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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 451 records · Page 25

Speciation mapping of the oxidation layer on aged uranium dioxide using scanning transmission x-ray spectromicroscopy

In this study, UO 2 was aged in humid air and prepared as a thin section using a focused ion beam (FIB) instrument. The specimen was measured using synchrotron radiation spectromicroscopy techniques at the Beamline 11.0.2 STXM end station of the Advanced Light Source (ALS). Non-negative matrix factorization (NMF) methods were used to identify and map three component x-ray absorption near-edge structure (XANES) spectra in the oxygen K-edge data, revealing a surface layer of U 4 O 9 with a thickness of 206 ± 21 nm, and the bulk of the sample remaining as UO 2 . Uranium N 4,5 -edge XANES spectromicroscopy supports these results. The diffusion-controlled parabolic rate constant for UO 2 oxidation to U 4 O 9 was calculated from the observed layer thickness and compared to literature values. Complementary transmission electron microscopy (TEM) was used to image the sample and identify the phases present in various regions, confirming the STXM results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

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+↗

Metalens formed by structured arrays of atomic emitters

Abstract Arrays of atomic emitters have proven to be a promising platform to manipulate and engineer optical properties, due to their efficient cooperative response to near‐resonant light. Here, we theoretically investigate their use as an efficient metalens. We show that, by spatially tailoring the (subwavelength) lattice constants of three consecutive two‐dimensional arrays of identical atomic emitters, one can realize a large transmission coefficient with arbitrary position‐dependent phase shift, whose robustness against losses is enhanced by the collective response. To characterize the efficiency of this atomic metalens, we perform large‐scale numerical simulations involving a substantial number of atoms (N∼ 5 × 10 5 ) that is considerably larger than comparable works. Our results suggest that low‐loss, robust optical devices with complex functionalities, ranging from metasurfaces to computer‐generated holograms, could be potentially assembled from properly engineered arrays of atomic emitters.

Materials Science↗

The Influence of Structural Dynamics in Two-Dimensional Hybrid Organic–Inorganic Perovskites on Their Photoluminescence Efficiency — Neutron Scattering Analysis

Two-dimensional hybrid organic–inorganic perovskites (HOIPs) have emerged as promising materials for light-emitting diode applications. In this study, by using time-of-flight neutron spectroscopy we identified and quantitatively separated the lattice vibrational and molecular rotational dynamics of two perovskites, butylammonium lead iodide (BA)2PbI4 and phenethyl-ammonium lead iodide (PEA) 2 PbI 4 . By examining the corresponding temperature dependence, we found that the lattice vibrations, as evidenced by neutron spectra, are consistent with the lattice dynamics obtained from Raman scattering. We revealed that the rotational dynamics of organic molecules in these materials tend to suppress their photoluminescence quantum yield (PLQY) while the vibrational dynamics did not show predominant correlations with the same. Additionally, we observed photoluminescence emission peak splitting for both systems, which becomes prominent above certain critical temperatures where the suppression of PLQY begins. This study suggests that the rotational motions of polarized molecules may lead to a reduction in exciton binding energy or the breaking of degeneracy in exciton binding energy levels, enhancing non-radiative recombination rates, and consequently reducing photoluminescence yield. These findings offer a deeper understanding of fundamental interactions in 2D HOIPs and could guide the design of more efficient light-emitting materials for advanced technological applications.

Rajeev, Haritha Sindhu [Univ. of Virginia, Charlot↗

Tracking the dynamics of catalytic Pt/CeO2 active sites during water-gas-shift reaction

Abstract Understanding the atomistic structure of the active site during catalytic reactions is of paramount importance in both fundamental studies and practical applications, but such studies are challenging due to the complexity of heterogeneous systems. Here, we use Pt/CeO 2 as an example to study the dynamic nature of active sites during the water-gas-shift reaction (WGSR) by combining multiple in situ characterization tools. We show that the different concentrations of interfacial Pt δ+ – O – Ce 4+ moieties at Pt/CeO 2 interfaces are responsible for the rank of catalytic performance of Pt/CeO 2 catalysts: Pt/CeO 2 -rod > Pt/CeO 2 -cube > Pt/CeO 2 -oct. For all the catalysts, metallic Pt is formed during the WGSR, leading to the transformation of the active sites to Pt 0 – O v – Ce 3+ and interface reconstruction. These findings shed light on the nature of the active site for the WGSR on Pt/CeO 2 and highlight the importance of combining complementary in situ techniques for establishing structure-performance relationships.

36 MATERIALS SCIENCE↗

Lifting Triplet Degeneracy Through Organic‐Cation Driven Structural Perturbation to Modulate Luminescence of Sb 3+ ‐Doped Double Perovskite

The spin-orbit coupling (SOC) and the Jahn-Teller effect (JTE) alter the orbital degeneracy in materials, leading to unique optical, electronic, and magnetic properties essential in spintronics, quantum computing, and light-emitting diodes (LEDs). Here, the study employs luminescent p-xylylenediammonium (PXA) instead of Cs+ in Cs2NaInCl6 to yield 2D Sb3+-doped (PXA)2NaInCl8 double perovskite and demonstrates a non-degenerate triplet state resulting from enhanced JTE in the strong SOC regime, featuring distinct emission centers. Consequently, a broadband emission from both PXA and [SbCl6]3− spans the entire spectrum (350–750 nm), representing a rare single-source multi-emissive 2D perovskite. With in-depth comparative structural, temperature-dependent photo-physical, and theoretical studies, it is elucidated that the synergistic effect of SOC and JTE on the Eg and T2g lattice modes modulate the electronic structure of [SbCl6]3− by splitting the doubly degenerate E levels of 3 T$^{*}_{1u}$ into non-degenerate states. The physical model, supported by theoretical studies, explains the energy level splitting required to realize two kinds of radiative minima in the relaxed excited state.

36 MATERIALS SCIENCE↗

The Optical Corrector for the Dark Energy Spectroscopic Instrument

The Dark Energy Spectroscopic Instrument (DESI) is currently measuring the spectra of 40 million galaxies and quasars, the largest such survey ever made to probe the nature of cosmological dark energy. The 4 m Mayall telescope at Kitt Peak National Observatory has been adapted for DESI, including the construction of a 3$_{.}^{°}$2 diameter prime focus corrector that focuses astronomical light onto a 0.8 m diameter focal surface with excellent image quality over the DESI bandpass of 360–980 nm. The wide-field corrector includes six lenses, as large as 1.1 m in diameter and as heavy as 237 kilograms, including two counterrotating wedged lenses that correct for atmospheric dispersion over zenith angles from 0° to 60°. The lenses, cells, and barrel assembly all meet precise alignment tolerances on the order of tens of microns. The barrel alignment is maintained throughout a range of observing angles and temperature excursions in the Mayall dome by use of a hexapod, which is itself supported by a new cage, ring, and truss structure. In this paper we describe the design, fabrication, and performance of the new corrector and associated structure, focusing on how they meet DESI requirements. In particular, we describe the prescription and specifications of the lenses, design choices and error budgeting of the barrel assembly, stray light mitigations, and integration and test at the Mayall telescope. We conclude with some validation highlights that demonstrate the successful corrector on-sky performance, and we list some lessons learned during the multiyear fabrication phase.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Exciton Dynamics in Layered Halide Perovskite Light‐Emitting Diodes

Abstract Layered halide perovskites have garnered significant interest due to their exceptional optoelectronic properties and great promises in light‐emitting applications. Achieving high‐performance perovskite light‐emitting diodes (PeLEDs) requires a deep understanding of exciton dynamics in these materials. This review begins with a fundamental overview of the structural and photophysical properties of layered halide perovskites, then delves into the importance of dimensionality control and cascade energy transfer in quasi‐2D PeLEDs. In the second half of the review, more complex exciton dynamics, such as multiexciton processes and triplet exciton dynamics, from the perspective of LEDs are explored. Through this comprehensive review, an in‐depth understanding of the critical aspects of exciton dynamics in layered halide perovskites and their impacts on future research and technological advancements for layered halide PeLEDs is provided.

Baek, Sung‐Doo↗

Application of Amber Suppression To Study the Role of Tyr M210 in Electron Transfer in Rhodobacter sphaeroides Photosynthetic Reaction Centers

The initial light-induced electron transfer (ET) steps in the bacterial photosynthetic reaction center (RC) have been extensively studied and provide a paradigm for connecting structure and function. Although RCs have local pseudo-C 2 symmetry, ET only occurs along the A branch of chromophores. Tyrosine M210 is a key symmetry-breaking residue adjacent to bacteriochlorophyll B A that bridges primary electron donor P and bacteriopheophytin acceptor H A . Here, we used amber suppression to incorporate phenylalanine variants with different electron-withdrawing/donating capabilities at position M210. X-ray data generally reveal no appreciable structural changes due to the mutations. P* decay and P + H A - formation are multi-exponential (~2-9, ~10-60, and ~100-300 ps) and temperature dependent. The 1020 nm transient-absorption band of P + B A - is barely resolved for a few variants at 295 K and for none at 77 K. The results indicate a change from two-step ET for wild-type RCs to dominance of one-step superexchange ET for the mutants. Resonance Stark spectroscopy reveals that the free energy of P + B A - changes by -57 to +66 meV among the phenylalanine variants. Because P+BA apparently lies above P* in all phenylalanine variants, the perturbations primarily affect the energy denominator for superexchange mixing. The findings deepen insight into primary ET in the bacterial RC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dual-Wavelength Simultaneous Patterning of Degradable Thermoset Supports for One-Pot Embedded 3D Printing

Vat photopolymerization (VP) techniques have enabled the fabrication of complex geometries while balancing high precision and fast processing times. 3D printed objects are traditionally built layer-by-layer with newly cured layers being structurally supported by previous ones. Fabricating unsupported features such as overhangs and arches risks misalignment and sagging, limiting the range of accessible designs. To overcome this issue, support structures are fabricated along with the primary object as temporary scaffolds that provide stability and conserve print fidelity. For VP specifically, patterning dissolvable sacrificial supports is attractive to avoid manual removal after printing. In this study, we demonstrate a base-degradable thermoset to pattern print supports in a one-pot formulation along with the primary structural material. Efficient printing is enabled using a dual-wavelength negative imaging (DWNI) DLP printer that patterns the degradable thermoset with visible light and the permanent network with UV light, which are simultaneously projected using a single digital micromirror device (DMD). Printed objects undergo thermal postprocessing to enhance the final conversion of the primary material, after which thermoset supports are degraded in a basic, aqueous solution. This approach provides a robust method for the dual-wavelength patterning of sacrificial thermoset supports, broadening the range of accessible 3D printable materials and geometries.

3D printing↗

Photophysics and Carrier Dynamics of Lasing in Quasi-2D Lead Halide Perovskites

Quasi-2D perovskites have recently been extensively studied due to their narrow-bandwidth-tunable emission, solution processability, and applicability as optical gain media. Quasi-2D perovskites are composed of inorganic perovskite crystal layers encapsulated with a bulky organic ligand such as phenylethylammonium, endowing the perovskite with a quantum-well structure and improved stability. In this article, we explore the photophysics of a quasi-2D metal halide perovskite as a promising light-harvesting and emitting medium. We find it exhibits high optical absorption (~10 5 cm -1 ) and an optically pumped amplified spontaneous emission threshold at 623 μJ/cm 2 . We study charge transfer processes in the complex mixed quantum wells of these perovskites through transient absorption and time-resolved photoluminescence measurements and develop a phenomenological model that incorporates optical gain for lasing. Further, while both free carriers and excitons are observed, we show surprisingly that photoluminescence is dominated by excitons despite the relatively small binding energy (~16 meV) of the low-energy band edge. Additionally, we extract the rates of exciton relaxation pathways, revealing a relatively large radiative term of 4.6 x 10 8 s -1 as well as an exciton-exciton annihilation term of 3.6 x 10 -13 cm 3 s -1 that is 3 orders of magnitude smaller than in similar quasi-2D perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transverse Spin and Momentum Structure of Hadrons in QCD (Final Technical Report)

This final technical report summarizes the work on the award DE-FG02-07ER41460, Transverse Spin and Momentum Structure of Hadrons in QCD. During the performance period, we addressed fundamental questions in nuclear physics, focusing on how hadrons—and, by extension, light nuclei—emerge from quark and gluon interactions within Quantum Chromodynamics (QCD).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ultra-light antennas via charge programmed deposition additive manufacturing

Abstract The demand for lightweight antennas in 5 G/6 G communication, wearables, and aerospace applications is rapidly growing. However, standard manufacturing techniques are limited in structural complexity and easy integration of multiple material classes. Here we introduce charge programmed multi-material additive manufacturing platform, offering unparalleled flexibility in antenna design and the capability for rapid printing of intricate antenna structures that are unprecedented or necessitate a series of fabrication routes. Demonstrating its potential, we present a transmitarray antenna composed of an interconnected, multi-layered array of dielectric/conductive S-ring unit cells, reducing 94% mass of conventional antenna configurations. A fully printed circular polarized transmitarray system fed by a source and a Risley prism antenna system operating at 19 GHz both show close alignment between testing results and numerical simulations. This printing method establishes a universal platform, propelling discovery of new antenna designs and enabling data-driven design and optimizations where rapid production of antenna designs is crucial.

Science & Technology - Other Topics↗

Capturing Coupled Structural and Electronic Motions During Excited-State Intramolecular Proton Transfer via Computational Multiedge Resonant Inelastic X-ray Scattering

Proton-transfer processes build the foundation of many chemical processes. In Excited State Intramolecular Proton Transfer (ESIPT) processes the proton transfer process is impulsively started through light. Here, in this study, we explore the changes in coupled atomic and electronic motions during and following ESIPT through computational time-resolved Resonant Inelastic X-ray Scattering (trRIXS). Excited-state Ab Initio Molecular Dynamics (AIMD) simulations combined with Time-Dependent Density Functional Theory (TDDFT) calculations were performed for 10-hydroxybenzo[h]quinoline to obtain trRIXS signatures. RIXS at both the nitrogen and oxygen K-edges were computed to resolve the dynamics electronic structure from both the proton donor and acceptor perspective. The results show how RIXS can reveal the local electronic structure, the coupling between different electronic states and how electronic structure and coupling change during the proton transfer process. Additionally, we observe a strong correlation between spectral changes and structural changes during ESIPT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum Light Imaging of the Plant Root─Rhizobacteria─System Using iLOV Fluorescence

It has been demonstrated recently that the use of specific quantum states of light for two-photon microscopy can lead to a substantial reduction of the intensity of light needed for the imaging of biological objects. This opens new ways to better understand the delicate mechanisms of the interactions of living organisms in the rhizosphere on an extended time scale without optical damage or alteration of their native behavior. Herein, we report a successful realization of entangled two-photon excited fluorescence microscopy of wheat plant roots and a set of biological samples, including purified iLOV protein, bacterial cells expressing iLOV, and combination of these under an extremely low excitation intensity. The entangled two-photon coupling strength of iLOV was modeled using electronic structure calculations which demonstrated that the FMN chromophore in the iLOV protein has an entangled two-photon absorption (ETPA) cross section that is large enough for imaging using weak quantum light for fluorescence excitation. Successful imaging of plant-associated Pantoea sp. YR343 cells expressing iLOV validates the feasibility of using iLOV as a molecular label for characterizing plant-microbe interactions based on entangled photon imaging. In conclusion, the results demonstrate the advantageous use of entangled photon imaging under noninvasive and nondestructive conditions.

Varnavksi, Oleg [Univ. of Michigan, Ann Arbor, MI ↗

Field-induced spin polarization in the lightly Cr-substituted layered antiferromagnet NiP S 3

Tuning magnetic properties in layered magnets is an important route to realize novel phenomenon related to two-dimensional (2D) magnetism. Recently, tuning antiferromagnetic (AFM) properties through substitution and intercalation techniques has been widely studied in MPX 3 compounds. Interesting phenomena, such as diverse AFM structures and even the signatures of ferrimagnetism, have been reported. However, long-range ferromagnetic (FM) ordering has remained elusive. Here, in this work, we explored the magnetic properties of the Cr-substituted NiP S 3 . We found that Cr substitution is extremely efficient in controlling spin orientation in NiP S 3 . Our study reveals a field-induced spin polarization in lightly (9%) Cr-substituted NiP S 3 , which is likely attributed to the attenuation of AFM interactions and magnetic anisotropy due to Cr doping. Our work provides a possible strategy to achieve FM phase in AFM MPX 3 , which could be useful for investigating 2D magnetism as well as potential device applications.

2-dimensional systems↗

Three-dimensional dispersion in the type-II Dirac semimetals PtTe 2 and PdTe 2 revealed through circular dichroism in angle-resolved photoemission spectroscopy

PtTe 2 and PdTe 2 are among the first transition metal dichalcogenides that were predicted to host type-II Dirac fermions, exotic particles prohibited in free space. These materials are layered and air stable, which makes them top candidates for technological applications that take advantage of their anisotropic magnetotransport properties. Here, in this work, we provide a detailed characterization of the electronic structure of PtTe 2 and PdTe 2 using angle-resolved photoemission spectroscopy (ARPES) and density functional theory calculations, offering an alternative interpretation for one of the Dirac-like dispersions in these materials. Through the use of circularly polarized light, we report a different behavior of such dispersion in PdTe 2 compared to PtTe 2 , that we relate to a symmetry analysis of the dipole matrix element. Such analysis reveals a link between the observed circular dichroism and the different momentum-dependent terms in the dispersion of these two compounds, despite their close similarity in crystal structure. Additionally, our data show a clear difference in the circular dichroic signal for the type-II Dirac cones characteristic of these materials, compared to their topologically protected surface states. Our paper provides a useful reference for the ARPES characterization of other transition metal dichalcogenides with topological properties and illustrates the use of circular dichroism as a guide to identify the topological character and attributes of two otherwise equivalent band dispersions.

angle-resolved photoemission spectroscopy↗

Steric and Electronic Influence of Excited-State Decay in Cu(I) MLCT Chromophores

For the past eleven years, a dedicated effort in our research group focused on fundamentally advancing the photophysical properties of cuprous bis-phenanthroline-based metal-to-ligand charge transfer (MLCT) excited states. We rationalized that by gaining control over the numerous factors limiting the more widespread use of Cu I MLCT photosensitizers, they would be readily adopted in numerous light-activated applications given the earth-abundance of copper and the extensive library of 1,10-phenanthrolines developed over the last century. Significant progress has been achieved by recognizing valuable structure-property concepts developed by other researchers in tandem with detailed ultrafast and conventional time-scale investigations, in-silico-inspired molecular designs to predict spectroscopic properties, and applying novel synthetic methodologies. Ultimately, we achieved a plateau in exerting cooperative steric influence to control Cu I MLCT excited state decay. This led to combining sterics with π-conjugation and/or inductive electronic effects to further exert control over molecular photophysical properties. The lessons gleaned from our studies of homoleptic complexes were recently extended to heteroleptic bis(phenanthrolines) featuring enhanced visible light absorption properties and long-lived room-temperature photoluminescence. Furthermore, this Account navigates the reader through our intellectual journey of decision-making, molecular and experimental design, and data interpretation in parallel with appropriate background information related to the quantitative characterization of molecular photophysics using Cu I MLCT chromophores as prototypical examples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗