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At least 127 records · Page 7

Reliable IR Line Lists for N2O and OCS Isotopologues for High Temperature Applications up to 2000 K

To address the needs of planetary and exoplanetary atmosphere studies towards JWST, HWO and future IR astronomy missions, theoretical IR line lists of Carbonyl Sulfide (OCS) and Nitrous Oxide (N2O) are generated to provide complete, reliable, and consistent IR reference data in the range of 0 - 15,000 cm-1, or wavelength longer than 0.67 Å, for temperature up to 2000 K. The line lists are quantum mechanically computed using spectroscopically accurate potential energy surfaces empirically refined with reliable high-resolution experimental data, and high-quality dipole moment surfaces constructed at CCSD(T) level with aug-cc-pVT/Q/5(+d)Z basis and extrapolations to complete basis set limit. The Ames N2O line list includes the primary isotopologue 14N2 16O (denoted "446") with J=0-210 and E' up to 25,000 cm-1, and 11 minor isotopologues of 15N and 17/18O with J=0-150 and lower E' cutoffs. For OCS, Ames "natural" 296 K line list includes 12 most abundant isotopologues. The intensity contribution of OCS minor isotopologues at higher temperature is non-negligible, e.g., 8.6 ± 4.9% at 1000 K. The 16O12C32S (93.7%) and 16O12C34S (4.2%) transitions are computed with J=0-240 and E'< 22,000 cm-1, plus J=0-150 and E' < 16,000 cm-1 for five more minor isotopologues. Reliable Effective Hamiltonian models (e.g., NOSL-296 for 14N2 16O), experimental data collections, and reliable HITRAN or MARVEL levels are combined with quantum rovibrational calculations to deliver accurate and consistent empirical corrections for line positions. The reliability and accuracy of our IR intensity predictions are demonstrated by comparison with available databases, line lists, and experiments, at both room temperature and at high temperature. The line lists will be freely available to public online at ZENODO and NAS data portal. We acknowledge the financial support from NASA XRP and APRA programs.

Planetary↗

NO Reduction with CO on Low‐loaded Platinum‐group Metals (Rh, Ru, Pd, Pt, and Ir) Atomically Dispersed on Ceria

Abstract Low‐loaded platinum‐group single‐atom catalysts on CeO 2 (M 1 /CeO 2 ) were synthesized via high‐temperature atom trapping (AT) and tested for the NO+CO reaction under dry and wet conditions. The activity of these catalysts for NO+CO reaction follows the order Rh>Pd≈Ru>Pt>Ir. For Rh, Ru, and Pd single‐atom catalysts, the N 2 O byproduct is formed but not clearly observed in Ir and Pt cases, which may result from the higher reaction temperature (>200 °C) required for Pt and Ir catalysts. The presence of water can promote the activity of these M 1 /CeO 2 catalysts for the NO+CO reaction. Under wet conditions, significant NH 3 formation occurred during the reaction, which is due to the co‐existence of water‐gas‐shift reaction on these catalysts. Compared with Pt, Pd and Ir, the Rh and Ru single‐atom catalysts show higher selectivity to NH 3 species, resulting from the hydride species on the surface. Among all tested catalysts, Ru 1 /CeO 2 shows the highest production of ammonia and highest CO conversion due to excellent water‐gas‐shift activity, whereas Pd 1 /CeO 2 shows lowest ammonia production. Rh 1 /CeO 2 shows the best low temperature NO reduction activity among all tested catalysts.

Tian, Jinshu↗

Structure sensitivity of n -butane hydrogenolysis on supported Ir catalysts

Hydrogenolysis of alkanes has been widely reported as structure sensitive reaction on transition metal heterogeneous catalysts with metal particle sizes ranging between 1 and 20 nm. In this work, a series of Ir/MgAl 2 O 4 and Ir/SiO 2 catalysts with different Ir particle sizes ranging from subnanometer clusters (<1 nm) to nanoparticles (1–3 nm) were prepared and tested for n-butane hydrogenolysis. Our results show that the activity towards n-butane hydrogenolysis increases as Ir particle size increases in the lower particle size range, goes through a maximum at ~1.4–1.6 nm and then drops with a further increase in particle size. In this work, the product distribution at low temperature (170–190 °C) is dominated by central and terminal CAC bond cleavage of n-butane, and less by two CAC bond cleavage or further hydrogenolysis of the propane and ethane products. The selectivity to central CAC bond cleavage is highly dependent on the size of Ir and increases with a decrease in particle size down to ~1.4 nm but remains constant with further decrease in size. The results show that an Ir size of ~1.4 nm is optimum for n-butane hydrogenolysis activity and selectivity towards ethane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Attenuated Total Reflectance Infrared Spectroelectrochemistry (ATR-IR-SEC) for the Characterization of Molecular Redox Processes on Surface-Proximal Doped Silicon ATR Crystal Working Electrodes

In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Distinct Mechanisms and Hydricities of Cp*Ir-Based CO 2 Hydrogenation Catalysts in Basic Water

Transition metal-catalyzed reversible hydrogenation of CO 2 to formate in aqueous solutions under ambient conditions is an attractive environmentally friendly strategy for the storage and transportation of H 2 in a liquid chemical form. Here, mechanistic details for the CO 2 hydrogenation by a series of pentamethylcyclopentadienyl iridium(III) (Cp*Ir) complexes with picolinamidate ligands are investigated through density functional theory and kinetic isotope effects (KIEs) calculations. Additionally, adopting a speciation approach at a pH of 8.2, CO 2 hydrogenation mechanisms of 37 distinct protonation states and conformers of Cp*Ir type complexes are investigated. This imposes a challenging test for the computational modeling in terms of providing a consistent correlation with experimental kinetics and KIE studies of multiple catalysts instead of a single complex. Overall, H 2 heterolysis to generate an iridium hydride intermediate was demonstrated to be the rate determining step, which proceeds via distinct pathways depending on the stereoelectronic properties of the ligand. A peculiar iridium dihydride route was also uncovered, which could be optimized to accelerate the H 2 heterolysis. We have further computed the thermodynamic and kinetic hydricities of 74 complexes with [Cp*Ir(L)(H)] q ( q = -1, 0, 1 depending on the ligand charge by deprotonation or protonation events) general formula. Hydricity values do not show any noticeable correlation with the thermodynamics (Δ G ) of [Cp*Ir(L)(HCO 2 – )] formation but exhibit linear correlation with the kinetics (Δ G ‡ ) of electrophilic CO 2 attack to iridium hydride species, especially when the charges and local structural effects of the metal hydrides are considered. Insights gained in this study on (i) the factors determining the preferred pathway for the rate-limiting H 2 heterolysis step, (ii) the correlation between thermodynamic hydricity and the kinetics of CO 2 insertion to iridium hydride species, and (iii) mechanistic analysis via combination of free energy profiles and KIE studies for a series of iridium catalysts will provide guidelines for the design of next-generation catalysts for the reversible H 2 storage through CO 2 utilization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO Oxidation on Ir 1 /TiO 2 : Resolving Ligand Dynamics and Elementary Reaction Steps

Identifying the rate-controlling steps and the evolution of the ligand environment throughout the catalytic cycle on supported single-atom catalysts is crucial to bridge the gap between heterogeneous and homogeneous catalysis. Here we identified the rate-controlling elementary steps for CO oxidation on TiO 2 -supported Ir single atoms and isolated the corresponding intermediate Ir complexes. Kinetic measurements, operando spectroscopy, and quantum-chemical calculations indicate that the reaction mechanism has two kinetically relevant steps, CO adsorption/oxidation and O 2 dissociation. By varying the reaction conditions, three Ir 1 complexes (states) along the reaction cycle were isolated and identified using in situ spectroscopy. Furthermore, we show that all the intermediate Ir 1 states share a common CO ligand that does not turn over. Finally, this study provides atomic level details on the active, intermediate complexes and reaction cycle of supported single-metal-atom catalysts, thereby offering future possibilities to control the ligand environment and reactivity.

36 MATERIALS SCIENCE↗

Electrospun Ti–Zr Oxide Heterostructures Enable Strongly Anchored Ultralow-Ir Anodes for Durable Acidic Oxygen Evolution

Proton-exchange-membrane water electrolysis (PEMWE) requires acidic oxygen-evolution-reaction (OER) anodes that combine high activity, high durability, and low Ir loading. Here, we report a Ti-Zr composite electrospun oxide (ESO) nanorod support that enables ultralow-Ir anodes for high-performance PEMWE. Zr-containing Ti oxide heterostructures stabilize anatase-rich TiO2, tune the local oxygen-coordination environment, and strengthen interfacial anchoring of IrOx under acidic anodic conditions. The electrospun nanorod network further creates an open, mechanically coherent catalyst layer that improves Ir utilization, ionomer penetration, and mass transport. At an anode loading of 0.2 mgIr cm-2, the optimized Ir/TiZr20-ESO anode delivers a PEMWE mass activity of 0.99 A mgIr-1 at 1.45 V, 28.3 and 43.0 times higher than commercial Ir black and commercial IrO2/TiO2, respectively. The same anode reaches 3.0 and 4.0 A cm-2 at 1.75 and 1.83 V, respectively, and sustains 2000 h operation at 2.0 A cm-2. Also, accelerated stress tests up to 525 hours over 31,500 cycles confirm promising long-term durability, with an insignificant performance decay of 0.4 μV per cycle. Density functional theory indicates that the Ti-Zr oxide heterostructure suppresses Ti demetallation and strengthens IrO2 interfacial binding, rationalizing the improved high-current-density stability.

25 ENERGY STORAGE↗

Strong mutual increase in the efficiency of isotope-selective laser IR dissociation of molecules under nonequilibrium thermodynamic conditions of the compression shock under irradiation in a bimolecular mixture

We have revealed a strong (by a factor of 2 to 5) mutual increase in the yield of IR molecular dissociation (by the example of CF{sub 2}HCl and CF{sub 3}Br) and a significant (by a factor of 1.5 to 3) lowering of dissociation thresholds in the nonequilibrium thermodynamic conditions of compression shock in the irradiation of the molecules by resonance IR laser radiation in the bimolecular mixture in comparison with their individual irradiation. This opens up the possibility to perform efficient isotope-selective IR dissociation of molecules at lower excitation energy densities (Φ ⩽ 1.5 – 2.0 J cm{sup −2}) and thereby to improve the dissociation selectivity. This was demonstrated by the example of chlorine- and bromine-isotope selective dissociation of the specified molecules, which are characterised by quite small (less than 0.25 cm{sup −1}) isotope shifts in the IR vibrational absorption spectra excited by laser radiation. The enrichment coefficients K {sub enr}({sup 35}Cl / {sup 37}Cl) = 0.90 ± 0.05 in the residual CF{sub 2}HCl gas and K {sub enr}({sup 79}Br / {sup 81}Br) in the resultant Br{sub 2} product are obtained when the CF{sub 2}HCl : CF{sub 3}Br = 1 : 1 molecular mixture and CF{sub 3}Br molecules, respectively, are irradiated by the 9R(30) CO{sub 2} laser line (frequency, 1084.635 cm{sup −1}) at an energy density Φ ≈ 1.3 J cm{sup −2}. (laser isotope separation)

36 MATERIALS SCIENCE↗

Mn-induced spin glass behavior in metallic Ir 3 Sn 7-x Mn x

Transition metal stannides are usually semiconductors with a narrow band gap. We report experimental investigation on metallic Ir 3 Sn 7– x Mn x ( x = 0 and 0.56). Single crystal x-ray diffraction refinement indicates that Ir 3 Sn 7– x Mn x crystals form a cubic structure (space group Im 3 - m ) with the lattice parameter a = 9.362(4) Å for x = 0 and 9.328(6) Å for x = 0.56. The electrical resistivity shows metallic behavior between 2 K and 300 K with T 2 dependence at T < 30 K for x = 0, reflecting the Fermi-liquid ground state. While Ir 3 Sn 7 exhibits weak diamagnetism, partial substitution of Sn by Mn results in spin glass behavior in Ir 3 Sn 7- x Mn x below T g ~ 13 K for x = 0.56. Remarkably, an upturn in the resistivity is observed in x = 0.56 below ~2 T g , suggesting strong spin fluctuation. This fluctuation is suppressed by the application of magnetic field, which is reflected in the observation of negative magnetoresistance. The unusual properties that emerge due to Mn doping are discussed.

Physics↗

Robust superconductivity and the suppression of charge-density wave in the quasi-skutterudites Ca 3 ( Ir 1 – x Rh x ) 4 Sn 13 single crystals at ambient pressure

Single crystals of the quasi-skutterudite compounds Ca 3 (Ir 1-x Rh x ) 4 Sn 13 (3–4–13) were synthesized by flux growth and characterized by x-ray diffraction, energy dispersive x-ray spectroscopy, magnetization, resistivity, and radio frequency magnetic susceptibility techniques. The coexistence and competition between the charge density wave (CDW) and superconductivity was studied by varying the Rh/Ir ratio. The superconducting transition temperature, T c , varies from 7 K in pure Ir (x = 0) to 8.3 K in pure Rh (x = 1). Temperature-dependent electrical resistivity reveals monotonic suppression of the CDW transition temperature, T CDW (x). The CDW starts in pure Ir, x = 0, at T CDW ≈ 40 K and extrapolates roughly linearly to zero at x c ≈ 0.53–0.58 under the superconducting dome. Magnetization and transport measurements show a significant influence of CDW on superconducting and normal states. Meissner expulsion is substantially reduced in the CDW region, indicating competition between the CDW and superconductivity. The low-temperature resistivity is higher in the CDW part of the phase diagram, consistent with the reduced density of states due to CDW gapping. Its temperature dependence just above T c shows signs of non-Fermi liquid behavior in a cone-like composition pattern. We conclude that the Ca 3 (Ir 1-x Rh x ) 4 Sn 13 alloy is a good candidate for a composition-driven quantum critical point at ambient pressure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

IR side of bounds on theories with spontaneously broken Lorentz symmetry

In nature, some UV features of dynamics are reflected in IR quantities. In fully relativistic theories, this connection can be probed through the analyticity properties of scattering amplitudes, allowing one to understand which IR theories respect the UV assumptions of quantum field theory. The ensuing analyticity bounds can usually be rephrased as the absence of faster-than-light propagation for low-energy excitations. While it is interesting to understand these relations and their IR characterization for theories that have less idealized properties, it is also more difficult to derive analyticity bounds in these cases. For theories that spontaneously break Lorentz symmetry, recent progress was made by considering correlators of conserved currents and their analyticity properties. In this work, we focus on such theories and work to close the gap from the IR side, finding a natural way to express the known analyticity bounds purely in terms of low-energy kinematical quantities. Our analysis shows that the bounds require gapped excitations to have a slower speed than the gapless ones, at least for momenta that are low with respect to the mass gap. These results suggest a way to interpret the UV/IR connection in more complex theories.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Three-dimensional lattice modulations in the charge density wave system Lu 2 Ir 3 Si 5

Using total and resonant x-ray scattering coupled to large-scale computer modeling, we study the lattice modulations in the complex charge density wave (CDW) material Lu 2 ⁢Ir 3 ⁢Si 5 . Here, we find that it is a unique quantum system where periodic lattice modulations related to emergent CDW order occur in three orthogonal atomic planes of the crystal lattice, leading to the emergence of an unusual three-dimensional (3D) pattern of short and long Ir-Ir and Lu-Lu bonds. The 3D character of observed lattice modulations explains the largely isotropic character of the changes in the electronic properties occurring when the CDW order sets in, demonstrating the strong electron-lattice coupling in Lu 2 ⁢Ir 3 ⁢Si 5 . The result is supported by DFT calculations based on the experimental structure data. Altogether, our work provides strong evidence for the presence of a relationship between the dimensionality of emergent lattice distortions and that of concurrent changes in the electronic properties of CDW materials. The relationship may need to be accounted for when these materials are explored for practical applications.

36 MATERIALS SCIENCE↗

Magnetism of Ir 5 + -based double perovskites: Unraveling its nature and the influence of structure

A combination of x-ray-diffraction, x-ray absorption, x-ray magnetic circular dichroism, macroscopic magnetization, and muon-spin relaxation measurements is used to investigate the interplay between structure (both crystallography and microstructure) and magnetism in Sr 2 YIrO 6 as a function of both chemical (Ca-doping) and physical (hydrostatic) pressure. X-ray absorption spectroscopy clearly shows that the physical pressure is more effective in modifying the structure. On the other hand, the dichroic measurements evidence a constant magnetic signal with physical pressure and strong differences with Ca-doping. Muon-spin relaxation reveals the presence of magnetic order, even when this is hidden in the magnetization data. From the combined analysis, the magnetic results are explained in terms of the presence of Ir 6+ or Ir 4+ ions in magnetic clusters, most likely located at and triggered by antisite disorder. The measurements under high physical pressure indicate that the magnetic state is independent of the crystallographic details such as Ir-O distances and Ir-O-Y angles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ferromagnetic cluster-glass phase in Ca(Co 1-x Ir x ) 2-y As 2 crystals

In this study, single crystals of Ca(Co 1-x Ir x ) 2-y As 2 with 0≤x≤0.35 and 0.10≤y≤0.14 have been grown using the self-flux technique and characterized by single-crystal x-ray diffraction (XRD), energy-dispersive x-ray spectroscopy, magnetization M, and magnetic susceptibility χ measurements versus temperature T, magnetic field H, and time t, and heat-capacity C p (H,T) measurements. The XRD refinements reveal that all the Ir-substituted crystals crystallize in a collapsed-tetragonal structure as does the parent CaCo 2-y As 2 compound. A small 3.3% Ir substitution for Co in CaCo 1.86 As 2 drastically lowers the A-type antiferromagnetic (AFM) transition temperature T N from 52 to 23 K with a significant enhancement of the Sommerfeld electronic heat-capacity coefficient. The A-type AFM structure consists of ab-plane layers of spins ferromagnetically aligned along the c axis with AFM alignment of the spins in adjacent layers along this axis. The positive Weiss temperatures obtained from Curie-Weiss fits to the χ(T>T N ) data indicate that the dominant magnetic interactions are ferromagnetic (FM) for all x. A magnetic phase boundary is inferred to be present between x=0.14 and x=0.17 from a discontinuity in the x dependencies of the effective moment and Weiss temperature in the Curie-Weiss fits. FM fluctuations that strongly increase with increasing x are also revealed from the χ(T) data. Furthermore, the magnetic ground state for x≥0.17 is a spin glass as indicated by hysteresis in χ(T) between field-cooled and zero-field-cooled measurements and from the relaxation of M in a small field that exhibits a stretched-exponential time dependence. The spin glass has a small FM component to the ordering and is hence inferred to be comprised of small FM clusters. The competing AFM and FM interactions along with crystallographic disorder associated with Ir substitution are inferred to be responsible for the development of a FM cluster-glass phase. A logarithmic T dependence of Cp at low T for x=0.14 is consistent with the presence of significant FM quantum fluctuations. This composition is near the T=0 boundary at x≈0.16 between the A-type AFM phase containing ferromagnetically-aligned layers of spins and the FM cluster-glass phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

UV massive resonance from IR double copy consistency

From the perspective of effective field theory (EFT), Wilson coefficients of the low energy theory are determined by integrating out modes of the full ultraviolet (UV) theory. The spectrum can be in principle resummed if one has access to all available infrared (IR) coefficients at low energies. In this work we show that there exists a general class of consistent massive resonance double-copy (CMRDC) models where UV massive residues are reconstructed through double-copy consistency conditions between the IR Wilson coefficients of the full EFT expansion. Through a color-dual bootstrap, we find surprisingly that double-copy consistency alone introduces the kinematic factors of CMRDC models that soften high energy behavior by exponentiating color-dual contacts. This bootstrap suggests that our massive resonance paradigm is an inevitable consequence of the duality between color and kinematics, thereby providing a path towards emergent UV structure directly from the IR. We then demonstrate how CMRDC models can capture a spectrum of massive modes compatible with general multiplicity, and use Padé extrapolation to solve the inverse problem of identifying massive UV resonance from a small number of IR Wilson coefficients. Published by the American Physical Society 2024

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Simultaneous IR and X-ray burst observation of Ser X-1

It has been suggested that the very bright IR bursts observed from the Rapid Burster (MXB 1730-335) are due to Type I X-ray bursts. If the suggestion is correct, similar bright IR bursts may, in general, accompany Type I X-ray bursts. This paper investigates this possibility for one specific case. During the 1977 coordinated worldwide burst watch, simultaneous X-ray and IR observations were made. On 00 h 00 min 25s June 17 UT, a Type I X-ray burst was observed, which was almost certainly emitted by Ser X-1 (MXB 1837+05, 4U1837+04). Simultaneous IR observations failed to detect any bursts.

Lewin, W. H. G.↗

Far-IR selected star formation regions

Detailed far-IR observations and complemenary submillimeter, 5 GHz continuum and c(18)0 observations of a sample of far-IR selected luminous regions of star formation. The clouds and that the exciting stars lie deep within these condensations. The far-IR sources have diversely shaped 40 micron to 180 micron spectra even through their 60 micron to 100 micron color temperatures are similar. The radio and far-IR results together show that the exciting stars are in clusters containing either zero-age main sequence and pre-main sequence stars or consisting entirely of premain sequence objects. C(18)0 and submillimeter observations imply gas densities approximately .00005 - high enough to make t(sub dust) approximately t(sub gas).

Jaffe, D. T.↗

High-spatial-resolution studies of young stellar objects. II - A thick disk surrounding Lynds 1551, IRS 5

Heavily oversampled, small (2 arcsec) beam 2 micron maps of the region surrounding Lynds 1551, IRS 5 provide the basis for reconstructing maximum-entropy 'images' which have an effective spatial resolution of about 0.6 arcsec. These images reveal an extended, cusp-like structure surrounding IRS 5. This structure most likely results as light from IRS 5 is scattered in our direction by dust grains located in a thick disk of diameter 1000 AU. The disk is viewed nearly edge-on and has a mass in dust grains of 2 to 5 x 10 to the -5th solar masses. Its polar axis lies along the observed direction of the bipolar mass outflow inferred from molecular line observations of the L1551 cloud. It is possible that the observed infrared disk may represent the inner regions of a much larger thick-disk structure, whose shape derives from the combined effects of disk rotation and the gravitational field of IRS 5.

Strom, S. E.↗