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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 1,531 records · Page 85
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Spectroscopic Studies of Mononuclear Molybdenum Enzyme Centers

A concise review is provided of the contributions that various spectroscopic methods have made to our understanding of the physical and electronic structures of mononuclear molybdenum enzymes. Contributions to our understanding of the structure and function of each of the major families of these enzymes is considered, providing a perspective on how spectroscopy has impacted the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

How Fast Can a Li-Ion Battery Be Charged? Determination of Limiting Fast Charging Conditions

Fast-charge protocols that prevent lithium plating are needed to extend the life span of lithium-ion batteries. Here, we describe a simple experimental method to estimate the minimum charging time below which it is simply impossible to avoid plating at a given temperature. We demonstrate that, by gauging and correcting the ohmic drop that is intrinsic to reference electrodes, the local potential at the anode surface can be reasonably approximated. This finer anode control enables the determination of the maximum average rate at which lithium deposition can be mitigated, establishing realistic boundaries that can inform the development of advanced charging protocols.

25 ENERGY STORAGE↗
DOE OSTI2023

Structural analysis of molten materials by a remote fiber optic Raman sensor

This study presents a novel in situ high-temperature fiber optic Raman probe that enables the study of the physical properties and structure of molten samples at temperatures up to 1400 °C. To demonstrate the functionality of the high-temperature fiber optic Raman probe, different composition mold fluxes were evaluated in this report. The Raman spectra at flux molten temperature were successfully collected and analyzed. A deconvolution algorithm was employed to identify peaks in the spectra associated with the molecular structure of the components in each sample. Here, the experimental results demonstrate that the composition-dependent Raman signal shift can be detected at high temperatures, indicating that molten materials analysis using a high-temperature Raman system shows significant promise. This flexible and reliable high-temperature Raman measurement method has great potential for various applications, such as materials development, composition and structure monitoring during high-temperature processing, chemical identification, and process monitoring in industrial production.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Photodriven electron-transfer dynamics in a series of heteroleptic Cu(I)–anthraquinone dyads

Solar fuels catalysis is a promising route to efficiently harvesting, storing, and utilizing abundant solar energy. To achieve this promise, however, molecular systems must be designed with sustainable components that can balance numerous photophysical and chemical processes. To that end, here we report on the structural and photophysical characterization of a series of Cu(I)–anthraquinone-based electron donor–acceptor dyads. The dyads utilized a heteroleptic Cu(I) bis-diimine architecture with a copper(I) bis-phenanthroline chromophore donor and anthraquinone electron acceptor. We characterized the structures of the complexes using x-ray crystallography and density functional theory calculations and the photophysical properties via resonance Raman and optical transient absorption spectroscopy. The calculations and resonance Raman spectroscopy revealed that excitation of the Cu(I) metal-to-ligand charge-transfer (MLCT) transition transfers the electron to a delocalized ligand orbital. The optical transient absorption spectroscopy demonstrated that each dyad formed the oxidized copper–reduced anthraquinone charge-separated state. Unlike most Cu(I) bis-phenanthroline complexes where increasingly bulky substituents on the phenanthroline ligands lead to longer MLCT excited-state lifetimes, here, we observe a decrease in the long-lived charge-separated state lifetime with increasing steric bulk. The charge-separated state lifetimes were best explained in the context of electron-transfer theory rather than with the energy gap law, which is typical for MLCT excited states, despite the complete conjugation between the phenanthroline and anthraquinone moieties.

14 SOLAR ENERGY↗
NASA NTRS1997

Modulated FT- Raman Fiber-Optic Spectroscopy: A technique for Remotely Monitoring High-Temperature Reactions in Real-Time

A modification to a commercial FT-Raman spectrometer is presented for the elimination of thermal backgrounds in FT-Raman spectra. The modification involves the use of a mechanical chopper to modulate the CW laser, remote collection of the signal via fiber optics, and connection of a dual-phase digital signal processor lock-in amplifier between the detector and the spectrometer's collection electronics to demodulate and filter the optical signals. The resulting modulated FT-Raman fiber-optic spectrometer is capable of completely eliminating thermal backgrounds at temperatures exceeding 370 C. In addition, the signal/noise of generated Raman spectra is greater than for spectra collected with the conventional FT-Raman under identical conditions and incident laser power. This is true for both room-temperature and hot samples. The method allows collection of data using preexisting spectrometer software. The total cost of the modification (excluding fiber optics) is approximately $3000 and requires less than 2 h to implement. This is the first report of Fr-Raman spectra collected at temperatures in excess of 300 C in the absence of thermal backgrounds.

Cooper, John B.↗
DOE OSTI2025

Ultra-high Information-content Chemical Imaging with Broadband Coherent Anti-Stokes Raman and Two-photon Fluorescence Lifetime Microscopy

Raman fingerprint spectroscopy and fluorescence lifetime imaging are emerging tools for studying metabolic profiles of biological specimens. While Raman fingerprint spectroscopy detects intrinsic molecular vibrations that reflect the molecular composition and chemical environment of a sample, fluorescence lifetime imaging measures changes in the excited-state lifetime of fluorophores that are sensitive to their microenvironments. Here, we present a multimodal imaging platform combining broadband coherent anti-Stokes Raman scattering (BCARS) and two-photon fluorescence lifetime imaging (2p-FLIM) microscopy that can acquire biologically relevant Raman fingerprint spectra and fluorescence lifetime signals in vivo and simultaneously. The tremendous chemical information obtained from spatially co-registered BCARS and 2p-FLIM images allows us to characterize the subtle differences between sub-cellular compartments and verify the potential false-positive results generated by fluorescence imaging alone. This is demonstrated by directly comparing the BCARS, 2p-FLIM, and two-photon excitation fluorescence(TPEF) signals simultaneously obtained from the same dye-stained organelle in the live, intact C. elegans expressing a green fluorescent protein (GFP) marker. In this work, we introduce the BCARS/2p-FLIM/TPEF setup scheme, the image acquisition steps, data processing, and representative results showing that the cross-modality imaging method enables rigorous characterization and in vivo detection at sub-cellular resolution. Furthermore, this protocol provides a framework for simultaneous chemical and fluorescence lifetime imaging to improve the accuracy of biological interpretation in complex living systems.

Xu, Haoyu [Georgia Institute of Technology, Atlant↗
DOE OSTI2020

Impact of the Lattice on Magnetic Properties and Possible Spin Nematicity in the S = 1 Triangular Antiferromagnet NiGa 2 S 4

NiGa 2 S 4 is a triangular lattice S = 1 system with strong two dimensionality of the lattice, actively discussed as a candidate to host spin-nematic order brought about by strong quadrupole coupling. Using Raman scattering spectroscopy we identify a phonon of E g symmetry which can modulate magnetic exchange J 1 and produce quadrupole coupling. Additionally, our Raman scattering results demonstrate a loss of local inversion symmetry on cooling, which we associate with sulfur vacancies. This will lead to disordered Dzyaloshinskii-Moriya interactions, which can prevent long-range magnetic order. Using magnetic Raman scattering response we identify 160 K as a temperature of an upturn of magnetic correlations. Here, the temperature range below 160 K, but above 50 K where antiferromagnetic correlations start to increase, is a candidate for spin-nematic regime.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Stabilizing Reversible Oxygen Redox Chemistry in Layered Oxides for Sodium‐Ion Batteries

Abstract Triggering oxygen‐related activity is demonstrated as a promising strategy to effectively boost energy density of layered cathodes for sodium‐ion batteries. However, irreversible lattice oxygen loss will induce detrimental structure distortion, resulting in voltage decay and cycle degradation. Herein, a layered structure P2‐type Na 0.66 Li 0.22 Ru 0.78 O 2 cathode is designed, delivering reversible oxygen‐related and Ru‐based redox chemistry simultaneously. Benefiting from the combination of strong Ru 4d‐O 2p covalency and stable Li location within the transition metal layer, reversible anionic/cationic redox chemistry is achieved successfully, which is proved by systematic bulk/surface analysis by in/ex situ spectroscopy (operando Raman and hard X‐ray absorption spectroscopy, etc.). Moreover, the robust structure and reversible phase transition evolution revealed by operando X‐ray diffraction further establish a high degree reversible (de)intercalation processes (≈150 mAh g −1 , reversible capacity) and long‐term cycling (average capacity drop of 0.018%, 500 cycles).

Cao, Xin↗
DOE OSTI2025

Multi-Dimensional Spectroscopy with Intense Entangled Beams: Entanglement-Enabled Phase Matching in a Collinear Beam Geometry

The experimental realization of quantum molecular spectroscopy with entangled photons remains challenging owing to the low signal-to-noise ratio resulting from the use of low-flux entangled photons. High-flux entangled photons via intense entangled beams can be used to improve the signal-to-noise ratio, but the presence of unentangled photons contaminates the quantum signal stemming from entangled photons. Here, we demonstrate how intense entangled beams can be used in multi-dimensional spectroscopy while retaining the advantage of photon entanglement. Our approach is broadly applicable to odd-ordered nonlinear spectroscopies, and it generates purely quantum spectroscopic signals. The proposed approach allows the recording of desired phase-matched signals even in a collinear beam geometry, which lifts the requirement of complicated beam geometry setups for phase matching in multi-dimensional spectroscopies.

Absorption spectroscopy↗
DOE OSTI2020

Understanding the chemical contribution to the enhancement mechanism in SERS: Connection with Hammett parameters

The enhancement mechanism due to the molecule-surface chemical interaction in surface-enhanced Raman scattering (SERS) has been characterized using a theoretical approach based on time dependent density functional theory. This includes a systematic study of the chemical mechanism (CM) to the SERS enhancement for halogen substituted benzenethiols interacting with a silver cluster. Changing the halogen on benzenethiol enables us to systematically modulate interactions between the benzenethiol ring and the metal cluster. We observe a decrease in the CM enhancement factor with an increase in atomic number of the halogen for para- substitutions. For meta- substitutions, there is no such trend. However, the results scale linearly with the Hammett parameters for both meta and para halogens, which provides an important predictive tool for interpreting chemical enhancements. We also study the effect of solvation on the CM, showing that there is a systematic increase in enhancement with increasing solvent dielectric constant. As a result, the correlation of CM with other properties, such as the amount of charge transfer between adsorbate and metal, or the excitation energies of charge transfer states, is much less predictive than the Hammett parameter correlation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Creation of color centers in diamond by recoil implantation through dielectric films

The need of near-surface color centers in diamond for quantum technologies motivates the controlled doping of specific extrinsic impurities into the crystal lattice. Further, recent experiments have shown that this can be achieved by momentum transfer from a surface precursor via ion implantation, an approach known as “recoil implantation.” Here, we extend this technique to incorporate dielectric precursors for creating nitrogen-vacancy (NV) and silicon-vacancy (SiV) centers in diamond. Specifically, we demonstrate that gallium focused-ion-beam exposure to a thin layer of silicon nitride or silicon dioxide on the diamond surface results in the introduction of both extrinsic impurities and carbon vacancies. These defects subsequently give rise to near-surface NV and SiV centers with desirable properties after annealing.

42 ENGINEERING↗
DOE OSTI2023

Magnetoelastic interactions in SrCu 2 (BO 3 ) 2 studied by Raman scattering experiments and first principles calculations

Dynamic and static crystal lattice properties of SrCu 2 (BO 3 ) 2 are studied by means of Raman scattering, magnetostriction, and thermal expansion measurements in magnetic fields to 45 T. Raman experiments versus temperature reveal that some phonon modes show an unusual behavior: their frequencies soften (modes at 200 and 450 cm –1 ) while others harden (modes at 385 and 478 cm –1 ) when decreasing the temperature below 15 K. Magneto-Raman experiments show that their field dependence correlates with their respective temperature dependencies; e.g., modes that are hardened with increasing temperature also harden with applied magnetic fields and modes that become softer with temperature also soften with applied fields. We use density functional theory to successfully model and compute the energies of these modes, classifying them into two types: pantograph (modes that soften when decreasing the temperature) and nonpantograph. We conclude that the former involves the modification of the intradimer exchange interaction J and the latter the interdimer J'. Lastly, dilatometry is used to correlate field-dependent Raman modes to the closing of the spin gap as well as fractional-magnetization stripe states M = 1/4 M s and M = 1/3 M s , where M s is the saturation magnetization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Charge transfer in transition metal dichalcogenide alloy heterostructures

Two-dimensional (2D) transition metal dichalcogenides and their alloys provide a unique platform for exploring interlayer charge transfer in van der Waals heterostructures. These structures are crucial for advancing the next-generation electronic, optoelectronic, and quantum devices. In this study, interlayer charge transfer in heterostructures composed of MoSe 2 , MoS 2 , and their alloy, MoSSe, is investigated using transient absorption, Raman, and photoluminescence spectroscopy. The experimental results reveal that electron transfer in the alloy heterostructures, MoSSe/MoS 2 and MoSe 2 /MoSSe, is faster than in the pure MoSe 2 /MoS 2 heterostructure, despite the smaller conduction band offsets of the alloy systems. Raman spectroscopy confirms that alloy layers support phonon modes matching those of the pure layers, aligning with theoretical models of phonon-assisted interlayer charge transfer. Additionally, efficient hole transfer is observed in both alloy heterostructures. The findings suggest transition metal dichalcogenides alloys can be used for engineering heterostructures with desired charge transfer properties. By leveraging compositionally tunable band gaps and optical properties, alloy-based heterostructures offer opportunities for designing tailored materials suitable for diverse applications such as photodetectors, light-emitting devices, and flexible electronics. Furthermore, the ultrafast charge transfer observed in these systems provides insights into the fundamental mechanisms governing interlayer interactions in 2D materials.

2D material↗
DOE OSTI2020

Direct SERDS sensing of molecular biomarkers in plants under field conditions

Molecular biomarkers such as microRNAs (miRNAs) play important roles in regulating various developmental processes in plants. Understanding these pathways will help bioengineer designing organisms for efficient biomass accumulation. Current methods for RNA analysis require sample extraction and multi-step sample analysis, hindering work in field studies. Recent work in the incorporation of nanomaterials for plant bioengineering research is leading the way of an agri-tech revolution. As an example, surface-enhanced Raman scattering (SERS)–based sensors can be used to monitor RNA in vivo. However, the use of SERS in the field has been limited due to issues with observing Raman signal over complex background. To this end, shifted-excitation Raman difference spectroscopy (SERDS) offers an effective solution to extract the SERS signal from high background based on a physical approach. In this manuscript, we report the first application of SERDS on SERS sensors. We investigated this technique on SERS sensor developed for the detection of a microRNA biomarker, miR858. We tested the technique on in vitro samples and validated the technique by detecting the presence of exogenous miR858 in plants directly under ambient light in a growth chamber. The possibility of moving the detection of nucleic acid targets outside the constraints of laboratory setting enables numerous important bioengineering applications. Finally, such applications can revolutionize biofuel production and agri-tech through the use of nanotechnology-based monitoring of plant growth, plant health, and exposure to pollution and pathogens.

09 BIOMASS FUELS↗
DOE OSTI2023

Raman spectroscopic characterization of SiO 2 phase transformation and Si substrate stress relevant to EBC performance

To accurately model the long-term durability of environmental barrier coatings (EBCs), a more complete understanding of the phase composition and transformations of the thermally grown oxide SiO 2 (TGO) is desired. For the TGO formed during thermal cycling in steam, cristobalite formation and the subsequent β- to α-cristobalite transformation has been identified as a potentially life-limiting mechanism. In this study, Raman micro-spectroscopy was used to quantify the cristobalite transformation on a polycrystalline Si coupon that was exposed to steam at 1350°C for 100 h. The phase transformation was mapped at 200–260°C on the TGO surface at different ramp rates using a heating stage and a micro-positioning stage. The stress in the Si substrate was also determined using Raman spectroscopy by measuring the stress induced peak shift. The α→β phase transformation produced a 300–500 MPa tensile stress in the Si substrate, which compared well to the stress predicted from the volumetric expansion of the cristobalite. In conclusion, quantifying the phase transformation and residual stress are critical tools in developing the next generation of high performance EBCs.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Structure of lunar glasses by Raman and soft X-ray spectroscopy.

X-ray spectra and Raman spectra have been measured from individual particles of lunar glasses. Each particle was analyzed separately by electron microprobe. Silicon emission shifts vary between parent rock types and can be interpreted as a range of Si-O distances from 1.612 to 1.637 A. Aluminum emission shifts relate to the amount of 4- and 6-coordinated Al in the glass. Raman spectra show broadened bands. Certain bands recur in many specimens and relate to the main normative minerals for the glass bulk composition, olivine, pyroxene, and anorthite.

Fabel, G. W.↗
DOE OSTI2025

Excitation Laser Energy Dependence of the Gap-Mode TERS Spectra of WS 2 and MoS 2 on Silver

In this work we present a systematic study of the dependence of the gap mode tip-enhanced Raman scattering (TERS) response of the mono- and bi-layer WS 2 and MoS 2 on silver as a function of the excitation laser energy in a broad spectral range from 473nm to 830 nm. For this purpose, we collected consecutive TERS maps of the same area in the sample containing mono-and bi-layer regions with the same TERS probe with 6 different excitation lasers. To decrease the number of collected TERS maps, we used for the first time to the best of our knowledge, concurrent excitation and collection with two lasers simultaneously. We found that the E 2g /A 1g peak intensity ratio for the bilayer WS 2 @Ag and the ratio of the A’/A 1g peak intensity of the out-of-plane mode for the mono- and the bilayer, change in a significantly non-monotonous way as the excitation laser energy is swept from 1.58 eV to 2.62 eV. The former ratio increases at energies corresponding to A and B excitons (~2.0 eV and 2.4 eV correspondingly) in bilayer WS 2 . The absolute intensity of the A’ peak in the monolayer, and correspondingly the A’/A 1g ratio, is surprisingly high at lower excitation energies, but dips dramatically at the energy corresponding to the A exciton, being restored partially in between A and B excitons, but still showing the descending trend as the excitation laser energy increases. A somewhat similar picture was observed in mono- and bi-layers of MoS 2 @Ag, though the existing set of excitation lasers did not match the excitonic profile of this material as nicely as for the case of WS 2 . We attribute the observed behavior to the presence of intermediate (Fano resonance) or strong (Rabi splitting) coupling between the excitons in transition metal dichalcogenides (TMDs) and the plasmons in the tip-substrate nanocavity. This is akin to the so-called Fano (Rabi) transparency experimentally observed in far field scattering from transition metal dichalcogenides between two plasmonic metals. The possibility of the formation of intermediate/strong coupling between the excitonic resonances in TMDs and the nanocavity re-evaluates the role of various resonances in the gap-mode TERS and should become an important factor to be considered by TERS practitioners during planning the experiments. Lastly, based on observed phenomena and its explanation, we propose the “ideal” substrate for efficient TERS and tip enhanced photoluminescence (TEPL) measurements.

Raman spectroscopy↗