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At least 685 records · Page 38

Colloidal Nanoribbons: From Infrared to Visible

Using the cation-exchange method, colloidal PbS nanoribbons are converted completely into CdS nanoribbons. This process expands the emission spectrum of the nanoribbons from infrared to visible. Here, the morphology of nanoribbons remains the same after cation exchange, but the crystal structure changes from rock salt to zincblende. CdS nanoribbons exhibit blue band-edge photoluminescence under ultraviolet-light excitation. Cathodoluminescence spectroscopy of the CdS nanoribbons shows multicolor (blue, green, and red) emissions. Further time-resolved photoluminescence spectroscopy studies show that the lifetime of the midgap states is more than 2 orders of magnitude longer than that of the band-edge states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Refreezing of a Marginal Ice Zone Across a Seafloor Distributed Acoustic Sensor

Abstract Seismic instruments such as broadband seismometers and distributed acoustic sensors (DAS) have a demonstrated potential for wide‐scale and continuous in situ monitoring of near‐surface environmental and anthropogenic processes. DAS is attractive for development as a multi‐geophysical observatory due to the prevalence of existing fiber infrastructure in regions with environmental, cultural, or strategic significance. Here we present results from a multi‐seasonal acquisition of DAS data on a seafloor cable in the Beaufort Sea, Alaska. During a November 2021 data collect we captured the rapid transition of ambient noise characteristics from an “ice‐free” state to an “ice‐bound” state. A sea ice formation front was plainly visible on the DAS record and was observed to propagate 20 km seaward over a period of 8 hr. Satellite‐based instrumentation were unable to record this event due to cloud cover, low light conditions, and orbital frequency.

Baker, Michael G.↗

AOI-2, A Novel Access Control Blockchain Paradigm for Cybersecure Sensor Infrastructure in Fossil Power Generation Systems

Fossil power generation systems are increasingly vulnerable to attack from both cybercriminals as well as internal threats. These vulnerabilities demand that emerging technologies such as blockchains be utilized to secure the data involved in the information flows within the Supervisory Control and Data Acquisition (SCADA) systems of the fossil power generation plants. The publicly accessible blockchain protocols, although secure, are visible to everyone. Even private blockchains currently are unable to support different levels of access to different participants, which is a critical requirement for the existing SCADA systems running the power plants. In light of the above, novel blockchain protocols that are specifically adapted to fossil power generation environments need to be developed in order to achieve the goal of cybersecure sensor networks. In this work, we address this question by creating a novel blockchain technology, namely smart private ledger, for cybersecure communication within the fossil power generation systems. A lab-scale sensor network consisting of strain and temperature sensors is constructed to develop the ledger. The technology has hierarchical access control which is compatible with the existing SCADA systems in fossil power plants. The sensor data is used with cryptographic digital signatures and secret sharing protocols within the nodes of the blockchain technology. The research results will lead to cybersecurity for machine-to-machine interactions, infrastructure for secure data logging for sensors, decentralized data storage, and second-layer technologies for high volume machine-to-machine interactions in the power plants. The work aims to largely address the concerns for the security of distributed sensor networks in such systems that can be compromised by insider threats and by cybercriminals. The research has led to the training of the next generation of engineers and scientists in the important areas of sensor engineering and blockchain technology.

01 COAL, LIGNITE, AND PEAT↗

Structural Evolution of Photoexcited Methylcobalamin toward a CarH-like Metastable State: Evidence from Time-Resolved X-ray Absorption and X-ray Emission

CarH is a protein photoreceptor that uses a form of B 12 , adenosylcobalamin (AdoCbl), to sense light via formation of a metastable excited state. Aside from AdoCbl bound to CarH, methylcobalamin (MeCbl) is the only other example – to date – of photoexcited cobalamins forming metastable excited states with lifetimes of nanoseconds or longer. The UV-visible spectra of the excited states of MeCbl and AdoCbl bound to CarH are similar. We have used transient Co K-edge X-ray absorption and X-ray emission spectroscopies in conjunction with transient absorption spectroscopy in the UV–visible region to characterize the excited states of MeCbl. These data show that the metastable excited state of MeCbl has a slightly expanded corrin ring and increased electron density on the cobalt, but only small changes in the axial bond lengths. Finally, this is similar to changes seen previously for CarH, suggesting that MeCbl may be a good model for AdoCbl in CarH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plot-level rapid screening for photosynthetic parameters using proximal hyperspectral imaging

Abstract Photosynthesis is currently measured using time-laborious and/or destructive methods which slows research and breeding efforts to identify crop germplasm with higher photosynthetic capacities. We present a plot-level screening tool for quantification of photosynthetic parameters and pigment contents that utilizes hyperspectral reflectance from sunlit leaf pixels collected from a plot (~2 m×2 m) in <1 min. Using field-grown Nicotiana tabacum with genetically altered photosynthetic pathways over two growing seasons (2017 and 2018), we built predictive models for eight photosynthetic parameters and pigment traits. Using partial least squares regression (PLSR) analysis of plot-level sunlit vegetative reflectance pixels from a single visible near infra-red (VNIR) (400–900 nm) hyperspectral camera, we predict maximum carboxylation rate of Rubisco (Vc,max, R2=0.79) maximum electron transport rate in given conditions (J1800, R2=0.59), maximal light-saturated photosynthesis (Pmax, R2=0.54), chlorophyll content (R2=0.87), the Chl a/b ratio (R2=0.63), carbon content (R2=0.47), and nitrogen content (R2=0.49). Model predictions did not improve when using two cameras spanning 400–1800 nm, suggesting a robust, widely applicable and more ‘cost-effective’ pipeline requiring only a single VNIR camera. The analysis pipeline and methods can be used in any cropping system with modified species-specific PLSR analysis to offer a high-throughput field phenotyping screening for germplasm with improved photosynthetic performance in field trials.

59 BASIC BIOLOGICAL SCIENCES↗

Deactivating Emission in Azulene via Solvent-Induced (Anti)Aromaticity

Anti-Kasha emission is a coveted feature in optoelectronics, with promise in areas such as imaging, sensing, and the production of white-light LEDs via dual-photon emission. Despite being a rare feature in organic systems, anti-Kasha emission is readily observed in the deceptively simple molecule azulene, which possesses two bright singlet states in the UV–visible spectrum and readily emits from the S 2 state. With dominant anti-Kasha emission and decades of synthetic study, azulene is a perfect candidate for novel material fabrication; however, large gaps persist in understanding the photophysics of even the simple parent compound. These range from competing, experimentally unverified models of azulene reactivity and aromaticity to the unexplained deactivation of anti-Kasha emission in a host of azulene derivatives. Herein, we use fluorescence and transient absorption spectroscopies to explore the detailed solvent dependence of azulene photophysics. We discover a tunable reduction in the S 2 lifetime via weak complexation with aromatic solvents. Interestingly, our results are independent of polarity, highlighting the primacy of peripherally delocalized 10-π Hückel aromaticity over zwitterionic character. When the dipolar character is enhanced through chemical functionalization, we observe even greater sensitivity to solvent aromaticity and more rapid quenching, revealing the role of conical intersections in azulenes with zwitterionic excited states. Overall, this work provides essential mechanistic insight into the photophysics of azulene and reveals a simple new approach to control the excited-state aromaticity and anti-Kasha emission in this class of materials.

Absorption↗

Zinc oxide (ZnO) hybrid metasurfaces exhibiting broadly tunable topological properties

Extreme light confinement observed in periodic photonic structures, such as the vortex singularities in momentum (k) space, has been associated with their topological nature. Consequently, by exploiting and tuning their topological properties, optical metasurfaces have been demonstrated as an attractive platform for active photonics. However, given the fact that most active media under external excitations can only provide limited refractive index change, the potential advancements offered by the topological character of active metasurfaces have remained mostly unexplored. Zinc oxide (ZnO), which has recently exhibited optically-induced extraordinarily large permittivity modulations at visible and near-infrared frequencies, is an excellent active material for dynamic metasurfaces exhibiting strong tuning. This work demonstrates that a hybrid metasurface consisting of an array of ZnO nanodisks on a silver backplane displays broadly tunable topological properties. In particular, by performing k-space scattering simulations using measured pump-fluence-dependent material properties of ZnO, we study in detail the light reflection from the hybrid metasurface. Our results validate that the large k-space topology tuning of the metasurface can result in enormously strong polarization manipulation of near-infrared light in the vicinity of the topological features. The observed polarization switching effect is highly sensitive to the polarization and wavelength of an incident wave, owing to the symmetry and dispersion characteristics of the proposed system. Our study indicates that leveraging a combination of the extraordinary material properties and the k-space topology, hybrid metasurfaces based on ZnO may open new avenues for creating all-optical switchable metadevices.

36 MATERIALS SCIENCE↗

The BDX detector prototype for dark matter searches in a Beam Dump eXperiment at JLAB

The Beam Dump eXperiment (BDX) is an electron-beam thick-target experiment aimed to investigate the existence of light dark matter particles in the MeV-GeV mass range at Jefferson Lab. A small-scale prototype (BDX-Proto) of the BDX detector has been constructed in order to validate the proposed design and to demonstrate with real measurements the capability to efficiently reject the cosmogenic backgrounds. Here we report the peformance of BDX-Proto extracted from a long campaign of cosmic ray measurements performed at INFN, Sez. Catania and INFN, LNS.

calorimeters↗

Coherent Acoustic Interferometry during the Photodriven Oxygen Evolution Reaction Associates Strain Fields with the Reactive Oxygen Intermediate (Ti–OH*)

The oxygen evolution reaction (OER) from water requires the formation of metastable, reactive oxygen intermediates to enable oxygen–oxygen bond formation. Conversely, such reactive intermediates could also structurally modify the catalyst. Here, a descriptor for the overall catalytic activity, the first electron and proton transfer OER intermediate from water, (M–OH*), has been associated with significant distortions of the metal–oxygen bonds upon charge-trapping. Time-resolved spectroscopy of in situ, photodriven OER on transition metal oxide surfaces has characterized M–OH* for the charge trapping and the symmetry of the lattice distortions by optical and vibrational transitions, respectively, but had yet to detect an interfacial strain field arising from a surface coverage M–OH*. Here, we utilize picosecond, coherent acoustic interferometry to detect the uniaxial strain normal to the SrTiO 3 /aqueous interface directly caused by Ti–OH*. The spectral analysis applies a fairly general methodology for detecting a combination of the spatial extent, magnitude, and generation time of the interfacial strain through the coherent oscillations’ phase. For lightly n-doped SrTiO 3 , we identify the strain generation time (1.31 ps), which occurs simultaneously with Ti–OH* formation, and a tensile strain of 0.06% (upper limit 0.6%). In addition to fully characterizing this intermediate across visible, mid-infrared, and now GHz-THz probes on SrTiO 3 , we show that strain fields occur with the creation of some M–OH*, which modifies design strategies for tuning catalytic activity and provides insight into photo-induced degradation so prevalent for OER. To that end, the work put forth here provides a unique methodology to characterize intermediate-induced interfacial strain across OER catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Leveraging the redox activities of cerium and dibenzotetrathiafulvalene to discover a photo-responsive magnetic material

Stimuli-responsive changes in lanthanide-based materials are a promising research direction. In this study, [DBTTF] 4 [Ce 2 Cl 10 ] DBTTF = dibenzotetrathiafulvalene (1) was synthesized by a light-induced crystallization, where photo-oxidation of DBTTF enables formation of the cerium dimer [Ce 2 Cl 10 ] 4− . Intermolecular interactions between the stacked organic units of the crystal result in charge transfer bands in the visible-NIR (near-infrared) region, evident in the solid-state absorption spectrum upon comparison with the solution spectrum. The assignments of the sublattice oxidation states were made with single-crystal X-ray diffraction (SC-XRD) structural characterization, Raman spectroscopy, X-ray absorption spectroscopy, and magnetometry. Continuous 532 nm laser irradiation of the microcrystalline solid modulates the redox states in 1, leading to ∼40% reduction in the observed magnetization at 2 K. Density functional theory PBE+U/HSE06 band structure calculations predict Mott insulating behavior in 1, with a bandgap of 0.54/0.81 eV, and further support the conjecture that the observed photo-induced change in magnetization results from electron transfer from the [Ce 2 Cl 10 ] 4− anions to the π-stacked [DBTTF] 2 2+ organic dimer subunits. An enhancement in conductivity is similarly observed upon 532 nm irradiation, determined by single-crystal transport measurements. The findings reveal that photo-responsive lanthanide-based materials can be achieved by integration of redox-active organic moieties with redox-active lanthanide cations for the realization of switchable, photo-magnetic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multifrequency stimulated Raman scattering of light in a calcite single crystal

Using pulses of multifrequency stimulated Raman scattering (SRS) in calcite, nonlinear photoluminescence in a stilbene molecular crystal is excited. When multifrequency SRS is excited by the radiation of a Nd{sup 3+} : YAG laser with a wavelength of 1064 nm, eleven anti-Stokes components are observed in the visible spectrum with an average frequency shift of 1086 cm{sup −1} between them. Using the second harmonic of the Nd {sup 3+} : YAG laser radiation allowed three anti-Stokes and four Stokes components to be recorded. The large spectral range of the frequency comb facilitated effective reduction in the duration and increase in the intensity of the radiation pulse of multifrequency SRS. (nonlinear optical phenomena)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Homogeneous broadening in the spectrum of a broadband erbium-doped fibre light source

Interference of wave trains separated out in an inhomogeneous emission spectrum of a superluminescent erbium-doped fibre source has been studied by scanning the wavelength of a spectrum analyser. The results demonstrate that, as the spectral resolution of the spectrum analyser decreases to a level corresponding to a sharp drop in interference fringe visibility relative to its original level, near 100 %, fringe visibility becomes dependent on the wavelength in the inhomogeneous spectrum of the source. The reason for this is that, at some characteristic resolution δλ (δλ > 0.5 nm in our case), the coherence time of wave trains is not limited by the spectral resolution of the spectrum analyser and is related to the inhomogeneous spectrum of the source, whose limiting width can be thought of as the homogeneous linewidth in the spectrum of the source. This feature can be used for evaluating homogeneous line broadening. (paper)

74 ATOMIC AND MOLECULAR PHYSICS↗

Light new physics in XENON1T

We examine the recently-reported low-energy electron recoil spectrum observed at the XENON1T underground dark matter direct detection experiment, in the context of new interactions with solar neutrinos. In particular we show that scalar and vector mediators with masses $\lesssim 50$ keV coupled to leptons could already leave a visible signature in the XENON1T experiment, similar to the observed peak below 7 keV. This signals that dark matter detectors are already competing with neutrino scattering experiments such as GEMMA, CHARM-II and Borexino. If these results from XENON1T are interpreted as a new signal of such physics, the parameters which fit the excess face challenges from astrophysics which seem very difficult to overcome. If they are rather viewed as a constraint on new couplings, they herald the start of an era of novel precise probes of physics beyond the standard model with dark matter detectors.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Stau pairs from natural SUSY at high luminosity LHC

Natural supersymmetry (SUSY) with light Higgsinos is perhaps the most plausible of all weak scale SUSY models while a variety of motivations point to (right) tau sleptons as the lightest of all the sleptons. We examine a SUSY model line with rather light right staus embedded within natural SUSY. For light τ ˜ 1 of a few hundred GeV, the decays τ ˜ 1 → τ χ ˜ 1 , 2 0 and ν τ χ ˜ 1 − occur at comparable rates where the (Higgsino-like) χ ˜ 1 ± and χ ˜ 2 0 release only small visible energy: in this case, the expected τ + τ − + E T signature is diminished from the usual expectations due to the presence of the nearly invisible decay mode τ ˜ 1 → ν τ χ ˜ 1 − . However, once m τ ˜ 1 ≳ m ( b i n o ) , decays to binos such as τ ˜ 1 → τ χ ˜ 3 0 open up where χ ˜ 3 0 decays to Higgsinos plus W ± , Z 0 , and h at comparable rates. For these heavier staus, the stau pair production gives rise to diboson + E T events, which may contain 0, 1, or 2 additional hard τ leptons. From these considerations, we examine the potential for future discovery of tau-slepton pair production at a high-luminosity LHC. While we do not find a 5 σ HL-LHC discovery reach for 3000 fb − 1 , we do find a 95% CL exclusion reach, ranging between m τ ˜ 1 : 100 – 450 GeV for m χ ˜ 1 0 ∼ 100 GeV . This latter reach disappears for m χ ˜ 1 0 ≳ 200 GeV . Published by the American Physical Society 2024

Astronomy & Astrophysics↗

Increased range and contrast in fog with circularly polarized imaging

Fogs, low lying clouds, and other highly scattering environments pose a challenge for many commercial and national security sensing systems. Current autonomous systems rely on optical sensors for navigation whose performance is degraded by highly scattering environments. In our previous simulation work, we have shown that polarized light can penetrate through a scattering environment such as fog. We have demonstrated that circularly polarized light maintains its initial polarization state better than linearly polarized light, even through large numbers of scattering events and thus ranges. This has recently been experimentally verified by other researchers. In this work, we present the design, construction, and testing of active polarization imagers at short-wave infrared and visible wavelengths. We explore multiple polarimetric configurations for the imagers, focusing on linear and circular polarization states. The polarized imagers were tested at the Sandia National Laboratories Fog Chamber under realistic fog conditions. Here, we show that active circular polarization imagers can increase range and contrast in fog better than linear polarization imagers. We show that when imaging typical road sign and safety retro-reflective films, circularly polarized imaging has enhanced contrast throughout most fog densities/ranges compared to linearly polarized imaging and can penetrate over 15 to 25 m into the fog beyond the range limit of linearly polarized imaging, with a strong dependence on the interaction of the polarization state with the target materials.

47 OTHER INSTRUMENTATION↗

Integrated freeform optical couplers

Reflecting light beams off of microscale three-dimensional (3D) freeform surfaces can yield highly efficient coupling into and out of optical waveguides, optical fibers, and photonic chips. The structure of the 3D freeform reflective surface determines the shape of the reflected beam. This allows freeform reflectors to control the mode profile, rotation angle, and divergence angle of light beams. Control of beam shape enables mode matching between source output mode and target input mode, which results in low-loss optical coupling. An inventive freeform reflective surface can direct light beams in plane or out of plane via specular reflection or total internal reflection. A photonic integrated circuit with this type of freeform optical coupler can operate with a bandwidth range of at least 400 nm, potentially encompassing all visible or telecommunications wavelengths, and can be volume manufactured in photonic chips.

Yu, Shaoliang↗

Elucidating the speciation of extracted lanthanides by diglycolamides

Many studies over the past few decades have been devoted to addressing the application of diglycolamides (DGAs) for hydrometallurgical-based, f-element separations. Work to date has shown the molecular structure of a DGA derivative can have a significant impact on intra-lanthanide partitioning patterns. More recent studies have pushed towards probing the structure function relationship of the lanthanide-DGA complex to enable the design of more efficient lanthanide separation systems. Spectroscopic techniques, such as UV–Visible, Fourier Transformed Infrared Spectroscopy (FT-IR), Nuclear Magnetic Resonance (NMR), and Extended X-ray Absorption Fine Structure (EXAFS), provide information regarding the inner-sphere coordination of a given lanthanide-DGA complex. Scattering techniques, such as Dynamic Light Scattering (DLS), Small-Angle X-ray Scattering (SAXS), and Small-Angle Neutron Scattering (SANS), address nanoscale structures including aggregate sizes and morphology. Here, this review assesses the current state-of-knowledge regarding lanthanide-DGA hydrometallurgical (i.e., solvent extraction systems) interrogated using spectroscopic and scattering techniques to characterize the extracted Ln 3+ DGA species. Of particular interest to this review is the impact of varied diluents, inclusion and variation of phase modifiers, and DGA derivatization on system characteristics. While there has been extensive literature on the application of DGAs for f-element separations, the literature lacks a collective assessment of the speciation of Ln 3+ in the organic phase. This review provides new insights into the field of DGA separations, explicitly with an application to intra-lanthanide separations. Specifically, this review illustrates the importance of both the co-extraction anion (Cl - , NO 3 - , or ClO 4 - ) as it pertains to both the aggregate size and Ln 3+ distribution coefficient. It is evident the ability of the anion to disrupt the hydrogen bonding network limits both aggregate size and distribution coefficients according to the Hoffmeister series. This suggests the importance of the large, softer anions with a low charge-to-surface area ratio on encouraging hydrogen bond interactions. In addition, the co-extracted cation (H + vs Na + ) is important for mitigating transfer of Ln 3+ from the aqueous to the organic phase through extensive hydrogen bonding networks. These networks are responsible for forming supramolecular aggregates where a change in morphology is observed with increasing concentrations of H + and/or Ln 3+ in the organic phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗