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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 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Ion-Pair Reorganization Regulates Reactivity in Photoredox Catalysts

Cyclometalated and polypyridyl complexes of d6 metals are promising photoredox catalysts, using light to drive reactions with high kinetic or thermodynamic barriers via the generation of reactive radical intermediates. However, while tuning of their redox potentials, absorption energy, excited-state lifetime and quantum yield are well-known criteria for modifying activity, other factors could be important. Here we show that dynamic ion-pair reorganization controls the reactivity of a photoredox catalyst, [Ir[dF(CF3)ppy]2(dtbpy)]X. Time-resolved dielectric-loss experiments show how counter-ion identity influences excited-state charge distribution, evincing large differences in both the ground- and excited-state dipole moment depending on whether X is a small associating anion (PF6-) that forms a contact-ion pair versus a large one that either dissociates or forms a solvent-separated pair (BArF4-). These differences correlate with the reactivity of the photocatalyst toward both reductive and oxidative electron transfer, amounting to a 4-fold change in selectivity toward oxidation versus reduction. These results suggest that ion pairing could be an underappreciated factor that modulates reactivity in ionic photoredox catalysts.

catalysis↗
DOE OSTI2024

Modeling aerosol transmission spectra from n(λ) and k(λ) infrared optical constants measurements of organic liquids and solids

The effects of light scattering and refraction play significantly different roles for aerosols than for bulk materials, making it challenging to identify aerosolized chemicals using traditional spectral methods or spectral reference libraries. Due to a potentially infinite number of particle morphologies, sizes, and compositions, constructing a database of laboratory-measured aerosol spectra is not a practical solution. Here, as an alternative approach, the measured n / k optical vectors of two example organic materials (diethyl phthalate and D-mannitol) are used in combination with particle absorption / scattering theory (Mie theory and FDTD) and the Beer-Lambert law to generate a series of synthetic infrared transmission / scattered light spectra. The synthetic spectra show significant differences versus simple slab transmission spectra, even for small changes in particle size (e.g., 5 vs. 10 µm) for both single particles and ensembles, potentially serving as useful reference data for aerosol sensing. For spherical single particles with diameters of 1 to 10 µm, FDTD simulations predict changes in the magnitudes of spectral shifts and the shapes of the peaks vs. particle size with only small deviations from Mie theory predictions, yet reliably capture the direction of the shifts. Typical spectral peak shifts in the longwave infrared correspond to Δλ ∼0.20 µm (∼34 cm -1 ) when compared to corresponding slab transmission spectra. Additionally, synthetic spectra generated from the n / k values derived using two different methods (KBr pellet transmission and single-angle reflectance) are compared using the Mie theory model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Manipulating Organic Semiconductor Morphology with Visible Light

A method is presented to manipulate the final morphology of roll-to-roll slot-die coated poly(3-hexylthiophene) (P3HT) by optically exciting the p-type polymer in solution while coating. These results provide a comprehensive picture of the entire knowledge chain, from demonstrating how to apply the authors’ method to a fundamental understanding of the changes in morphology and physical properties induced by exciting P3HT while coating. By combining results from density functional theory and molecular dynamics simulations with a variety of X-ray experiments, absorption spectroscopy, and THz spectroscopy, the relationship between morphology and physical properties of the thin film is demonstrated. Specifically, in P3HT films excited with light during deposition, changes in crystallinity and texture with more face-on orientation and increased out-of-plane charge mobility are observed.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Time-resolving state-specific molecular dissociation with XUV broadband absorption spectroscopy

The electronic and nuclear dynamics inside molecules are essential for chemical reactions, where different pathways typically unfold on ultrafast timescales. Extreme ultraviolet (XUV) light pulses generated by free-electron lasers (FELs) allow atomic-site and electronic-state selectivity, triggering specific molecular dynamics while providing femtosecond resolution. Yet, time-resolved experiments are either blind to neutral fragments or limited by the spectral bandwidth of FEL pulses. Here, we combine a broadband XUV probe pulse from high-order harmonic generation with an FEL pump pulse to observe dissociation pathways leading to fragments in different quantum states. We temporally resolve the dissociation of a specific O 2 + state into two competing channels by measuring the resonances of ionic and neutral fragments. This scheme can be applied to investigate convoluted dynamics in larger molecules relevant to diverse science fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Evidence of excited-state lifetime enhancement in dimyristoyl-phosphocholine nanodiscs by ultraviolet absorption spectroscopy

Ultraviolet absorption spectroscopy is an analytical tool that is commonly utilized to determine protein concentrations, primarily due to characteristic absorption of tryptophan and tyrosine at 280 nm. Accurate concentration determination is essential to the accuracy of many biophysical techniques, and ultraviolet absorption provides a convenient and rapid method to assess protein concentration. However, the widespread usage of this method assumes that ultraviolet absorption is the same for individual amino acids in aqueous solution (where the molar extinction coefficient was measured) as for the amino acid in the conformational environment of the protein of interest. We demonstrate that additional considerations may be necessary for the membrane scaffold protein in dimyristoyl-phosphocholine nanodiscs through ultraviolet absorption spectroscopy of nanodiscs, liposomes, the membrane scaffold protein, and a mixture of liposomes and the non-nanodisc-associated protein. The aromatic amino acids of the membrane scaffold protein absorb significantly less light at 280 nm when associated with lipids in a lipoprotein assembly, which we plausibly attribute to an enhancement of chromophore excited-state lifetimes due to reduced intramolecular motion in the nanodisc. We caution that using the molar absorptivity of the membrane scaffold protein alone to determine nanodisc concentrations may not yield accurate results. Instead, the molar absorptivity of each nanodisc formulation should be explored independently to account for the unique conformational environment of each nanodisc.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Long-range cooperative resonances in rare-earth ion arrays inside photonic resonators

Engineering arrays of active optical centers to control the interaction Hamiltonian between light and matter has been the subject of intense research recently. Collective interaction of atomic arrays with optical photons can give rise to directionally enhanced absorption or emission, which enables engineering of broadband and strong atom-photon interfaces. Here, we report on the observation of long-range cooperative resonances in an array of rare-earth ions controllably implanted into a solid-state lithium niobate micro-ring resonator. We show that cooperative effects can be observed in an ordered ion array extended far beyond the light’s wavelength. We observe enhanced emission from both cavity-induced Purcell enhancement and array-induced collective resonances at cryogenic temperatures. Engineering collective resonances as a paradigm for enhanced light-matter interactions can enable suppression of free-space spontaneous emission. The multi-functionality of lithium niobate hosting rare-earth ions can open possibilities of quantum photonic device engineering for scalable and multiplexed quantum networks.

42 ENGINEERING↗
DOE OSTI2025

Shifting the MLCT of d 6 metal complexes to the red and NIR

Light-active d 6 -coordination compounds hold great promise for light energy conversion, sensors and therapeutic applications. However, the activity in the red-to-NIR spectral region is highly desirable to convert solar light more efficiently, use low-cost red-light sources and activate these chromophores in biological tissue environment. Due to their versatility, tunability and broad intense absorption, d 6 -coordination compounds with metalto-ligand charge transfer (MLCT) transitions are especially interesting. This review article offers a comprehensive collection of strategies to tune MLCT excited states in d 6 metal complexes and gives insights on group 6 to group 9 transition metals and their respective state-of-the-art MLCT engineering towards red-shifted absorption and emission properties with long-lived excited states. Strategies comprise lowering the π* level of the ligands, destabilizing and mixing of the metal-based HOMO, switching within a group of transition metals, matrix effects and insights into dealing with excited state deactivation in the context of the energy gap law.

Metal to ligand charge transfer (MLCT)↗
DOE OSTI2022

Shape memory in self-adapting colloidal crystals

We report reconfigurable, mechanically responsive crystalline materials are central components in many sensing, soft robotic, and energy conversion and storage devices1,2,3,4. Crystalline materials can readily deform under various stimuli and the extent of recoverable deformation is highly dependent upon bond type1,2,5,6,7,8,9,10. Indeed, for structures held together via simple electrostatic interactions, minimal deformations are tolerated. By contrast, structures held together by molecular bonds can, in principle, sustain much larger deformations and more easily recover their original configurations. In this report we study the deformation properties of well-faceted colloidal crystals engineered with DNA. These crystals are large in size (greater than 100 µm) and have a body-centred cubic (bcc) structure with a high viscoelastic volume fraction (of more than 97%). Therefore, they can be compressed into irregular shapes with wrinkles and creases, and, notably, these deformed crystals, upon rehydration, assume their initial well-formed crystalline morphology and internal nanoscale order within seconds. For most crystals, such compression and deformation would lead to permanent, irreversible damage. The substantial structural changes to the colloidal crystals are accompanied by notable and reversible optical property changes. For example, whereas the original and structurally recovered crystals exhibit near-perfect (over 98%) broadband absorption in the ultraviolet–visible region, the deformed crystals exhibit significantly increased reflection (up to 50% of incident light at certain wavelengths), mainly because of increases in their refractive index and inhomogeneity.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Advances in the photon avalanche luminescence of inorganic lanthanide-doped nanomaterials

Photon avalanche (PA)—where the absorption of a single photon initiates a ‘chain reaction’ of additional absorption and energy transfer events within a material—is a highly nonlinear optical process that results in upconverted light emission with an exceptionally steep dependence on the illumination intensity. Over 40 years following the first demonstration of photon avalanche emission in lanthanide-doped bulk crystals, PA emission has been achieved in nanometer-scale colloidal particles. The scaling of PA to nanomaterials has resulted in significant and rapid advances, such as luminescence imaging beyond the diffraction limit of light, optical thermometry and force sensing with (sub)micron spatial resolution, and all-optical data storage and processing. In this review, we discuss the fundamental principles underpinning PA and survey the studies leading to the development of nanoscale PA. Finally, we offer a perspective on how this knowledge can be used for the development of next-generation PA nanomaterials optimized for a broad range of applications, including mid-IR imaging, luminescence thermometry, (bio)sensing, optical data processing and nanophotonics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Nonlinear fluorescence spectroscopy of layered perovskite quantum wells

Interest in layered organohalide perovskites is motivated by their potential for use in optoelectronic devices. In these systems, the smallest and largest quantum wells are primarily concentrated near the glass and air interfaces of a film, thereby establishing a gradient in the average values of the bandgaps. It has been suggested that this layered architecture promotes the funneling of electronic excitations through space in a manner similar to light-harvesting processes in photosynthetic antennae. Whereas energy and charge transfer are difficult to distinguish by conventional transient absorption techniques, it has recently been shown that these competing relaxation mechanisms may be separately targeted with nonlinear fluorescence (NLFL) and photocurrent “action spectroscopies.” Here, we present perturbative rate functions to describe NLFL experiments conducted on layered perovskite systems. The formulas reproduce the patterns of resonances observed in experimental measurements and show how signatures of energy transfer manifest in two-dimensional spectra. Overall, this work suggests that NLFL spectroscopy may be used to fully reveal the trajectories of electronic excitations by correlating ultrafast energy transfer pathways to fluorescence emission from the thickest quantum wells.

Ouyang, Zhenyu↗
DOE OSTI2023

Faraday effect in collisional magnetized plasmas

Faraday rotation is a valuable diagnostic tool for investigating laboratory and astrophysical plasmas, but it has almost exclusively been treated in the collisionless limit (despite the non-negligible role of Coulomb collisions in many laboratory plasmas). Here, we show that Faraday rotation can occur in collisional plasmas and that the usual effect is curiously altered by collisions. Namely, an initially linearly polarized light wave—propagating parallel to a uniform magnetic field—becomes elliptically polarized in the collisional plasma, and collisional absorption of the wave also occurs. Moreover, the ellipticity and rotation angle are quantifiably sensitive to the fidelity of the collisional transport coefficients. As we will demonstrate with particle-in-cell EPOCH simulations, these effects offer a stringent diagnostic tool for benchmarking multi-scale plasma simulation codes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Application of machine learning approaches in the analysis of mass absorption cross-section of black carbon aerosols: Aerosol composition dependencies and sensitivity analyses

Physics-based models typically require an in-depth understanding of a phenomenon and assumptions of the underlying process(es), which are often hard to obtain in practice, whereas data-driven machine learning models learn the structure and patterns in the training data without any prior theoretical assumptions and then use inference to develop useful predictions. A novel machine learning-based algorithm has been previously developed for the prediction of black carbon mass absorption cross-section (MAC BC ) and applied to a variety of different atmospheric environments. In contrast to light scattering theories which require assumptions about the underlying physics, this algorithm uses time-series data of aerosol properties to estimate the temporally-varying MAC BC at 870 nm. Here, we analyze our algorithm and discuss the influence of aerosol optical properties (such as Ångström exponents and single scattering albedo) and chemical composition on the model outputs and the associated accuracy. Additionally, we conduct sensitivity analyses on our models to understand how the predictions change in response to different sets of input variables. Our support vector machine (SVM) for regression model is the least sensitive to variations in the input variables, although all models tend to exhibit a degradation to their accuracy when scattering Ångström exponents are less than one.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

An Indirect Search for Weakly Interacting Massive Particles in the Sun Using Upward-going Muons in NOvA

I present the first Dark Matter search results using the full data set collected with the upward-going muon trigger in NOvA. Weakly Interactive Massive Particles (WIMPs) are a theoretical non-baryonic form of Dark Matter. The nature of Dark Matter is one of the most exciting open questions in modern physics. Though its existence can be inferred by astrophysical evidence, its properties are not yet understood. If we assume that Dark Matter particles can produce Standard Model particles through their interactions, an indirect search can help shed light on this mystery.The NOvA collaboration has built a 14 kton, fine-grained, low-Z, total absorption tracking calorimeter at an off-axis angle to the NuMI neutrino beam. Even though the detector is optimized to observe electron neutrino appearance from a muon neutrino beam, it has a unique potential for more exotic searches given its excellent granularity and energy resolution and relatively low-energy neutrino thresholds. In fact, with an efficient upward-going muon trigger and sufficient background suppression offline, NOvA is capable of a competitive indirect Dark Matter search for low-mass WIMPs.The idea of the upward-going muon trigger is first to select high-quality muon tracks, then use the timing information of all of the hits of each track to estimate directionality. In this way, the background flux is suppressed by more than a factor of 10^5 at trigger level to a rate of approximately 1 Hz. To further optimize this search, we use only upward-going muons that point to the Sun, so our search occurs at night when the Sun is on the other side of the Earth. This strategy also allows us to use the time when the Sun is above the horizon as a control region to estimate the background. Ultimately, implementation of a cut based and maximum likelihood analysis provides a powerful tool for rejecting background and selecting a sample of neutrino-induced upward-going muons. The overall background rejection power achieved by the analysis is substantial and impressive. Starting with approximately 150,000 events per second, we reduced it to 40 events per year. Since no statistically significant excess was found, a 90\% C.L. upper limit on the expected muon flux of upward-going muons has been set using the upper limit on the number of events given the number of observed events in the signal region. Lastly, by assuming the theory behind the upward-going muon flux, a limit on the WIMP-nucleon spin-dependent cross-section in the Sun was estimated. Although the limits on the spin-dependent cross-section do not appear to be competitive with previous indirect Dark Matter searches, the upward-going muon flux limits are promising. The upward-going muon flux limits could extend these results to a broader class of models that are not specific to the dark matter theory but produce upward-going muons, leading to competitive results.

Principato, Cristiana↗
DOE OSTI2020

Real-time interface investigation on degradation mechanism of organic light-emitting diode by in-operando X-ray spectroscopies

Understanding the chemical evolution at the interface of organic light-emitting diodes (OLEDs) under working conditions is critical for addressing device failure and further improving performance. In this work, an in-operando approach was developed employing synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the electronic structures and chemical degradation mechanisms of a model tris(8-hydroxyquinoline) aluminum (Alq 3 )-based OLED device under working condition. The results identify that Mg atoms from the electrode migrate into the Alq 3 organic layer under a potential bias and replace Al atom sites, forming the unstable Mgq 3 species which lead to device degradation. Here, the findings from the classic and simple model device elucidate the degradation mechanisms occurred at the interface of OLED devices, which may facilitate the development of more efficient and stable OLED devices with complex structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Structural and optical properties of Sm{sup 3+}-doped borate glasses for luminescent applications

In this work, most interesting optical investigations are carried out with the glass composition (20 − x) CdCO{sub 3} + 15 Li{sub 2}CO{sub 3} + 15 Na{sub 2}CO{sub 3} + 50 H{sub 3}BO{sub 3} + xSm{sub 2}O{sub 3} (where x = 0.1, 0.5, 1.0, 3.0, 4.0 and 5.0 mol%) prepared with conservative melt-quenching technique. DSC verifies the annealing temperature and thermal stability of the prepared glass. X-ray diffraction technique is employed to inspect the amorphous structure of the glasses. FTIR technique helps to view the vibrational band positions of the host material. For optical studies, optical absorption and emission measurements are used. From the absorption spectra, Judd–Ofelt (JO) parameters (Ω{sub 2}, Ω{sub 4}, Ω{sub 6}), rms value of oscillator strength (δ{sub rms}), nephelauxetic parameter ( β-bar ), bonding parameter (δ) and optical band gaps are evaluated. Radiative properties such as radiative transition probabilities (A{sub T}), branching ratios (β{sub cal}, β{sub exp}) and stimulated emission cross section (σ{sub emi}) are calculated using JO theory. The higher stimulated emission cross section (14.39 × 10{sup −22} cm{sup 2}), optical gain (36.69 × 10{sup −25} cm{sup 2} s) indicate that 1.0 mol% of Sm{sup 3+}-doped borate glass would be a potential gain medium for solid state laser application at 603 nm. Color coordinates of the glasses located in the reddish-orange region could be useful for white light-emitting application.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Wavelength-Dependent Spin Excitation with Circularly Polarized Light in CdSe Nanoplatelets

Zinc-blende (ZB) cadmium selenide (CdSe) nanoplatelets (NPLs) have drawn increasing attention as an ideal condensed-phase material for facilitating photon-to-spin transduction in quantum networks. Yet, a systematic investigation of their fidelity in converting circularly polarized light (CPL) to exciton spin polarization as a function of excitation wavelength is lacking. Here, this work demonstrates using time-resolved transient absorption (TA) spectroscopy combined with density functional theory calculations that ZB CdSe NPLs exhibit wavelength-dependent CPL-induced spin polarization. The capacity of CPL to inject spin polarization is maximized for resonant excitation of band-edge valence-to-conduction band (VB/CB) transitions, and the degree to which CPL induces spin polarization can be modified for non-resonant excitation wavelengths as excitation occurs at k-points away from the Γ point from VB states with varying degrees of mixed heavy-hole (HH) and light-hole (LH) characters. Furthermore, it is highlighted that spin polarization within the LH exciton (LX) population created from resonant LH/CB excitation is retained upon LX → HH exciton (HX) relaxation due to the slow electron spin-flip rate (~1.1 ps) compared to the LH → HH inter-band relaxation rate (~200 fs).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

CBET-induced nonuniformity in direct-drive implosions on OMEGA [Slides]

Three dimensional polarization-dependent CBET plus beam balance and pointing are required to model nonuniformity in direct-drive implosions on OMEGA. Uniform laser energy absorption is essential for successful laser-direct-drive inertial confinement fusion but a growing body of evidence suggests OMEGA implosions are more asymmetric than predictions. By measuring the intensity and polarization of light scattered from individual beams, we have identified OMEGA’s polarization smoothing via distributed polarization rotators (DPR’s) as one previously unrealized source of nonuniformity. Polarization-dependent CBET along with beam energy balance, and beam pointing require three-dimensional modeling. Laser absorption mode 1 predictions from a fully three-dimensional CBET model correlate well with the observed direction of the core flow.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗