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At least 181 records · Page 10

Esterification of 3-quinuclidinol, a marker for the incapacitant BZ, for analysis by EI-GC-MS in OPCW test matrices

The analysis by EI-GC-MS of 3-quinuclidinol (3Q), a marker for the riot control and incapacitating agent quinuclinidyl benzilate (BZ), using several, new acylation strategies is described. After evaluating and optimizing conditions for the acylations, these were tested on their ability to successfully derivatize 3Q in three different matrices featured in the 44th Organisation for the Prohibition of Chemical Weapons (OPCW) proficiency test (PT). As 3Q is a highly polar compound, the work here describes acylation strategies that generate 3Q analogs with superior gas chromatographic profiles relative to the underivatized material. The acyl groups studied in this work included acetyl, benzoyl, pentafluorobenzoyl and the bis(3,5-trifluoromethyl)benzoyl. The acylated 3Q products provide sharp, detectable peaks with significantly different retention times from that of the unmodified 3Q. Thus, the retention times for acetyl-, benzoyl-, pentafluorobenzoyl- and 3,5-bis(trifluoromethyl)benzoyl-3Q were determined to be 15.9, 24.9, 22.8 and 22.1 min respectively, in stark contrast to the unmodified 3Q which provides a sharp peak with a retention time centered at ~ 13.5 min only at high concentrations (> 10 µg/mL or µg/g) while a broad peak (RT ~ 15–15.5 min) at low concentrations (< 5 µg/mL or µg/g). The developed protocol was used to derivatize 3Q in three separate matrices. The first two matrices were liquid samples featured during the 44th OPCW PT at two separate concentrations in each (5 and 50 µg/mL). The last matrix was a soil sample featured in the same 44th OPCW PT wherein the 3Q had been spiked at a 12 µg/g concentration. The approach involves the extraction of 3Q from all matrices followed by its acylation resulting in a second reportable analytical method for an OPCW PT. The presented derivatization strategies should find wide applicability particularly in laboratories involved with the analysis of this chemical weapon agent degradation product and those participating in the yearly OPCW PTs.

3-quinuclidinol↗

Abrupt cloud clearing of marine stratocumulus in the subtropical southeast Atlantic

We document rapid and abrupt clearings of large portions of the subtropical marine low cloud deck that have implications for the global radiation balance and climate sensitivity. Over the southeast Atlantic, large areas of stratocumulus are quickly eroded, yielding partial or complete clearing along sharp transitions hundreds to thousands of kilometers in length that move westward at 8 to 12 meters per second and travel as far as 1000+ kilometers from the African coast. The westward-moving cloudiness reductions have an annual peak in occurrence in the period from April through June. The cloud erosion boundaries reduce cloud at ≈10-kilometer scale in less than 15 minutes, move approximately perpendicular to the mean flow, and are often accompanied by small-scale wave features. Observations suggest that the cloud erosion is caused by atmospheric gravity waves.

Science & Technology - Other Topics↗

Preparing for the Next Generation of EUV Lithography at the Center for X-ray Optics

The introduction of EUV lithography into high-volume semiconductor manufacturing this year represents a monumental milestone for EUV technology. After nearly 30 years of development, the EUV research community has overcome many of the key obstacles required to enable the long-awaited integration of EUV lithography into the lab. These obstacles have included: the development of a stable, high-powered EUV source to ensure adequate exposure tool reliability; controlling EUV mask defects and mask contamination; and the development of EUV resists with adequate sensitivity, resolution, and line width roughness to meet the tolerances required for high-volume manufacturing. As EUV moves into its second generation, there will be new challenges facing the community as it works to push EUV technology into the future. Smaller feature sizes will be achieved using higher numerical aperture optics, which are planned to have an anamorphic geometry (asymmetric magnification and numerical aperture between horizontal and vertical axes) to overcome 3D effects at the mask. This new geometry and its larger angle ranges make understanding mask absorber and multilayer effects all the more important. New methods for high-NA wavefront metrology need to be tested to ensure that these optical systems can be aligned to operate with minimal aberrations. Mask defects need to continue to be studied, and the inclusion of EUV pellicles in the roadmap requires that mask inspection and review systems adapt accordingly. Finally, new resists must be developed to support the increased resolution of feature sizes below 8 nm half pitch. The Center for X-ray Optics (CXRO) at Berkeley Lab has been a leader in EUV research for the past 25 years. Leveraging 13.5 nm EUV light from the Advanced Light Source synchrotron facility, CXRO is home to several EUV and soft X-ray (SXR) research tools that have provided important insights into EUV resists, masks, and coatings. The 0.3 NA Microfield exposure tool (MET) and Dose Calibration Tool (DCT) have played an instrumental role in the development of the current generation of high-resolution EUV resists. The Actinic Inspection Tool (AIT) and its successor, SHARP, have enabled aerial image analysis, providing key insights into mask defects, 3D mask effects, illumination, and aberrations. And the CXRO Reflectometer continues to be the industry standard in multilayer coating and EUV mask scattering metrology. To address the new challenges facing the next generation of EUV lithography, CXRO has upgraded its suite of EUV research tools. The 0.5 NA MET5 is a newly commissioned projection lithography tool that is capable of printing feature sizes down to 8 nm half pitch. A new radiation chemistry program is deploying several techniques aimed at dissecting the role of primary photoelectrons and secondary electrons in EUV resists. The SHARP microscope has been outfitted with anamorphic zone plate lenses that can emulate the geometry of next-generation EUV scanners, and the reflectometer has been applied to new scattering experiments for the purpose of understanding the 3D effects of EUV mask multilayers, as well as determining mask properties using scattering profiles. In parallel with these tools, the CXRO High-NA Wavefront Sensing Program is developing high-resolution wavefront sensors suitable for measuring aberrations at high NA. This article presents an overview of these programs and describes how they will address the primary challenges that face the EUV community as it moves to the next generation of EUV lithography.

47 OTHER INSTRUMENTATION↗

Mineral-Filled Fractures as Indicators of Multigenerational Fluid Flow in the Pahrump Hills Member of the Murray Formation, Gale Crater, Mars

Mineral-filled fractures (veins) are valuable indicators of deformation and fluid flow within a sedimentary package. Information obtained from vein morphology, texture, and chemistry may elucidate the sequence and nature of postdepositional fluid events. Additional information from vein patterns and interactions between veins and host rock provides insight into fracture formation mechanism(s). The widespread occurrence of veins and other diagenetic features in the sedimentary rock record preserved in Gale crater, Mars, indicates that postdepositional fluids were regionally active considerably later in time than the primary fluviolacustrine environments responsible for the deposition of Mount Sharp strata. Here we report a suite of veins within the Murray formation at the Pahrump Hills locality that were investigated using the scientific payload of the Mars Science Laboratory Curiosity rover. Based on an analysis of vein color, morphology, and texture, and corroborated by vein chemistry, we interpret three distinct vein types at Pahrump Hills: gray veins, white veins, and dark-toned veins. These veins represent distinct, separate episodes of postdepositional fluid flow, suggesting a protracted history of fluid stability in Gale crater. Additionally, we utilize vein patterns across multiple lithologies at the Pahrump Hills field site to suggest hydrofracture as the primary mechanism of fracture formation.

58 GEOSCIENCES↗

A Small Fullerene (C{sub 24}) may be the Carrier of the 11.2 μ m Unidentified Infrared Band

We analyze the spectrum of the 11.2 μ m unidentified infrared band (UIR) from NGC 7027 and identify a small fullerene (C{sub 24}) as a plausible carrier. The blurring effects of lifetime and vibrational anharmonicity broadening obscure the narrower, intrinsic spectral profiles of the UIR band carriers. We use a spectral deconvolution algorithm to remove the blurring, in order to retrieve the intrinsic profile of the UIR band. The shape of the intrinsic profile—a sharp blue peak and an extended red tail—suggests that the UIR band originates from a molecular vibration–rotation band with a blue band head. The fractional area of the band-head feature indicates a spheroidal molecule, implying a nonpolar molecule and precluding rotational emission. Its rotational temperature should be well approximated by that measured for nonpolar molecular hydrogen, ∼825 K for NGC 7027. Using this temperature, and the inferred spherical symmetry, we perform a spectral fit to the intrinsic profile, which results in a rotational constant implying C{sub 24} as the carrier. We show that the spectroscopic parameters derived for NGC 7027 are consistent with the 11.2 μ m UIR bands observed for other objects. We present density functional theory (DFT) calculations for the frequencies and infrared intensities of C{sub 24}. The DFT results are used to predict a spectral energy distribution (SED) originating from absorption of a 5 eV photon, and characterized by an effective vibrational temperature of 930 K. The C{sub 24} SED is consistent with the entire UIR spectrum and is the dominant contributor to the 11.2 and 12.7 μ m bands.

79 ASTRONOMY AND ASTROPHYSICS↗

Origin of anomalous magnetotransport in kagome superconductors 𝐴⁢V 3 ⁢Sb 5 (𝐴 = K,Rb,Cs)

Multiple anomalous features in electronic spectra of metals with a kagome lattice structure—van Hove singularities, Dirac points, and flat bands—imply that materials containing this structural motif may lie at a nexus of topological and correlated electron physics. Due to the prospects of such exceptional electronic behavior, the recent discovery of superconductivity coexisting with charge-density wave (CDW) order in the layered kagome metals 𝐴⁢V 3 ⁢Sb 5 (𝐴 = K,Rb,Cs) has attracted considerable attention. Notably, these archetypal kagome metals express unconventional magnetotransport behavior, including an unexpected linear-in-𝐻 diagonal resistivity at low fields, and an even more peculiar, nonmonotonic sign-changing behavior of the Hall resistivity, which has been speculated to arise from a chiral CDW. We argue here that this unusual magnetotransport derives not from such unconventional phenomena, but rather from the unique fermiology of the 𝐴⁢V 3 ⁢Sb 5 materials. Specifically, it is caused by a large, concave hexagonal Fermi surface sheet formed in the close proximity to the van Hove singularities, which is backfolded into a small hexagonal sheet and two large triangular sheets in the CDW state. We introduce and analyze a model of the electronic structure of these Fermi surface sheets that allows for a full analytical treatment within Boltzmann kinetic theory and that enables semi-quantitative fits of our transport data. Specifically, we find that the anomalous magnetotransport behavior is caused by the confluence of strong reduction of the Fermi velocity near the van Hove singularities located near the vertices of the hexagonal sheet and sharp corners in Fermi surface generated by the CDW reconstruction. In conclusion, our analytical approach not only explains the anomalous magnetotransport in the kagome superconductors but also can be extended to a variety of metallic systems hosting singular features in their Fermi surfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High Resolution Polar Kerr Effect Studies of CsV 3 Sb 5 : Tests for Time-Reversal Symmetry Breaking below the Charge-Order Transition

We report high resolution polar Kerr effect measurements on CsV 3 Sb 5 single crystals in search for signatures of spontaneous time reversal symmetry breaking below the charge order transition at T * = 94 K. Utilizing two different versions of zero-area loop Sagnac interferometers operating at 1550 nm wavelength, each with the fundamental attribute that without a time reversal symmetry breaking sample at its path, the interferometer is perfectly reciprocal, we find no observable Kerr effect to within the noise floor limit of the apparatus at 30 nanoradians. Simultaneous coherent reflection ratio measurements confirm the sharpness of the charge order transition in the same optical volume as the Kerr measurements. At finite magnetic field we observe a sharp onset of a diamagnetic shift in the Kerr signal at T *, which persists down to the lowest temperature without change in trend. Since 1550 nm is an energy that was shown to capture all features of the optical properties of the material that interact with the charge order transition, we are led to conclude that it is highly unlikely that time reversal symmetry is broken in the charge ordered state in CsV 3 Sb 5 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Convective Transition Statistics over Tropical Oceans for Climate Model Diagnostics: GCM Evaluation

To assess deep convective parameterizations in a variety of GCMs and examine the fast-time-scale convective transition, a set of statistics characterizing the pickup of precipitation as a function of column water vapor (CWV), PDFs and joint PDFs of CWV and precipitation, and the dependence of the moisture–precipitation relation on tropospheric temperature is evaluated using the hourly output of two versions of the GFDL Atmospheric Model, version 4 (AM4), NCAR CAM5 and superparameterized CAM (SPCAM). The 6-hourly output from the MJO Task Force (MJOTF)/GEWEX Atmospheric System Study (GASS) project is also analyzed. Contrasting statistics produced from individual models that primarily differ in representations of moist convection suggest that convective transition statistics can substantially distinguish differences in convective representation and its interaction with the large-scale flow, while models that differ only in spatial–temporal resolution, microphysics, or ocean–atmosphere coupling result in similar statistics. Most of the models simulate some version of the observed sharp increase in precipitation as CWV exceeds a critical value, as well as that convective onset occurs at higher CWV but at lower column RH as temperature increases. While some models quantitatively capture these observed features and associated probability distributions, considerable intermodel spread and departures from observations in various aspects of the precipitation–CWV relationship are noted. For instance, in many of the models, the transition from the low-CWV, nonprecipitating regime to the moist regime for CWV around and above critical is less abrupt than in observations. Additionally, some models overproduce drizzle at low CWV, and some require CWV higher than observed for strong precipitation. For many of the models, it is particularly challenging to simulate the probability distributions of CWV at high temperature.

54 ENVIRONMENTAL SCIENCES↗

Half-Integer Conductance Plateau at the ν = 2 / 3 Fractional Quantum Hall State in a Quantum Point Contact

The v = 2/3 fractional quantum Hall state is the hole-conjugate state to the primary Laughlin v = 1/3 state. Here, we investigate transmission of edge states through quantum point contacts fabricated on a GaAs/AlGaAs heterostructure designed to have a sharp confining potential. When a small but finite bias is applied, we observe an intermediate conductance plateau with G = 0.5⁢(e 2 /ℎ). This plateau is observed in multiple QPCs, and persists over a significant range of magnetic field, gate voltage, and source-drain bias, making it a robust feature. Using a simple model that considers scattering and equilibration between counterflowing charged edge modes, we find this half-integer quantized plateau to be consistent with full reflection of an inner counterpropagating -1/3 edge mode while the outer integer mode is fully transmitted. In a QPC fabricated on a different heterostructure which has a softer confining potential, we instead observe an intermediate conductance plateau at G = (1/3)⁢(e 2 /ℎ). These results provide support for a model at v = 2/3 in which the edge transitions from a structure having an inner upstream -1/3 charge mode and outer downstream integer mode to a structure with two downstream 1/3 charge modes when the confining potential is tuned from sharp to soft and disorder prevails.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A structural coarse-grained model for clays using simple iterative Boltzmann inversion

Cesium-137 is a crucial byproduct of nuclear energy generation and is environmentally threatening due to its long half-life and affinity for naturally occurring micaceous clays. Current experimental observations of illite and phlogopite mica indicate that Cs+ is capable of exchanging with K+ bound in the anhydrous interlayers of layered silicates, forming sharp exchange fronts, leading to interstratification of Cs- and K-illite. We introduce here a coarse-grained (CG) model of the anhydrous illite interlayer developed using iterative Boltzmann inversion that qualitatively and quantitatively reproduces features of a previously proposed feedback mechanism of ion exchange. The CG model represents a 70-fold speedup over all-atom models of clay systems and predicts interlayer expansion for K-illite near ion exchange fronts. Contrary to the longstanding theory that ion exchange in a neighboring layer increases the binding of K in lattice counterion sites leading to interstratification, we find that the presence of neighboring exchanged layers leads to short-range structural relaxations that increase basal spacing and decrease cohesion of the neighboring K-illite layers. We also provide evidence that the formation of alternating Cs- and K-illite interlayers (i.e., ordered interstratification) is both thermodynamically and mechanically favorable compared to exchange in adjacent interlayers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tunneling between two systems of interacting chiral fermions

Here, we develop a theory of tunneling between two systems of spinless chiral fermions. This setup can be realized at the edge of a quantum Hall bilayer structure. We find that the differential conductance of such a device in the absence of interactions has an infinitely sharp peak as a function of applied voltage. Interaction between fermions results in broadening of the conductance peak. We focus on the regime of strong interactions, in which the shape of the peak manifests well defined features associated with the elementary excitations of the system.

36 MATERIALS SCIENCE↗

Spin phases of the helimagnetic insulator $\mathrm{Cu_2 OSeO_3}$ probed by magnon heat conduction

Here, we report studies of thermal conductivity as functions of magnetic field and temperature in the helimagnetic insulator $\mathrm{Cu_2 OSeO_3}$ that reveal novel features of the spin-phase transitions as probed by magnon heat conduction. The tilted conical spiral and low-temperature skyrmion phases, recently identified in small-angle neutron scattering studies, are clearly identified by sharp signatures in the magnon thermal conductivity.Magnon scattering associated with the presence of domain boundaries in the tilted conical phase and regions of skyrmion and conical-phase coexistence are identified.

36 MATERIALS SCIENCE↗

Evaluation of the interactive stratospheric ozone (O3v2) module in the E3SM version 1 Earth system model

Stratospheric ozone affects climate directly as the predominant heat source in the stratosphere and indirectly through chemical reactions controlling other greenhouse gases. The U.S. Department of Energy's Energy Exascale Earth System Model version 1 (E3SMv1) implemented a new ozone chemistry module that improves the simulation of the sharp tropopause gradients, replacing a version based partly on long-term average climatologies that poorly represented heating rates in the lowermost stratosphere. The new O3v2 module extends seamlessly into the troposphere and preserves the naturally sharp cross-tropopause gradient, with 20 %–40 % less ozone in this region. Additionally, O3v2 enables the diagnosis of stratosphere–troposphere exchange flux of ozone, a key budget term lacking in E3SMv1. Here, we evaluate key features in ozone abundance and other closely related quantities in atmosphere-only E3SMv1 simulations driven by observed sea surface temperatures (SSTs, years 1990–2014), comparing them with satellite observations of ozone and also with the University of California, Irvine chemistry transport model (UCI CTM) using the same stratospheric chemistry scheme but driven by European Centre forecast fields for the same period. In terms of stratospheric column ozone, O3v2 shows reduced mean bias and improved northern midlatitude variability, but it is not quite as good as the UCI CTM. As expected, SST-forced E3SMv1 simulations cannot synchronize with observed quasi-biennial oscillations (QBOs), but they do show the typical QBO pattern seen in column ozone. This new O3v2 E3SMv1 model mostly retains the same climate state and climate sensitivity as the previous version, and we recommend its use for other climate models that still use ozone climatologies.

54 ENVIRONMENTAL SCIENCES↗

Sharp and Tunable Crystal/Fano-Type Resonances Enabled by Out-of-Plane Dipolar Coupling in Plasmonic Nanopatch Arrays

Tuning resonance lineshapes of plasmonic structures is essential to create customized media with compelling optical properties for optimized light–matter interactions. The diversity of available metals and the variety of design architectures provide a rich portfolio for statically controlling the resonance lineshape. However, dynamic tuning of resonance attributes (e.g., the resonance wavelength and linewidth) are yet to be more expanded, especially when a narrow resonance linewidth is on demand. Here, using a plasmonic nanopatch array, sharp plasmonic crystal (PC) resonances are demonstrated across a wide spectral range of 230 nm, with full-width at half-maximum of only ≈6 nm. The combination of angle-resolved ellipsometry and full-wave simulations shows that diffractive coupling of out-of-plane electric dipoles is the principal contributor in the formation of such sharp PC resonances. In addition, the designed nanopatch PC supports a plasmonic Fabry–Pérot-like resonance that can be interfered with the PC resonance to generate complex Fano-type lineshapes. Finally, the coexistence of tunable resonance features renders the designed structures as a rich platform for applications seeking enhanced light–matter interactions and optical signal processing.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Emission from quantum-dot high-β microcavities: transition from spontaneous emission to lasing and the effects of superradiant emitter coupling

Measured and calculated results are presented for the emission properties of a new class of emitters operating in the cavity quantum electrodynamics regime. The structures are based on high-finesse GaAs/AlAs micropillar cavities, each with an active medium consisting of a layer of InGaAs quantum dots (QDs) and the distinguishing feature of having a substantial fraction of spontaneous emission channeled into one cavity mode (high β-factor). This paper demonstrates that the usual criterion for lasing with a conventional (low β-factor) cavity, that is, a sharp non-linearity in the input–output curve accompanied by noticeable linewidth narrowing, has to be reinforced by the equal-time second-order photon autocorrelation function to confirm lasing. The article also shows that the equal-time second-order photon autocorrelation function is useful for recognizing superradiance, a manifestation of the correlations possible in high-β microcavities operating with QDs. In terms of consolidating the collected data and identifying the physics underlying laser action, both theory and experiment suggest a sole dependence on intracavity photon number. Evidence for this assertion comes from all our measured and calculated data on emission coherence and fluctuation, for devices ranging from light-emitting diodes (LEDs) and cavity-enhanced LEDs to lasers, lying on the same two curves: one for linewidth narrowing versus intracavity photon number and the other for g( 2 )(0) versus intracavity photon number.

36 MATERIALS SCIENCE↗

Optical conductivity of layered topological semimetal TaNiTe 5

Here, we present an infrared spectroscopy study of the layered topological semimetal TaNiTe 5 , a material with a quasi-one-dimensional structure and strong in-plane anisotropy. Despite its structural features, infrared reflectivity and electronic transport measurements along the 𝑎 and 𝑐 crystallographic axes show metallic behavior without evidence of reduced dimensionality. Optical conductivity reveals an anisotropic but conventional metallic response with low scattering rates and a single sharp infrared-active phonon mode at 396cm −1 ⁢(49meV). Ab initio calculations closely match the experimental optical data and confirm a three-dimensional electronic structure. Our results demonstrate that TaNiTe 5 behaves as a three-dimensional anisotropic semimetal in its electronic and optical properties.

36 MATERIALS SCIENCE↗

Printability and Overall Cooling Performance of Additively Manufactured Holes With Inlet and Exit Rounding

Abstract To improve cooling effectiveness of gas turbine hardware, various film cooling hole shapes have previously been researched. Unique design modifications have recently been made possible through the design freedom allotted by additive manufacturing (AM). As one example, creating a rounded inlet for a film-cooling hole can mitigate separation at the inlet. This study explores various geometric features by exploiting the uses of additive manufacturing for shaped film cooling holes at engine scale. Both printability and cooling performance were evaluated. Resulting from this study, additively manufactured holes with hole inlet and exit rounding were printed with some variations from the design intent (DI). The largest deviations from the design intent occurred from dross roughness features located on the leeward side of the hole inlet. The measured overall effectiveness indicated that an as-built inlet fillet decreased in-hole convection as well as decreased jet mixing compared to the as-built sharp inlet. Including an exit fillet, which prevented an overbuilt diffuser exit, was also found to decrease jet mixing. A particular insight gained from this study is the importance of the convective cooling within the hole to the overall cooling performance. In-hole roughness, which is a result of additive manufacturing, increased convective cooling within the holes but also increased jet mixing as the coolant exited the hole. The increased jet mixing caused low overall effectiveness downstream of injection.

Engineering↗

Influence of TiH{sub 2} on Interfacial Reaction Features Between Cubic Boron Nitride and Cu-Sn-Ti Active Filler Metals

Cubic boron nitride (CBN) grains are brazed by Cu-Sn-Ti filler metal in vacuum at 1223 K. Wetting behaviors, reaction layer features, and elemental distribution characteristics have been systematically investigated through scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The results show that when the TiH{sub 2} content is 5 wt pct, virtually no sharp-edged, partially coated, and uncoated CBN grains can be observed, indicating that adequate wetting could be achieved. Moreover, a continuous reaction layer with uniform thickness (1.30 μm) consisting of TiN, TiB{sub 2}, and TiB is obtained, which indicates that large numbers of TiN, TiB{sub 2}, and TiB compounds could have been formed at the interface. However, when the TiH{sub 2} content exceeds 5 wt pct, the thickness of the reaction layer is no longer significantly expanding and excessive Ti present in the matrix will lower the volume percentage of Cu{sub 3}Sn{sub 1} phase, which will reduce the bonding strength of the brazing samples. Wear tests indicate that the minimum weight loss also occurs at 5 wt pct TiH{sub 2}.

36 MATERIALS SCIENCE↗