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At least 649 records · Page 36

Expanded Analogs of Three-Dimensional Lead-Halide Hybrid Perovskites

Replacing the Pb-X octahedral building unit of A I PbX 3 perovskites (X=halide) with a pair of edge-sharing Pb-X octahedra affords the expanded perovskite analogs: A II Pb 2 X 6 . We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with AII=pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the band gap transition of A II Pb 2 X 6 . The organic-molecule-based conduction band and the inorganic-ion-based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum Interferometric Pathway Selectivity in Difference-Frequency-Generation Spectroscopy

Even-order spectroscopies such as sum-frequency generation (SFG) and difference-frequency generation (DFG) can serve as direct probes of molecular chirality. Such signals are usually given by the sum of several interaction pathways that carry different information about matter. Here we focus on DFG, involving impulsive optical–optical–IR interactions, where the last IR pulse probes vibrational transitions in the ground or excited electronic state manifolds, depending on the interaction pathway. Spectroscopy with classical light can use phase matching to select the two pathways. In this theoretical study, we propose a novel quantum interferometric protocol that uses entangled photons to isolate individual pathways. Importantly, this additional selectivity originates from engineering the state of light using a Zou–Wang–Mandel interferometer combined with coincidence detection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric processing and aerosol aging responsible for observed increase in absorptivity of long-range-transported smoke over the southeast Atlantic

Biomass burning aerosol (BBA) from agricultural fires in southern Africa contributes about one-third of the global carbonaceous aerosol load. These particles have strong radiative effects in the southeast Atlantic (SEA), which depend in part on the radiative contrast between the aerosol layer in the free troposphere (FT) and the underlying cloud layer. However, there is large disagreement in model estimates of aerosol-driven climate forcing due to uncertainties in the vertical distribution, optical properties, and life cycle of these particles. This study applies a novel method combining remote sensing observations with regional model outputs to investigate the aging of the BBA and its impact on the optical properties during transatlantic transport from emission sources in Africa to the SEA. Results show distinct variations in extinction Ångström exponent (EAE) and single-scattering albedo (SSA) as aerosols age. Near the source, fresh aerosols are characterized by low mean SSA (0.84) and high EAE (1.85), indicating smaller, highly absorbing particles. By isolating marine contributions from the total column during BBA transport across the SEA, our analysis reveals an initial decrease in BBA absorptivity, with mean FT SSA of 0.87 after 6–7 d, followed by increased absorptivity with mean FT SSA of 0.84 after 10 d, suggesting enhanced absorption due to chemical aging. These findings indicate that BBA becomes more absorbing during extended transport across the SEA, with implications for reducing model uncertainties. Our remote-sensing-based results agree well with previous in situ studies and offer new insights into aerosol–radiation interactions and the energy balance over the SEA.

54 ENVIRONMENTAL SCIENCES↗

Structural Insight into a Sixteen Cyanine Dye Construct via Exciton–Exciton Annihilation

Molecular (dye) aggregates play a prominent role in light harvesting and are of interest in quantum information science; however, there are limited reports hat programmably assemble many (>4) dye aggregates featuring strong coupling and exciton delocalization. Using oligonucleotides with four Cy5s covalently linked in series along the phosphate backbone, we bring four, eight, and sixteen Cy5s in close proximity by assembling four-armed junctions. We elucidate their structure via gel electrophoresis and steady-state and transient optical spectroscopy. We find that Cy5 has a strong propensity to form tetramer clusters, where the exciton is delocalized over all four Cy5s, that the exciton is not delocalized beyond tetramer clusters in the eight and sixteen Cy5 constructs, and that the sixteen Cy5 construct may consist of pairs of tetramer clusters that are isolated from one another. Many-dye aggregates such as these may serve useful as antennae for their intense light absorption and spatially directed energy transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Changes in Cloud Simulations from E3SM Version 1 to Version 2

This study documents clouds simulated by the Energy Exascale Earth System Model (E3SM) version 2 (E3SMv2) and attempts to understand what causes the model behavior change in clouds relative to E3SMv1. This is done by analyzing the last 30-year (1985–2014) data from the 165-year historical simulations using E3SMv1 and v2 and four sensitivity tests to isolate the impact of changes in model parameter choices in its turbulence, shallow convection, and cloud macrophysics parameterization (CLUBB), microphysical parameterization (MG2), and deep convection scheme (ZM), as well as model physics changes in convective triggering. It is shown that E3SMv2 significantly improves the simulation of subtropical coastal stratocumulus clouds (Sc) and clouds with optical depth larger than 3.6 over the stratocumulus to cumulus transition regimes, where Shortwave Cloud Radiative Effect (SWCRE) is also improved, and the Southern Ocean (SO) while seeing an overall slight degradation in low clouds over other tropical and subtropical oceans. The better performance in E3SMv1 over those regions is partially due to error compensation between its simulated optically thin and intermediate low clouds for which E3SMv2 actually improves simulation of optically intermediate low clouds. Sensitivity tests indicate that the changes in low clouds are primarily due to the tuning made in CLUBB. The impact of the ZM tuning is mainly on optically intermediate and thick high clouds, contributing to improved SWCRE and Longwave Cloud Radiative Effect (LWCRE). The impact of the MG2 tuning and the new convective trigger is primarily on the high latitudes and the Southern Ocean (SO). They have a relatively smaller impact on clouds than do the CLUBB and ZM tunings. This study offers additional insights about clouds simulated in E3SMv2 by utilizing multiple data sets and the COSP diagnostic tool as well as through sensitivity tests. The improved understanding will benefit the future E3SM developments.

54 ENVIRONMENTAL SCIENCES↗

New accelerometers under development

The commercial viability of the Space Station requires that it provide a micro-g, or submicro-g environment to users. This represents significant improvement over existing systems. Attainment of the lowest micro-g levels requires isolation systems. Passive and active systems have been evaluated. Best performance is achieved using active approaches where accelerometer sensors close feedback loops. Two emerging accelerometer technologies are presented that have promise for meeting performance goals while achieving reductions of package size, weight, and power. The technologies addressed are Honeywell's design concept for an optical cavity locking accelerometer and the recent development of an integrated silicon accelerometer for government applications.

Wald, Jerry↗

Adaptive structures; Proceedings of the ASME Winter Annual Meeting, San Francisco, CA, Dec. 10-15, 1989

The present conference on adaptive structures discusses piezoelectric and electrostrictive sensors and actuators for adaptive structures and smart materials, real-time control for composite structures with embedded actuators and sensors, a laminated-shell theory incorporating embedded distributed actuators, traveling-wave power flow techniques, uncertainty modeling for the control of an active structure, and active vibration isolation in the presence of unmodeled structural dynamic response. Also discussed are the control of flexible beams via free-free active truss, truss structure control using member actuators with latch mechanism, neural processors for smart-structure control, the effect of imperfections on the static control of adaptive structures, adaptive structures for segmented optical systems, and the shape-control of flexible structures.

Wada, Ben K.↗

A Study of the Vertical Structure of Tropical (20 deg S-20 deg N) Optically Thin Clouds from SAGE II Observations

The tropical cloud data obtained by the satellite instrument of the Stratospheric Aerosol and Gas Experiment (SAGE) II from October 1984 to May 1991 have been used to study cloud vertical distribution, including thickness and multilayer structure, and to estimate cloud optical depth. The results indicate that the SAGE-II-observed clouds are generally optically thin clouds, corresponding to a range of optical depth between approximately 8 x 10(exp -4) and 3 x 10(exp -1) with a mean of about 0.035. Two-thirds are classified as subvisual cirrus and one-third thin cirrus. Clouds between 2- to 3-km thick occur most frequently. Approximately 30% of the SAGE II cloud measurements are isolated single-layer clouds, while 65% are high clouds contiguous with an underlying opaque cloud that terminates the SAGE II profile. Thin clouds above detached opaque clouds at altitudes greater than 6.5 km occur less often. Only about 3% of the SAGE II single-layer clouds are located above the tropopause, while 58% of the cloud layers never reach the tropopause. More than one-third of the clouds appear at the tropopause. This study also shows that clouds occur more frequently and extend higher above the tropopause over the western Pacific than than over the eastern Pacific, especially during northern winter. The uncertainty of the derived results due to the SAGE II sampling constraints, data processing, and cloud characteristics is discussed.

Wang, Pi-Huan↗

A Chemist’s Guide to Solid-State Qubits: Diamond Color Centers as Embedded Vacancy-Centered Molecules

Diamond point defects or color centers are at the crux of solid-state quantum technology applications, from computing to sensing. Modeling molecular qubits has advanced by leaps and bounds mainly due to the advanced quantum mechanical (QM) tools in the arsenal of quantum chemists for modeling (isolated) molecular systems, which should be easily translatable for analogous systems in the solid state. Here, we simulate a series of diamond defects: a carbon vacancy (V C ) and second row substitutions that are adjacent to a V C or D C V C , with D = B, N, and O, to evaluate their magnetic and optical properties. We applied molecular orbital principles, an embedded cluster method, and a multiconfigurational QM theory to computationally characterize the above-mentioned defects for a multitude of spin, charge, and excited states. Our computational approach delivered high-quality QM insights that compare well with experiments. Furthermore, with this framework, we confirm the spin-triplets B C V C – and O C V C 0 to be analogous to N C V C – , with calculated bright transitions that respectively correspond to UV (3.80 eV) and blue (2.65 eV) light absorption and emission lifetimes (τ) of 2.3 and 5.6 ns, which are higher in energy and more short-lived (and thus brighter) than that for N C V C – : green (2.26 eV), τ = 9.5 ns.

Martirez, John Mark P. [Princeton Plasma Physics L↗

Magnetically responsive nanocultures for direct microbial assessment in soil environments

Cultivating microorganisms in native-like conditions is vital for bioprospecting and accessing now unculturable species. However, there remains a gap in scalable tools that can both mimic native microenvironments and enable targeted recovery of microbes from complex settings. Such approaches are essential to advance our understanding of microbial ecology, predict community functions, and discover previously unidentified biotherapeutics. We present magnetic nanocultures—a high-throughput microsystem for isolating and growing environmental microbes under near-native conditions. These nanoliter-scale bioreactors are encapsulated in semipermeable membranes that form magnetic polymeric microcapsules using iron oxide nanoparticles within polydimethylsiloxane-based shells. This design offers mechanical stability and magnetic actuation, enabling efficient retrieval from soil-like environments. The nanocultures are optimized for optical and biological properties to support microbial encapsulation, growth, and sorting. Our study demonstrates the feasibility of using magnetically responsive microenvironments to cultivate elusive microbes, offering a promising platform for bioprospecting previously uncultured or unknown microbial species.

Usman, Huda [Department of Chemical Engineering, C↗

A systematic investigation of edge-on starburst galaxies: Evidence for supernova-driven superwinds

We are completing a project designed to realistically assess the global/cosmological significance of superwinds by attempting to systematize our understanding of them (determine their incidence rate and the dependence of their properties on the star-formation that drives them). Specifically, we are analyzing data from an optical spectroscopic and narrow-band imaging survey of an infrared flux-limited sample of about 50 starburst galaxies whose stellar disks are viewed nearly edge-on. This edge-on orientation is crucial because the relevant properties of the superwind can be far more easily measured when the flow is seen in isolation against the sky rather than projected onto the much brighter gas associated with the starburst galaxy itself.

Lehnert, Matthew D.↗

Symmetric Waveguide Orthomode Junctions

Imaging applications at millimeter and submillimeter wavelengths demand precise characterization of the amplitude, spectrum, and polarization of the electromagnetic radiation. The use of a waveguide orthomode transducer (OMT) can help achieve these goals by increasing spectral coverage and sensitivity while reducing exit aperture size, optical spill, instrumental polarization offsets, and lending itself to integration in focal plane arrays. For these reasons, four-fold symmetric OMTs are favored over a traditional quasi-optical wire grid for focal plane imaging arrays from a systems perspective. The design, fabrication, and test of OMTs realized with conventional split-block techniques for millimeter wave-bands are described. The design provides a return loss is -20 dB over a full waveguide band (40% bandwidth), and the cross-polarization and isolation are greater than -40 dB for tolerances readily achievable in practice. Prototype examples realized in WR10.0 and WR3.7 wavebands will be considered in detail.

Wollack, E. J.↗

Symmetric Waveguide Orthomode Junctions

Imaging applications at millimeter and submillimeter wavelengths demand precise characterization of the amplitude, spectrum, and polarization of the electromagnetic radiation. The use of a waveguide orthomode transducer (OMT) can help achieve these goals by increasing spectral coverage and sensitivity while reducing exit aperture size, optical spill, instrumental polarization offsets, and lending itself to integration in focal plane arrays. For these reasons, four-old symmetric OMTs are favored over a traditional quasi-optical wire grid for focal plane imaging arrays from a systems perspective. The design, fabrication, and test of OMTs realized with conventional split-block techniques for millimeter wave-bands are described. The design provides a return loss is -20 dB over a full waveguide band (40% bandwidth), and the cross-polarization and isolation are greater than -40 dB for tolerances readily achievable in practice. Prototype examples realized in WR10.0 and WR3.7 wavebands will be considered in detail.

Wollack, E. J.↗

NASA Tech Briefs, November 2010

Topics covered include: Portable Handheld Optical Window Inspection Device; Salience Assignment for Multiple-Instance Data and Its Application to Crop Yield Prediction; Speech Acquisition and Automatic Speech Recognition for Integrated Spacesuit Audio Systems ; Predicting Long-Range Traversability from Short-Range Stereo-Derived Geometry; Browser-Based Application for Telemetry Monitoring of Robotic Assets; Miniature Low-Noise G-Band I-Q Receiver; Methods of Using a Magnetic Field Response Sensor Within Closed, Electrically Conductive Containers; Differential Resonant Ring YIG Tuned Oscillator; Microfabricated Segmented-Involute-Foil Regenerator for Stirling Engines; Reducing Seal Adhesion in Low Impact Docking Systems; Optimal Flow Control Design; Corrosion-Resistant Container for Molten-Material Processing; Reusable Hot-Wire Cable Cutter; Deployment of a Curved Truss; High-Volume Airborne Fluids Handling Technologies to Fight Wildfires; Modeling of Alkane Oxidation Using Constituents and Species; Fabrication of Lanthanum Telluride 14-1-11 Zintl High-Temperature Thermoelectric Couple; A Computer Model for Analyzing Volatile Removal Assembly; Analysis of Nozzle Jet Plume Effects on Sonic Boom Signature; Optical Sidebands Multiplier; Single Spatial-Mode Room-Temperature-Operated 3.0 to 3.4 micrometer Diode Lasers; Self-Nulling Beam Combiner Using No External Phase Inverter; Portable Dew Point Mass Spectrometry System for Real-Time Gas and Moisture Analysis; Maximum Likelihood Time-of-Arrival Estimation of Optical Pulses via Photon-Counting Photodetectors; Handheld White Light Interferometer for Measuring Defect Depth in Windows; Decomposition Algorithm for Global Reachability on a Time-Varying Graph; Autonomous GN and C for Spacecraft Exploration of Comets and Asteroids; Efficient Web Services Policy Combination; Using CTX Image Features to Predict HiRISE-Equivalent Rock Density; Isolation of the Paenibacillus phoenicis, a Spore-Forming Bacterium; Monolithically Integrated, Mechanically Resilient Carbon-Based Probes for Scanning Probe Microscopy; Cell Radiation Experiment System; Process to Produce Iron Nanoparticle Lunar Dust Simulant Composite; Inversion Method for Early Detection of ARES-1 Case Breach Failure; Use of ILTV Control Laws for LaNCETS Flight Research;and Evaluating Descent and Ascent Trajectories Near Non-Spherical Bodies.

Source record↗

Surface chemical trapping of optical cycling centers

Quantum information processors based on trapped atoms utilize laser-induced optical cycling transitions for state preparation and measurement. These transitions consist of an electronic excitation from the ground to an excited state and a decay back to the initial ground state, associated with a photon emission. While this technique has been used primarily with atoms, it has also recently been shown to work for some divalent metal hydroxides ( e.g. SrOH) and alkoxides ( e.g. SrOCH 3 ). Additionally, this extension to molecules is possible because these molecules feature nearly isolated, atomic-like ground and first-excited electronic states centered on the radical metal atom. We theoretically investigate the extension of this idea to a larger scale by growing the alkyl group, R, beyond the initial methyl group, CH 3 , while preserving the isolated and highly vertical character of the electronic excitation on the radical metal atom, M. Theory suggests that in the limit as the size of the ligand carbon chain increases, it can be considered a functionalized diamond (or cubic boron nitride) surface. Several requirements must be observed for the cycling centers to function when bound to the surface. First, the surface must have a significant band gap that fully encapsulates both the ground and excited states of the cycling center. Second, while the surface lattice imposes strict limits on the achievable spacing between the SrO– groups, at high coverage, SrO– centers can interact, and show geometric changes and/or electronic state mixing. We show that the coverage of the diamond surface with SrO– cycling centers needs to be significantly sub-monolayer for the functionality of the cycling center to be preserved. Having the lattice-imposed spatial control of SrO– placements will allow nanometer-scale proximity between qubits and will eliminate the need for atom traps for localized cycling emitters. Our results also imply that a functionalization could be done on a scanning microscope tip for local quantum sensing or on photonic structures for optically-mediated quantum information processing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Incorporation of rare earth elements $\text{Sc}$, $\text{Y}$ and $\text{La}$ into gibbsite

Rare earth elements (REE) are increasingly critical resources in technological applications, but the current understanding of their separation by uptake into minerals remains limited. We examined the adsorption and solubilization of scandium (Sc), yttrium (Y), and lanthanum (La) into aluminum hydroxide (gibbsite, Al(OH) 3 ). Based on spectroscopic investigations such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and time of flight-secondary ion mass spectrometry (ToF-SIMS), only Sc exhibited favorable incorporation and adsorption (0.66 and 0.06 atom%, respectively). Analysis of solid state 45 Sc magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) indicated that Sc exhibits an octahedral coordination consistent with isolated substitutions for Al in the gibbsite structure, leading to a increase in lattice constants detectable by X-ray diffraction. Density functional theory (DFT) calculations reinforced this interpretation by reproducing the detected structural distortion as well as demonstrating the relatively favorable energetic basis for Sc incorporation into gibbsite by substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular-Scale Characterization of Photoinduced Charge Separation in Mixed-Dimensional InSe–Organic van der Waals Heterostructures

Layered indium selenide (InSe) is an emerging two-dimensional semiconductor that has shown significant promise for high-performance transistors and photodetectors. The range of optoelectronic applications for InSe can potentially be broadened by forming mixed-dimensional van der Waals heterostructures with zero-dimensional molecular systems that are widely employed in organic electronics and photovoltaics. Here, we report the spatially resolved investigation of photoinduced charge separation between InSe and two molecules (C 70 and C 8 -BTBT) using scanning tunneling microscopy combined with laser illumination. We experimentally and computationally show that InSe forms type-II and type-I heterojunctions with C 70 and C 8 -BTBT, respectively, due to an interplay of charge transfer and dielectric screening at the interface. Laser-excited scanning tunneling spectroscopy reveals a ~0.25 eV decrease in the energy of the lowest unoccupied molecular orbital of C 70 with optical illumination. Furthermore, photoluminescence spectroscopy and Kelvin probe force microscopy indicate that electron transfer from InSe to C 70 in the type-II heterojunction induces a photovoltage that quantitatively matches the observed downshift in the tunneling spectra. In contrast, no significant changes are observed upon optical illumination in the type-I heterojunction formed between InSe and C 8 -BTBT. Density functional theory calculations further show that, despite the weak coupling between the molecular species and InSe, the band alignment of these mixed-dimensional heterostructures strongly differs from the one suggested by the ionization potential and electronic affinities of the isolated components. Self-energy-corrected density functional theory indicates that these effects are the result of the combination of charge redistribution at the interface and heterogeneous dielectric screening of the electron–electron interactions in the heterostructure. In addition to providing specific insight for mixed-dimensional InSe–organic van der Waals heterostructures, this work establishes a general experimental methodology for studying localized charge transfer at the molecular scale that is applicable to other photoactive nanoscale systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nano-G Laboratory

Freely floating platform isolated from all but gravity gradient forces. Report discribes conceptual orbiting spacecraft laboratory that creates environment where acceleration does not exceed 10 to the negative 9th power that of normal acceleration at surface of Earth. Consists of two parts: outer part (spacecraft) and separable inner free-floating part housing experimental apparatus. Equipped with radio and/or optical communication links for control of experiment and recording of data. Used for research in such delicate phenomena as the lambda transition in helium, growth of crystals, and formation of alloys separating into constituents before solidification if gravitation (G) present.

Von Bun, Friedrich O.↗