catalyst for durable proton-exchange membrane water electrolysis

While mixing iridium (Ir) with ruthenium oxide (RuO 2 ) has proven to be an effective strategy for reducing Ir loading in anode catalysts for proton-exchange membrane (PEM) water electrolysers, achieving industrially relevant long-term stability typically requires an Ir-rich, Ru-lean combination. Here, in this study, by combining density functional theory with Metropolis Monte Carlo methods, we discovered that sufficient stabilization in the RuO 2 lattice could be achieved with less than 50 at.% of Ir, and that Ir in the first subsurface layer plays a critical role. By effectively dispersing Ir dopants within the RuO 2 lattice, we demonstrated an Ir:Ru atomic ratio of only 1:6 that exhibited exceptional stability for over 1,500 h of continuous water electrolysis at 2 A cm −2 . Our Ru 6 IrO x catalyst has the potential to reduce Ir loading by 80% compared with current commercial PEM water electrolysers, and its stability was further validated under industrial testing conditions in a 25-cm 2 PEM electrolyser.

36 MATERIALS SCIENCE↗

Electronic structure of the honeycomb iridate Cu 2 ⁢IrO 3 at high pressure

Cu 2 IrO 3 has attracted recent interest due to its proximity to the Kitaev quantum spin liquid state and the complex structural response observed at high pressures. We use x-ray spectroscopy and scattering as well as electrical transport techniques to unveil the electronic structure of Cu 2 IrO 3 at ambient and high pressures. Despite featuring a Ir 4+ J eff = 1/2 state at ambient pressure, Ir L 3 -edge resonant inelastic x-ray scattering reveals broadened electronic excitations that point to the importance of Ir 5d-Cu 3d interaction. High pressure first drives an Ir-Ir dimer state with collapsed < L · S > and < L z >/< S z >, signaling the formation of 5d molecular orbitals. A novel Cu → Ir charge transfer is observed above 30 GPa at low temperatures, leading to an approximate Ir 3+ and Cu 1.5+ valence, with persistent insulating electrical transport seemingly driven by charge segregation of Cu 1+ /Cu 2+ ions into distinct sites. Concomitant x-ray spectroscopy and diffraction measurements through different thermodynamic paths demonstrate a strong electron-lattice coupling, with J eff = 1/2 and Ir 3+ /Cu 1.5+ electronic states occurring only in phases 1 and 5, respectively. Remarkably, the charge-transfer state can only be reached if Cu 2 IrO 3 is pressurized at low temperature, suggesting that phonons play an important role in the inhibiting this phase. Furthermore, these results point to the choice of thermodynamic path across interplanar collapse transition as a key parameter to access novel states in intercalated iridates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural, electronic, and magnetic properties of nearly ideal J eff = 1/2 iridium halides

Heavy transition metal magnets with J e f f = 1 2 electronic ground states have attracted recent interest due to their penchant for hosting new classes of quantum spin liquids and superconductors. Unfortunately, model systems with ideal J e f f = 1 2 states are scarce due to the importance of noncubic local distortions in most candidate materials. In this work, we identify a family of iridium halide systems [i.e., K 2 Ir Cl 6 , K 2 Ir Br 6 , ( NH 4 ) 2 Ir Cl 6 , and Na 2 Ir Cl 6 · 6 ( H 2 O ) ] with Ir 4 + electronic ground states exhibiting extremely small deviations from the ideal J e f f = 1 2 limit. We also find ordered magnetic ground states for the three anhydrous systems, with single-crystal neutron diffraction on K 2 Ir Br 6 revealing type-I antiferromagnetism. This spin configuration is consistent with expectations for significant Kitaev exchange in a face-centered-cubic magnet. This work establishes that incorporating isolated Ir X 6 octahedra in materials, where X is a halogen ion with a low electronegativity, is an effective design principle for realizing unprecedented proximity to the pure J e f f = 1 2 state. However, at the same time, we highlight undeniable deviations from this ideal state, even in clean materials with ideal Ir X 6 octahedra as inferred from the global cubic crystal structures.

36 MATERIALS SCIENCE↗

Design concept for a second interaction region for the Electron-Ion Collider

In addition to the day-one primary Interaction Region (IR), the design of the Electron Ion Collider (EIC) must support operation of a 2nd IR potentially added later. The 2nd IR is envisioned in an existing experimental hall at RHIC IP8, compatible with the same beam energy combinations as the 1st IR over the full center of mass energy range of ~20 GeV to ~140 GeV. The 2nd IR is designed to be complementary to the 1st IR. In particular, a secondary focus is added in the forward ion direction of the 2nd IR hadron beamline to optimize its capability in detecting particles with magnetic rigidities close to those of the ion beam. We provide the current design status of the 2nd IR in terms of parameters, magnet layout and beam dynamics.

Gamage, B. R.↗

STATUS OF THE SECOND INTERACTION REGION DESIGN FOR ELECTRON-ION COLLIDER

Provisions are being made in the Electron Ion Collider (EIC) design for future installation of a second Interaction Region (IR), in addition to the day-one primary IR. The envisioned location for the second IR is the existing experi- mental hall at RHIC IP8. It is designed to work with the same beam energy combinations as the first IR, covering a full range of the center-of-mass energy of ?20 GeV to ?140 GeV. The goal of the second IR is to complement the first IR, and to improve the detection of scattered particles with magnetic rigidities similar to those of the ion beam. To achieve this, the second IR hadron beamline features a secondary focus in the forward ion direction. The design of the second IR is still evolving. This paper reports the current status of its pa- rameters, magnet layout, and beam dynamics and discusses the ongoing improvements being made to ensure its optimal performance.

Gamage, B.↗

STATUS OF THE SECOND INTERACTION REGION DESIGN FOR ELECTRON-ION COLLIDER

Provisions are being made in the Electron Ion Collider (EIC) design for future installation of a second Interaction Region (IR), in addition to the day-one primary IR. The envisioned location for the second IR is the existing experi- mental hall at RHIC IP8. It is designed to work with the same beam energy combinations as the first IR, covering a full range of the center-of-mass energy of ?20 GeV to ?140 GeV. The goal of the second IR is to complement the first IR, and to improve the detection of scattered particles with magnetic rigidities similar to those of the ion beam. To achieve this, the second IR hadron beamline features a secondary focus in the forward ion direction. The design of the second IR is still evolving. This paper reports the current status of its pa- rameters, magnet layout, and beam dynamics and discusses the ongoing improvements being made to ensure its optimal performance.

Gamage, B.↗

Debris Disk Results from the Gemini Planet Imager Exoplanet Survey's Polarimetric Imaging Campaign

We report the results of a ∼4 yr direct imaging survey of 104 stars to resolve and characterize circumstellar debris disks in scattered light as part of the Gemini Planet Imager (GPI) Exoplanet Survey. We targeted nearby (≲150 pc), young (≲500 Myr) stars with high infrared (IR) excesses (L {sub IR}/L {sub ⋆} > 10{sup −5}), including 38 with previously resolved disks. Observations were made using the GPI high-contrast integral field spectrograph in H-band (1.6 μm) coronagraphic polarimetry mode to measure both polarized and total intensities. We resolved 26 debris disks and 3 protoplanetary/transitional disks. Seven debris disks were resolved in scattered light for the first time, including newly presented HD 117214 and HD 156623, and we quantified basic morphologies of five of them using radiative transfer models. All of our detected debris disks except HD 156623 have dust-poor inner holes, and their scattered-light radii are generally larger than corresponding radii measured from resolved thermal emission and those inferred from spectral energy distributions. To assess sensitivity, we report contrasts and consider causes of nondetections. Detections were strongly correlated with high IR excess and high inclination, although polarimetry outperformed total intensity angular differential imaging for detecting low-inclination disks (≲70°). Based on postsurvey statistics, we improved upon our presurvey target prioritization metric predicting polarimetric disk detectability. We also examined scattered-light disks in the contexts of gas, far-IR, and millimeter detections. Comparing H-band and ALMA fluxes for two disks revealed tentative evidence for differing grain properties. Finally, we found no preference for debris disks to be detected in scattered light if wide-separation substellar companions were present.

79 ASTRONOMY AND ASTROPHYSICS↗

Infrared Galaxies Detected by the Atacama Cosmology Telescope

We report on 167 infrared (IR) galaxies selected by AKARI and IRAS and detected in the Atacama Cosmology Telescope (ACT) Data Release 5 (DR5) sky maps at the 98, 150, and 220 GHz frequency bands. Of these detections, 134 (80%) of the millimeter counterparts are first-time identifications with ACT. We expand the previous ACT extragalactic source catalogs, by including new 98 GHz detections and measurements from ACT DR5. We also report flux density measurements at the 98, 150, and 220 GHz frequency bands. We compute α 98-150 , α 98-220 , and α 150-220 millimeter-wave spectral indices and far-IR to millimeter-wave spectral indices between 90 μm and 98, 150, and 220 GHz. We specify the galaxy type, based on α 150-220 . We combine publicly available multiwavelength data—including ultraviolet, optical, near-IR, mid-IR, far-IR, and the millimeter measurements obtained in this work—and perform spectral energy distribution (SED) fitting with CIGALE. With the radio emission decomposition advantage of CIGALE V2022.0, we identify the origins of the millimeter emissions for 69 galaxies in our sample. Our analysis also shows that millimeter data alone indicates the need for a radio synchrotron component in the SEDs that are produced by active galactic nuclei (AGNs) and/or star formation. We present SEDs and measured physical properties of these galaxies, such as the dust luminosity, AGN luminosity, the total IR luminosity, and the ratio of the IR and radio luminosity. We quantify the relationships between the total IR luminosity and the millimeter-band luminosities, which can be used in the absence of SED analysis.

79 ASTRONOMY AND ASTROPHYSICS↗

Detection of moisture and moisture related phenomena from Skylab

The author had identified the following significant results. Soil moisture and precipitation variations were not detectable as tonal variations on the S19OA IR B and W photography. Some light tonal areas contained high precipitation .83 inches and high moisture content 21.1% while other light tonal areas contained only .02 inches precipitation and as little as 0.7% moisture. Similar variations were observed in dark tonal areas. This inconsistency may be caused by a lapse of 3 to 4 days from the time precipitation occurred until the photographs were taken and the fact that in the first inch of soil the measured soil moisture was generally less than 5.0%. For overall tonal contrast, the aerial color, color IR and aerial B and W appear to be the best. Cities stand out from the landscape best in the aerial color and color IR, however, to see major street patterns a combination of the two aerial B and W bands and the two IR B and W bands may be desirable. For mapping roads it is best use all 6 bands. For lake detection, the IR B and W bands would be the best but for streams the aerial B and W band would be better. The aerial color, color IR, and the two IR B and W bands are best for distinguishing cultivated and non-cultivated areas, whereas the two aerial B and W bands are better for seeing local relief. Clouds may be best seen in the aerial color and color IR bands.

Eagleman, J. R.↗

Infrared spectroscopy of stars

This paper reviews applications of IR techniques in stellar classification, studies of stellar photospheres, elemental and isotopic abundances, and the nature of remnant and ejected matter in near-circumstellar regions. Qualitative IR spectral classification of cool and hot stars is discussed, along with IR spectra of peculiar composite star systems and of obscured stars, and IR characteristics of stellar populations. The use of IR spectroscopy in theoretical modeling of stellar atmospheres is examined, IR indicators of stellar atmospheric composition are described, and contributions of IR spectroscopy to the study of stellar recycling of interstellar matter are summarized. The future of IR astronomy is also considered.

Merrill, K. M.↗

Radio emission from pre-main-sequence stars in Corona Australis

The central region of the Corona Australis molecular cloud surrounding the stars R and TY CrA has been studied using the VLA at 6 cm. Eleven radio sources are detected including five associated with pre-main-sequence objects. The most striking is associated with the near-IR source IRS 7 and shows a complex structure comprising two strong pointlike sources positioned either side of the deeply embedded IR source and two extended lobes of radio emission. The IRS 7 radio source appears to be similar to that associated with Lynds 1551 IRS 5 but has a considerably larger angular size. The other detected sources include the massive pre-main-sequence star TY CrA, the near-IR sources IRS 1 and IRS 5, and the Herbig-Haro object HH 101. The stars R and T CrA were not detected.

Brown, Alexander↗

Accretion rate of extraterrestrial matter: Iridium deposited over the last 70 million years

In order to quantify the accretion rate of extraterrestrial matter during the Cenozoic, Ir concentrations were measured in a continuous series of 450 samples across most of the length of piston core LL44-GPC3. LL44-GPC3 is a 25-meter-long, large-diameter piston core of abyssal clay from the central North Pacific. This core contains a nearly continuous record of sedimentation over the last 70 Ma, as this site migrated from a region near the Equator in the late Cretaceous to its present position north of Hawaii. The first-cut survey across the core is nearing completion, and all of the conclusions of the earlier study, in which was reported the concentrations of Ir, Co, and Sb across 9 meters of this core, remain unchanged. The only strongly enhanced Ir concentrations occur at the Cretaceous-Tertiary (K-T) boundary and outside the K-T boundary Ir correlates well with Co, a terrestrial element which is largely present in hydrogenous ferromanganese oxide precipitates from seawater. Concentrations of both elements appear to be inversely correlated with the sedimentation rate. Although the K-T Ir anomaly is unique in magnitude in this core, there are several small bumps in the Ir profile which may reflect smaller accretionary events. The most promising Ir enhancement was observed in a 30 cm section approximately 1 m below the K-T boundary. Preliminary data suggest deposition of an excess across this interval at a time estimate to be approximate 1 Ma before the K-T impact event, but there is insufficient evidence at present to prove that this reflects enhanced accretion of extraterrestrial matter. A detailed model is being prepared of the chemical record of sedimentation in this core using a combined database of 39 elements in approximately 450 samples across the Cenozoic. Preliminary working model indicates that the only sedimentary sources which contribute significantly to the Ir budget in this core are the hydrogenous precipitates and extraterrestrial particulates.

Kyte, Frank T.↗

High-resolution IRCCD images of the Galactic center at 2.2 and 3.5 microns

An IRCCD camera was used to obtain high-resolution images at 2.2 and 3.5 microns of the Galactic center at subarcsecond resolution. These images show that the compact nonthermal radio source Sgr A-asterisk is not coincident with any part of IRS 16; Sgr A-asterisk is found to be 1.1 + or - 0.3 arcsec west of IRS 16C. At 3.5 microns, IRS 16 is a complex object. IRS 16SW is resolved into two sources, and IRS 16C may be double or extended. From the colors and sizes of the various components, it is difficult to explain these objects as stellar clusters; the required stellar density would be too high. Finally, there is evidence that there is a blue and a red source, separated by about 1 arcsec, for each of the northern arm sources, IRS 1W, IRS 5, and IRS 10.

Tollestrup, Eric V.↗

Characterization of Iridium Coated Rhenium Used in High-Temperature, Radiation-Cooled Rocket Thrusters

Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.

Stulen, R. H.↗

12 and 20 micron imaging of the starburst galaxy NGC 253

The study presents 12- and 20-micron imaging of the starburst galaxy NGC 253 with a spatial resolution of 0.8 arcsec. A positional uncertainty of 1.6 arcsec in these images is estimated on the basis of previous ground-based mid-IR studies to determine the absolute position of the images. It is concluded that the proposed 'nucleus' of NGC 253, i.e., the dominant, bright, flat-spectrum radio source identified by Turner & Ho (1985) (TH 2), is not associated with the mid-IR peak, but rather is located 2.2 arcsec to the northeast. The mid-IR peak, IRS 1, is placed midway between TH 6 and TH 7. Several coincidences with the present 12-micron image are found: IRS 1 falls within 1 arcsec of the 2-micron peak; a second significantly weaker IR source, IRS 2, coincides with TH 2; and the brightest steep-spectrum 6-cm radio source, TH 9, coincides with a 'tongue' of emission extending to the southwest of IRS 1.

Pina, R. K.↗

Near- and mid-infrared imaging of the planetary nebulae BD +30 deg 3639 and IC 418

We present near- and mid-IR images of the planetary nebulae BD +30 deg 3639 and IC 418, with a unique combination of high spatial and spectral resolution. The mid-IR images were obtained with MIRAC, a new IR array camera. For BD +30 deg 3639, the mid-IR images at 10.0, 11.2, 12.4, 12.8, and 13.2 microns have allowed us to separate the various spectral emission components such as the broad UIR features, the 12.8-micron forbidden Ne II emission feature, and continuum emission, to determine the distribution of these components in the nebula. For IC 418, we have obtained high-resolution images in both the near- and mid-IR. The images in the near-IR at J, H, and K are important for determining the source of the IR excess; one component of the excess is located near the central star. We have also imaged the halo emission at H and K, which has been detected in earlier studies, and have determined its spatial extent. The mid-IR images at 9.8 and 11.7 microns show continuum emission coincident with the ionized zone and suggest that SiC emission originates from the region near the central star.

Hora, Joseph L.↗

High-Temperature Oxidation Behavior of Iridium-Rhenium Alloys

The life-limiting mechanism for radiation-cooled rockets made from iridium-coated rhenium (Ir/Re) is the diffusion of Re into the Ir layer and the subsequent oxidation of the resulting Ir-Re alloy from the inner surface. In a previous study, a life model for Ir/Re rockets was developed. It incorporated Ir-Re diffusion and oxidation data to predict chamber lifetimes as a function of temperature and oxygen partial pressure. Oxidation testing at 1540 deg C suggested that a 20-wt percent Re concentration at the inner wall surface should be established as the failure criterion. The present study was performed to better define Ir-oxidation behavior as a function of Re concentration and to supplement the data base for the life model. Samples ranging from pure Ir to Ir-40 wt percent Re (Ir-40Re) were tested at 1500 deg C, in two different oxygen environments. There were indications that the oxidation rate of the Ir-Re alloy increased significantly when it went from a single-phase solid solution to a two-phase mixture, as was suggested in previous work. However, because of testing anomalies in this study, there were not enough dependable oxidation data to definitively raise the Ir/Re rocket failure criterion from 20-wt percent Re to a Re concentration corresponding to entry into the two-phase region.

Reed, Brian D.↗