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Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1)-S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n).02) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt-OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1) - S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n) central dot O2) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt.OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗

Investigation of Oxygen-Induced Quenching of Phosphorescence in Photoexcited Aromatic Molecules by Positron Annihilation Spectroscopy

Platinum OctaEthyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state P(T(Sup 1)) is readily quenched by the oxygen O2 molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the P(T(Sup 1) approaches P(S(Sub O)) transitions is still unknown. The diamagnetic singlet states P(S(Sub n)), which feed P(T(Sub 1)) states via intersystem crossings, would presumably not be affected by O2. It must be only the magnetic P(T(Sub 1)) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of O2P(S(Sub n)), complexes which can also eventually reduce the population of the P(T(Sub 1)) states (i.e., quench phosphorescence). This reduction is possible because higher triplet states in (Pt.OEP) are admixed with the P(S(Sub 1)), states via spin orbit interactions. The experimental procedures and the results of various measurements are presented in this paper.

Singh, Jag J.↗

The Ultrafine Mineralogy of a Molten Interplanetary Dust Particle as an Example of the Quench Regime of Atmospheric Entry Heating

Melting and degassing of interplanetary dust particle L2005B22 at approx. 1200 C was due to flash heating during atmospheric entry. Preservation of the porous particle texture supports rapid quenching from the peak heating temperature whereby olivine and pyroxene nanocrystals (3 nm-26 nm) show partial devitrification of the quenched melt at T approx. = 450 C - 740 C. The implied ultrahigh cooling rates are calculated at approx. 105 C/h-106 C/h, which is consistent with quench rates inferred from the temperature-time profiles based on atmospheric entry heating models. A vesicular rim on a nonstoichiometric relic forsterite grain in this particle represents either evaporative magnesium loss during flash heating or thermally annealed ion implantation texture.

Rietmeijer, Frans J. M.↗

The Tensile Properties of Advanced Nickel-Base Disk Superalloys During Quenching Heat Treatments

There is a need to increase the temperature capabilities of superalloy turbine disks. This would allow full utilization of higher temperature combustor and airfoil concepts under development. One approach to meet this goal is to modify the processing and chemistry of advanced alloys, while preserving the ability to use rapid cooling supersolvus heat treatments to achieve coarse grain, fine gamma prime microstructures. An important step in this effort is to understand the key high temperature tensile properties of advanced alloys as they exist during supersolvus heat treatments. This could help in projecting cracking tendencies of disks during quenches from supersolvus heat treatments. The objective of this study was to examine the tensile properties of two advanced disk superalloys during simulated quenching heat treatments. Specimens were cooled from the solution heat treatment temperatures at controlled rates, interrupted, and immediately tensile tested at various temperatures. The responses and failure modes were compared and related to the quench cracking tendencies of disk forgings.

Gabb, Timothy P.↗

Quench Module Insert Capabilities and Development Test Results

The Quench Module Insert is a directional solidification furnace that will operate in the Materials Science Research Rack (MSRR) on the International Space Station. It will provide high thermal gradient and quench capabilities for processing metals and alloys in microgravity. Numerical analyses and breadboard testing conducted to date show that the QMI can produce an axial temperature gradient approaching 150 C per centimeter in a 1 centimeter diameter aluminum sample with a maximum molten sample temperature of 1100 C. Breadboard testing and analysis have also shown that the quench capabilities of the furnace are sufficient to rapidly solidify at least a 5mm axial portion of a 1 centimeter diameter molten aluminum sample in significantly less than the required 2 seconds and prevent significant backmelt. This paper presents the furnace requirements and capabilities and a status of the associated development testing and analyses.

Carswell, William E.↗

Collisional quenching of OH radio emission from comet Hale-Bopp

Observations of comets in the 18-cm OH transitions offer a means to probe gas production, kinematics, and OH excitation in comets. We present initial results of OH observations of comet Hale-Bopp obtained with the NRAO 43 m antenna located in Greenbank, WV. Maps of the emission provide strong constraints on the amount of quenching of the inversion of the OH ground state A-doublet in the coma. Analysis of the total radio OH flux and maps of its radial brightness distribution indicate a quenched region on the order of approximately 500,000 km during March and April 1997. This large value is generally consistent with previous observations of radio OH quenching in lower production rate comets when the high production rate of comet Hale-Bopp is considered.

NASA Discipline Exobiology↗

Quenching of Excited Na due to He Collisions

The quenching and elastic scattering of excited Sodium by collisions with Helium have been investigated for energies between 10(exp -13) eV and 10 eV. With the ab initio adiabatic potentials and nonadiabatic radial and rotational couplings obtained from multireference single- and double-excitation configuration interaction approach, we carried out scattering calculations by the quantum-mechanical molecular-orbital close-coupling method. Cross sections for quenching reactions and elastic collisions are presented. Quenching and elastic collisional rate coefficients as a function of temperature between 1 micro-K and 10,000 K are also obtained. The results are relevant to modeling non-LTE effects on Na D absorption lines in extrasolar planets and brown dwarfs.

Lin, C. Y.↗

Co2(nu2)-o Quenching Rate Coefficient Derived from Coincidental SABER-TIMED and Fort Collins Lidar Observations of the Mesosphere and Lower Thermosphere

Among the processes governing the energy balance in the mesosphere and lower thermosphere (MLT), the quenching of CO2(nu2) vibrational levels by collisions with O atoms plays an important role. However, there is a factor of 3-4 discrepancy between the laboratory measurements of the CO2-O quenching rate coefficient, k(sub VT),and its value estimated from the atmospheric observations. In this study, we retrieve k(sub VT) in the altitude region85-105 km from the coincident SABER/TIMED and Fort Collins sodium lidar observations by minimizing the difference between measured and simulated broadband limb 15 micron radiation. The averaged k(sub VT) value obtained in this work is 6.5 +/- 1.5 X 10(exp -12) cubic cm/s that is close to other estimates of this coefficient from the atmospheric observations.However, the retrieved k(sub VT) also shows altitude dependence and varies from 5.5 1 +/-1 10(exp -12) cubic cm/s at 90 km to 7.9 +/- 1.2 10(exp -12) cubic cm/s at 105 km. Obtained results demonstrate the deficiency in current non-LTE modeling of the atmospheric 15 micron radiation, based on the application of the CO2-O quenching and excitation rates, which are linked by the detailed balance relation. We discuss the possible model improvements, among them accounting for the interaction of the non-thermal oxygen atoms with CO2 molecules.

SABER/TIMED↗

Cryogenic Spray Quenching of A Simulated Propellant Storage Tank Wall With Heat Transfer Enhancement By A Thin-Film Coating and Flow Pulsing in Microgravity

Human space exploration to the Moon, Mars, and possibly asteroids is NASA’s biggest challenge for the new millennium. One of the critical elements to this mission is the effective, sufficient, and reliable supply of cryogenic propellant fluids. Future lower-earth-orbiting (LEO) propellant fuel depots and human-carrying orbital transfer spacecraft flying to the moon and Mars will have to utilize the high thrust and high efficiency of liquid cryogenic chemical propulsion or nuclear thermal propulsion. Efficient in-space tank-to-tank propellant transfer (propellant fuel depot to orbital transfer spacecraft) of cryogenic propellants is an enabling technology for the planned Crewed Mars Surface Mission. The transfer of cryogenic propellants in space, however, has yet to be accomplished, solely due to the unavailability of cryogenic quenching heat transfer data during chilldown (quenching) and filling of the propellant receiver tank in reduced gravity and microgravity as liquid propellant cannot be stored in a required liquid state until the tank is quenched down to the liquid temperature. Therefore, highly energy efficient thermal-fluid management breakthrough concepts to conserve and minimize the cryogen consumption during propellant transfer have become the focus of research and engineering development, especially for the deep-space mission to Mars. In this paper, we introduce such concepts and demonstrate their feasibility for cryogenic storage tank chilldown in parabolic flights under a simulated space microgravity condition. In order to maximize the storage tank chilldown efficiency for the least amount of cryogen consumption, the technology adopted included cryogenic spray cooling, Teflon thin-film coating of the simulated tank surface, and spray flow pulsing. The completed flight experiments successfully demonstrated that spray cooling is the most efficient cooling method for the tank chilldown in microgravity. In microgravity, Teflon coating alone can improve the efficiency up to 72% and the efficiency can be improved up to 59% by flow pulsing alone. However, Teflon coating together with flow pulsing was found to substantially enhance the chilldown efficiency in microgravity for up to 113%.

spray↗

Heterovalent Substitution of K 2 SrP 2 O 7 :Cr 3+ to Achieve Anti-Thermal-Quenching Broadband Near-Infrared Luminescence

Broadband near-infrared (NIR) light sources based on phosphor-converted light-emitting diodes are highly desirable for biochemical analysis and medical diagnosis applications. However, thermal quenching remains a demanding challenge for developing efficient NIR phosphors. Herein, we report the enhancement of both quantum efficiency and thermal stability in Cr 3+ -activated K 2 SrP 2 O 7 phosphors through a heterovalent substitution strategy by replacing Sr 2+ with Al 3+ in K 2 Sr 1–x Al x P 2 O 7 (0.05 ≤ x ≤ 0.2) to obtain optimized broadband NIR emission. Structural modulation via Al 3+ substitution leads to the optimized composition, K 2 Sr 0.88 Al 0.1 P 2 O 7 :0.02Cr 3+ , which emits across a broad NIR range of 650–1100 nm peaking at 807 nm with a full width at half-maximum of ∼130 nm under 448 nm excitation. Remarkably, its emission intensity at 150 °C remains 120% of the initial value at room temperature, demonstrating a rare antithermal-quenching behavior. Temperature-dependent XRD studies further reveal that Al 3+ substitution effectively suppresses lattice expansion at elevated temperatures, indicating enhanced lattice stability under thermal excitation. Detailed structural and spectral analyses show that the substitution enhances local site symmetry, reduces electron–phonon coupling, increases thermally induced absorption probability, and fortifies energetic barriers against nonradiative transitions. These synergistic effects collectively endow this NIR phosphor with a superior thermal stability. Furthermore, NIR light-emitting diodes fabricated with this phosphor exhibit strong potential for applications in information identification, nondestructive detection, and night vision technologies. This study demonstrates a local structure engineering strategy for designing thermally robust Cr 3+ -activated NIR phosphors, offering valuable insights into material discovery and NIR spectroscopy device development.

Cr3+↗

Computational analysis of flame initiation, quenching, and re-ignition in a prechamber natural gas engine under varying EGR-dilution levels

The on-road natural-gas (NG) fueled transportation relies on stoichiometric spark-ignition engines for the advantages of simple after-treatment system despite the efficiency penalty relative to lean-burn combustion strategies. Exhaust gas recirculation (EGR) has the potential to reduce this efficiency gap at low to moderate loads without the need for complex lean-exhaust aftertreatment systems. However, EGR dilution leads to reduced combustion stability and increased cycle-to-cycle variability. A promising technology that has the potential to achieve reliable operation under diluted conditions is the prechamber ignition (or turbulent jet ignition) which uses chemically active turbulent jets generated from combustion inside a prechamber to initiate, stabilize and accelerate combustion of the mixture inside the main chamber. The present work focusses on developing a RANS-based CFD approach to accurately reproduce in-cylinder phenomena in a stoichiometric NG prechamber-assisted heavy-duty engine without relying on complex combustion models that account for turbulence-chemistry interactions. This is necessary because reactive prechamber jets at high EGR dilution tend to extinguish while emerging into the main chamber, which is followed by a phase of re-ignition — a phenomenon that conventional G-equation or well-stirred reactor combustion models cannot reproduce. With addition of a damping multiplier to the well-stirred reactor model, the predictions are seen to show good agreement with experimental pressure evolution and combustion images acquired from a single cylinder Cummins N-14 optical diesel engine retrofitted with a prechamber ignition system. Model predictions of local heat release in the flame and temperature evolution inside the flame are used to investigate combustion dynamics in the prechamber and the main chamber. It is seen that the well-stirred reactor model with the inclusion of damping is able to reproduce the temporary reduction in heat release within the flame, which can be considered equivalent to quenching of jets, and the subsequent re-ignition of the flame inside the main chamber. The delay between quenching and re-ignition depends on the amount of dilution, as explained by an illustration of flame evolution in a Borghi diagram.

Prechamber ignition↗

Quench protection for high-temperature superconductor cables using active control of current distribution

Superconducting magnets of future fusion reactors are expected to rely on composite high-temperature superconductor (HTS) cable conductors. In presently used HTS cables, current sharing between components is limited due to poorly defined contact resistances between superconducting tapes or by design. The interplay between contact and termination resistances is the defining factor for power dissipation in these cables and ultimately defines their safe operational margins. However, the current distribution between components along the composite conductor and inside its terminations is a priori unknown, and presently, no means are available to actively tune current flow distribution in real-time to improve margins of quench protection. Also, the lack of ability to electrically probe individual components makes it impossible to identify conductor damage locations within the cable. In this work, we address both problems by introducing active current control of current distribution between components using cryogenically operated metal-oxide-semiconductor-field-effect transistors (MOSFETs). We demonstrate through simulation and experiments how real-time current controls can help to drastically reduce heat dissipation in a developing hot spot in a two-conductor model system and help identify critical current degradation of individual cable components. Finally, prospects of other potential uses of MOSFET devices for improved voltage detection, AC loss-driven active quench protection, and remnant magnetization reduction in HTS magnets are also discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Environmental Quenching of Low-surface-brightness Galaxies Near Hosts from Large Magellanic Cloud to Milky Way Mass Scales

Low-surface-brightness galaxies (LSBGs) are excellent probes of quenching and other environmental processes near massive galaxies. We study an extensive sample of LSBGs near massive hosts in the local universe that are distributed across a diverse range of environments. The LSBGs with surface-brightness ${\mu }_{\mathrm{eff},{g}}\gt 24.2\,\mathrm{mag}\,{\mathrm{arcsec}}^{-2}$ are drawn from the Dark Energy Survey Year 3 catalog while the hosts with masses $9.0\lt \mathrm{log}({{ \mathcal M }}_{\star }/{M}_{\odot })\lt 11.0$ comparable to the Milky Way and the Large Magellanic Cloud are selected from the z0MGS sample. We study the projected radial density profiles of LSBGs as a function of their color and surface brightness around hosts in both the rich Fornax–Eridanus cluster environment and the low-density field. We detect an overdensity with respect to the background density, out to 2.5 times the virial radius for both hosts in the cluster environment and the isolated field galaxies. When the LSBG sample is split by g − i color or surface brightness μ eff, g , we find the LSBGs closer to their hosts are significantly redder and brighter, like their high-surface-brightness counterparts. The LSBGs form a clear “red sequence” in both the cluster and isolated environments that is visible beyond the virial radius of the hosts. This suggests preprocessing of infalling LSBGs and a quenched backsplash population around both host samples. More so, the relative prominence of the “blue cloud” feature implies that preprocessing is ongoing near the isolated hosts compared to the cluster environment where the LSBGs are already well processed.

79 ASTRONOMY AND ASTROPHYSICS↗

Bulge Growth and Quenching Since Z=2.5 in Candels/3D-HST

Exploiting the deep high-resolution imaging of all 5 CANDELS fields, and accurate redshift informationprovided by 3D-HST, we investigate the relation between structure and stellar populations fora mass-selected sample of 6764 galaxies above 1010 M, spanning the redshift range 0.5 z 2.5.For the first time, we fit 2-dimensional models comprising a single Sersic fit and two-component (i.e.,bulge + disk) decompositions not only to the H-band light distributions, but also to the stellar massmaps reconstructed from resolved stellar population modeling. We confirm that the increased bulgeprominence among quiescent galaxies, as reported previously based on rest-optical observations, remainsin place when considering the distributions of stellar mass. Moreover, we observe an increaseof the typical Sersic index and bulge-to-total ratio (with median BT reaching 40-50) among starforminggalaxies above 1011 M. Given that quenching for these most massive systems is likely tobe imminent, our findings suggest that significant bulge growth precedes a departure from the starformingmain sequence. We demonstrate that the bulge mass (and ideally knowledge of the bulge andtotal mass) is a more reliable predictor of the star-forming versus quiescent state of a galaxy thanthe total stellar mass. The same trends are predicted by the state-of-the-art semi-analytic model bySomerville et al. In the latter, bulges and black holes grow hand in hand through merging andordisk instabilities, and AGN-feedback shuts off star formation. Further observations will be requiredto pin down star formation quenching mechanisms, but our results imply they must be internal to thegalaxies and closely associated with bulge growth.

Quenching↗

Search for jet quenching with dijets from high-multiplicity pPb collisions at $\sqrt{s_{NN}}$ = 8.16 TeV

The first measurement of the dijet transverse momentum balance xj in proton-lead (pPb) collisions at a nucleon-nucleon center-of-mass energy of $\sqrt{s_{NN}}$ = 8.16 TeV is presented. The xj observable, defined as the ratio of the subleading over leading jet transverse momentum in a dijet pair, is used to search for jet quenching effects. The data, corresponding to an integrated luminosity of 174.6 nb −1 , were collected with the CMS detector in 2016. The x j distributions and their average values are studied as functions of the charged-particle multiplicity of the events and for various dijet rapidity selections. The latter enables probing hard scattering of partons carrying distinct nucleon momentum fractions x in the proton- and lead-going directions. The former, aided by the high-multiplicity triggers, allows probing for potential jet quenching effects in high-multiplicity events (with up to 400 charged particles), for which collective phenomena consistent with quark-gluon plasma (QGP) droplet formation were previously observed. The ratios of x j distributions for high- to low-multiplicity events are used to quantify the possible medium effects. These ratios are consistent with simulations of the hard-scattering process that do not include QGP production. These measurements set an upper limit on medium-induced energy loss of the subleading jet of 1.26% of its transverse momentum at the 90% confidence level in high multiplicity pPb events.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Quenching of the quantum p -strength in light exotic nuclei

One-nucleon spectroscopic overlaps, their strength or spectroscopic factors (SFs), and nucleon removal cross sections for light nuclei in the mass range A≤12 were evaluated using the fully correlated Quantum Monte Carlo (QMC) wave functions (WFs). Harder (AV18+UX) and softer (NV2+3) bare interactions were used providing consistent results. The SFs were also taken from simple Shell Model (SM) calculations. This structure information was incorporated in the standard three-body Faddeev/Alt-Grassberger-Sandhas reaction formalism to evaluate the (p,pN) cross sections. The results further our understanding of the quenching of the quantum p-shell strength obtained from structure and reactions. We have found the ratios of the total QMC sums of SFs to the SM ones to be uniform and ∼ 3/4. The corresponding ratios of the sums Below Particle Threshold (BPT) of SFs, as well as of total cross sections, deviate strikingly from the uniform trend in some special cases. We find these ratios to be close to unit for 9 Li → 8 Li + n and 9 C → 8 B + p. In contrast, they are strongly reduced for 11 C → 10 C + n and 11 B → 10 Be + p mirror transitions, resulting from the quenching of the strength for low-lying 2 + final state transitions. The QMC theoretical cross section BPT for 11 C(p,pn) is about two times smaller than the experimental data.

(p,pN) reactions↗

Structural Evolution and Photoluminescence Quenching across the FASnI 3– x Br x ( x = 0–3) Perovskites

One of the primary methods for band gap tuning in metal halide perovskites has been halide (I/Br) mixing. Despite widespread usage of this type of chemical substitution in perovskite photovoltaics, there is still little understanding of the structural impacts of halide alloying, with the assumption being the formation of ideal solid solutions. The FASnI 3–x Br x (x = 0–3) family of compounds provides the first example where the assumption breaks down, as the composition space is broken into two unique regimes (x = 0–2.9; x = 2.9–3) based on their average structure with the former having a 3D and the latter having an extended 3D (pseudo 0D) structure. Pair distribution function (PDF) analyses further suggest a dynamic 5s 2 lone pair expression resulting in increasing levels of off-centering of the central Sn as the Br concentration is increased. These antiferroelectric distortions indicate that even the x = 0–2.9 phase space behaves as a nonideal solid-solution on a more local scale. Solid-state NMR confirms the difference in local structure yielding greater insight into the chemical nature and local distributions of the FA + cation. In contrast to the FAPbI 3–x Br x series, a drastic photoluminescence (PL) quenching is observed with x ≥ 1.9 compounds having no observable PL. In conclusion, our detailed studies attribute this quenching to structural transitions induced by the distortions of the [SnBr 6 ] octahedra in response to stereochemically expressed lone pairs of electrons. This is confirmed through density functional theory, having a direct impact on the electronic structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗