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Results for “RAMAN SPECTRA”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Harmonic Infrared and Raman Spectra in Molecular Environments Using the Polarizable Embedding Model

We present a fully analytic approach to calculate infrared (IR) and Raman spectra of molecules embedded in complex molecular environments modeled using the fragment-based polarizable embedding (PE) model. We provide the theory for the calculation of analytic second-order geometric derivatives of molecular energies and first-order geometric derivatives of electric dipole moments and dipole–dipole polarizabilities within the PE model. The derivatives are implemented using a general open-ended response theory framework, thus allowing for an extension to higher-order derivatives. The embedding-potential parameters used to describe the environment in the PE model are derived through first-principles calculations, thus allowing a wide variety of systems to be modeled, including solvents, proteins, and other large and complex molecular environments. Here, we present proof-of-principle calculations of IR and Raman spectra of acetone in different solvents. This work is an important step toward calculating accurate vibrational spectra of molecules embedded in realistic environments.

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

Simulations of the IR and Raman spectra of water confined in amorphous silica slit pores

Water in nano-scale confining environments is a key element in many biological, material, and geological systems. The structure and dynamics of the liquid can be dramatically modified under these conditions. Probing these changes can be challenging, but vibrational spectroscopy has emerged as a powerful tool for investigating their behavior. A critical, evolving component of this approach is a detailed understanding of the connection between spectroscopic features and molecular-level details. In this paper, this issue is addressed by using molecular dynamics simulations to simulate the linear infrared (IR) and Raman spectra for isotopically dilute HOD in D 2 O confined in hydroxylated amorphous silica slit pores. The effect of slit-pore width and hydroxyl density on the silica surface on the vibrational spectra is also investigated. The primary effect of confinement is a blueshift in the frequency of OH groups donating a hydrogen bond to the silica surface. This appears as a slight shift in the total (measurable) spectra but is clearly seen in the distance-based IR and Raman spectra. Analysis indicates that these changes upon confinement are associated with the weaker hydrogen-bond accepting properties of silica oxygens compared to water molecules.

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

Controlling the Fluctuating Tip-Enhanced Raman Spectra of Chloramben on Silver Nanocubes

Tip-enhanced Raman (TER) scattering from molecules residing at plasmonic junctions can be used to detect, identify, and image single molecules. This is most evident for flat molecules interrogated under extreme conditions of temperatures and pressure. It is also the case for (bio)molecular systems that feature preferred orientations/conformations under ambient laboratory conditions. More complex molecules that can adopt multiple conformations and/or that feature different protonation and/or charge states give rise to complex TER spectra. Here we illustrate how the latter can be controlled in the case of chloramben molecules coated onto plasmonic silver nanocubes. We show that characteristic molecular Raman spectra cannot be obtained when tunneling plasmons are operative, i.e., when the tip is in direct contact with the chemically functionalized plasmonic nanoparticles. We rationalize these observations and propose an approach to less invasive, and hence, more analytical TER spectral imaging.

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

Measuring Plant Metabolite Abundance in Spearmint ( Mentha spicata L.) with Raman Spectra to Determine Optimal Harvest Time

A fast field-deployable method utilizing Raman spectroscopy to determine the optimal harvest time of plants to extract the highest abundance of target metabolites is presented. Rosmarinic acid is a metabolite extracted from spearmint (Mentha spicata L.). Leaves from commercial “Native” and proprietary clonal line “KI110” spearmint were measured as a function of cell type and age to determine rosmarinic acid abundance. A linear regression model with leave-one-out cross-validation (R 2 CV = 0.61, RMSECV = 11.1 mg/g) was developed between selected Raman peak areas and rosmarinic acid concentrations determined by high-performance liquid chromatography (HPLC). A principal component analysis (PCA) model was also developed to determine rosmarinic acid abundance. The method may be suited to the analysis of many agriculturally relevant plant species and metabolites with distinct Raman peaks.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Analysis of picosecond coherent anti-Stokes Raman spectra for gas-phase diagnostics

We present a hybrid frequency- and time-domain solution, applicable to the case of picosecond coherent anti-Stokes Raman scattering (CARS), for gas-phase diagnostics. A solution has been derived based on both physical arguments and four-wave mixing equations for picosecond CARS, with pulse durations that are comparable to the dephasing time scale for gas-phase Raman coherence—a regime where commonly employed solutions for impulsive (femtosecond) or cw (nanosecond) pump/Stokes forcing are not strictly valid. We present the ps-CARS spectrum in the form of incoherent sums of CARS intensity spectra, calculated from the fundamental solution for impulsive pump/Stokes Raman preparation. The solution was examined for temperatures from 1000–3000 K, for four plausible experimental configurations, with laser pulse durations of 50–150 ps, and probe pulse delays from −20 to 240 ps. Approximations based on cw and impulsive pump/Stokes preparation to fit picosecond CARS spectra at atmospheric pressure were examined and the relative thermometric accuracy and computational cost of these approximations were quantified for the case of a zero nonresonant CARS contribution, and a nonresonant susceptibility equal to 10% of the Raman-resonant value at the N 2 bandhead. The nanosecond CARS approximation can result in large fitting errors when the probe pulse time delay is less than the probe pulse duration. Errors as large as 10–20% are observed in the fit temperatures for a zero picosecond probe pulse delay, when the nonresonant background is neglected, largely due to an inability of the time-independent cw model to capture transient frequency spread dephasing effects at the Q -branch bandhead. The inclusion of a nonresonant background results in 40–60% thermometry errors with a nanosecond model at a zero-probe delay. Time-dependent impulsive calculations used for femtosecond CARS better approximate the structure of the N 2 bandhead, reducing temperature fitting errors to 5–10% at a short probe pulse delay. The impulsive approximation results in errors up to 10% at intermediate probe pulse delays, where the coherence of the pump and probe pulses leads to multiple terms in the picosecond CARS solution. Both approximations improve as the probe pulse delay exceeds the probe duration. The nanosecond approximation results in a 2–3% error, while the impulsive model results in differences of less than 1% in some cases. Fits to experimental data obtained using short, ∼60ps pulses at a zero probe time delay and longer 100 ps pulses at a substantial 200 ps delay are presented with accuracies of 1–3% in the fit temperature.

Kearney, Sean P.↗
DOE OSTI2024

Uncertainty analysis of Raman spectra for measuring ortho-parahydrogen compositions

Determining ortho-parahydrogen compositions at cryogenic temperatures is an important quality control for liquid hydrogen custody exchange. High orthohydrogen compositions lead to an exothermic reaction resulting in increased boil off and increased venting losses of liquid hydrogen product by either the supplier or consumer. Traditional methods for measuring ortho-parahydrogen compositions such as hot-wire anemometry, nuclear magnetic resonance, and infrared spectroscopy are typically inconvenient at best. As the number of cryogenic hydrogen systems continue to increase, there is an increased need for flexible, standardized techniques for post processing composition measurements. A Raman spectrometer implemented in the Cryo-Catalysis Hydrogen Experimental Facility (CHEF) has demonstrated incredible flexibility for composition measurements of cryogenic hydrogen flows through a wide range of temperatures and pressures with the Raman probe in-situ at cryogenic temperatures. This article analyzes the uncertainty of Raman spectroscopy data of cryogenic hydrogen equilibrated at temperatures in IONEX catalyst. Spectra from hydrogen catalyzed to the equilibrium ortho-parahydrogen composition are processed and compared to expected statistical distributions for method verification.

08 HYDROGEN↗
DOE OSTI2026

Raman Spectra of U3Ox

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Miskowiec, Andrew [ORNL] (ORCID:0000000203612614)↗
DOE OSTI2020

Higher-order phonon scattering: advancing the quantum theory of phonon linewidth, thermal conductivity and thermal radiative properties

Phonon scattering plays a central role in the quantum theory of phonon linewidth, which in turn governs important properties including infrared spectra, Raman spectra, lattice thermal conductivity, thermal radiative properties, and also signifi- cantly affects other important processes such as hot electron relaxation. Since Maradudin and Fein’s classic work in 1962, three-phonon scattering had been considered as the dominant intrinsic phonon scattering mechanism and has seen tremendous advances. However, the role of the higher-order four-phonon scattering had been persistently unclear and so was ignored. The tremendous complexity of the formalism and computational challenges stood in the way, prohibiting the direct and quantitative treatment of four-phonon scattering. In 2016, a rigorous four-phonon scattering formalism was developed, and the prediction was realized using empirical potentials. In 2017, the method was extended using first-principles calculated force constants, and the thermal conductivities of boron arsenides (BAs), Si and diamond were predicted. The predictions for BAs were later confirmed by several independent experiments. Four-phonon scattering has since been investigated in a range of materials and established as an important intrinsic scattering mechanism for thermal transport and radiative properties. Specifically, four-phonon scattering is important when the fourth-order scattering potential or phase space becomes relatively large. The former scenario includes: (i) nearly all materials when the temperature is high; (ii) strongly anharmonic (low thermal conductivity) materials, including most rocksalt compounds, halides, hydrides, chalcogenides and oxides. The latter scenario includes: (iii) materials with large acoustic–optical phonon band gaps, such as XY compounds with a large atomic mass ratio between X and Y; (iv) two- dimensional materials with reflection symmetry, such as single-layer graphene, single-layer boron nitride and carbon nanotubes; and (v) phonons with a large density of states, such as optical phonons, which are important for Raman, infrared and thermal radiative properties. Four-phonon scattering is expected to gain broad interest in various technologically important materials for thermoelectrics, thermal barrier coatings, thermal energy storage, phase change, nuclear power, ultra-high temperature ceramics, infrared spectra, Raman spectra, radiative transport, hot electron relaxation and radiative cooling. Four-phonon scattering has been, and will continue to be, established as an important intrinsic phonon scattering mechanism beyond three-phonon scattering. The prediction of four-phonon scattering will transition from a breakthrough to a new routine in the next decade.

Feng, Tianli↗
DOE OSTI2021

Quantitative analysis of Raman spectral parameters for carbon fibers: practical considerations and connection to mechanical properties

Although the literature on the Raman spectra of carbon fibers is vast, no consistent, robust predictive relationship between mechanical properties of carbon fibers and spectral parameters exists. This shortcoming is due to the use of numerous fitting functions to evaluate Raman spectra of carbon fibers and the inconsistencies in establishing the best fitting models in a statistically robust fashion. To address this gap, we present a comprehensive work on the Raman spectra of carbon fibers that combines a vast library of experimental data with a robust numerical analysis and a statistical evaluation of a wide range of suggested fitting models. This manuscript begins with a brief review of the commonly applied fitting models. Then, the Raman spectra of 32 commercially available polyacrylonitrile-based carbon fibers collected at excitation wavelengths 532, 633, and 785 nm are presented and the best fit for all fibers is evaluated based on several statistical criteria in conjunction with numerical calculations and physical arguments. The results suggest that high-performance fibers must be fit with at least five peaks, whereas high-tensile modulus fibers are best fit with at least six distinct peaks. Finally, we employ simultaneous fitting of the Raman spectra of specific fibers and wavelengths and demonstrate that strong correlations exist between mechanical properties and the D1 peak position and shape across the range of evaluated mechanical properties. Finally, we suggest straightforward improvements in fitting analysis procedures that can be implemented to increase coherency in the understanding of the underlying carbon fiber microstructure intuited from Raman spectroscopy.

36 MATERIALS SCIENCE↗
DOE OSTI2024

E(n)-Equivariant cartesian tensor message passing interatomic potential

Machine learning potential (MLP) has been a popular topic in recent years for its capability to replace expensive first-principles calculations in some large systems. Meanwhile, message passing networks have gained significant attention due to their remarkable accuracy, and a wave of message passing networks based on Cartesian coordinates has emerged. However, the information of the node in these models is usually limited to scalars, and vectors. In this work, we propose High-order Tensor message Passing interatomic Potential (HotPP), an E(n) equivariant message passing neural network that extends the node embedding and message to an arbitrary order tensor. By performing some basic equivariant operations, high order tensors can be coupled very simply and thus the model can make direct predictions of high-order tensors such as dipole moments and polarizabilities without any modifications. The tests in several datasets show that HotPP not only achieves high accuracy in predicting target properties, but also successfully performs tasks such as calculating phonon spectra, infrared spectra, and Raman spectra, demonstrating its potential as a tool for future research.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

A Novel Non‐Destructive Rapid Tool for Estimating Amino Acid Composition and Secondary Structures of Proteins in Solution

Abstract Amino‐acid protein composition plays an important role in biology, medicine, and nutrition. Here, a groundbreaking protein analysis technique that quickly estimates amino acid composition and secondary structure across various protein sizes, while maintaining their natural states is introduced and validated. This method combines multivariate statistics and the thermostable Raman interaction profiling (TRIP) technique, eliminating the need for complex preparations. In order to validate the approach, the Raman spectra are constructed of seven proteins of varying sizes by utilizing their amino acid frequencies and the Raman spectra of individual amino acids. These constructed spectra exhibit a close resemblance to the actual measured Raman spectra. Specific vibrational modes tied to free amino and carboxyl termini of the amino acids disappear as signals linked to secondary structures emerged under TRIP conditions. Furthermore, the technique is used inversely to successfully estimate amino acid compositions and secondary structures of unknown proteins across a range of sizes, achieving impressive accuracy ranging between 1.47% and 5.77% of root mean square errors (RMSE). These results extend the uses for TRIP beyond interaction profiling, to probe amino acid composition and structure.

Chemistry↗
DOE OSTI2022

Raman spectroscopy of thermally perturbed carbon fibers: Discriminating spectral responses of modulus classes and defect types

The mechanical strength properties of carbon fibers are generally thought to be correlated with the presence of underlying atomic-level defects. These defects serve to break the underlying translational symmetry of the graphitic or graphene subunits of the fiber construction, resulting in the emergence of new Raman-active spectral features. However, historical attempts to classify the precise origin of defect contributions to the Raman spectra have been challenging because of indistinct and overlapping features in the carbon fiber Raman spectra. Further, while substantial research exists on high-temperature exposure in inert atmospheres for carbon fiber composites, comparatively less addresses microscale behaviors and Raman spectral alterations to monofilament carbon fibers exposed to high-temperature atmospheric environments. Here, we report Raman spectral responses of nine commercially available high-performance, polyacrylonitrile-based carbon fibers exposed to various atmospheric heat treatments. In this work, we introduce a model-independent characterization method, the integrated absolute difference, to quantify the spectral responses to heat treatment of different fiber modulus classes. We combine this new method with a newly reported strategy to standardize spectral fitting for carbon fibers. With this approach, we show that atomic-scale defects in the underlying fiber microstructure manifest in measurably distinct manners and have distinct responses to thermal perturbation. These combined approaches may lay the foundation for disentangling contributions from specific defects in the Raman spectra of carbon fibers.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A Spectroscopic Study of Mars-analog Materials with Amorphous Sulfate and Chloride Phases: Implications for Detecting Amorphous Materials on the Martian Surface

The Chemistry and Mineralogy X-ray diffraction (XRD) instrument aboard the Curiosity rover consistently identifies amorphous material at Gale Crater, which is compositionally variable, but often includes elevated sulfur and iron, suggesting that amorphous ferric sulfate (AFS) may be present. Understanding how desiccating ferric sulfate brines affect the spectra of Martian material analogs is necessary for interpreting complex/realistic reaction assemblages. Visible and near-infrared reflectance (VNIR), mid-infrared attenuated total reflectance (MIR, FTIR-ATR), and Raman spectra, along with XRD data are presented for basaltic glass, hematite, gypsum, nontronite, and magnesite, each at three grain sizes (<25, 25–63, and 63–180 μm), mixed with ferric sulfate (+/–NaCl), deliquesced, then rapidly desiccated in 11% relative humidity or via vacuum. All desiccated products are partially or completely XRD amorphous; crystalline phases include starting materials and trace precipitates, leaving the bulk of the ferric sulfate in the amorphous fraction. Due to considerable spectral masking, AFS detectability is highly dependent on spectroscopic technique and minerals present. This has strong implications for remote and in situ observations of Martian samples that include an amorphous component. AFS is only identifiable in VNIR spectra for magnesite, nontronite, and gypsum samples; hematite and basaltic glass samples appear similar to pure materials. Sulfate features dominate Raman spectra for nontronite and basaltic glass samples; the analog material dominates Raman spectra of hematite and gypsum samples. MIR data are least affected by masking, but basaltic glass is almost undetectable in MIR spectra of those mixtures. NaCl produces similar FTIR-ATR and Raman features, regardless of analog material.

58 GEOSCIENCES↗
DOE OSTI2024

Improving understanding of NpO 2 and Np 2 O 5 through vibrational spectroscopy

Raman spectra of three NpO 2 samples and two samples produced from a modified direct denitration (MDD) process were collected. The spectral features of the NpO 2 samples were consistent and indicated only NpO 2 . The spectra of the MDD samples indicated the presence of NpO 2 and an additional phase attributed to the neptunium binary oxide Np 2 O 5 . These Raman spectra are the first reported of Np 2 O 5 , and the proportions of these neptunium oxide phases varied within the samples, suggesting significant sample inhomogeneity. Peaks in the Raman spectra of Np 2 O 5 at 569 and 782 cm –1 were tentatively assigned to concerted, symmetric stretches of the neptunyl cations. Finally, laser-induced heating of regions in the MDD samples that were rich in Np 2 O 5 showed spectral features that indicated conversion to NpO 2 .

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

Raman spectroscopic investigation of selected natural uranyl sulfate minerals

Uranyl sulfates are important constituents of uranium ores and represent a significant fraction of U(VI) minerals discovered in recent years owing to their propensity to form in mine tailings and legacy sites related to uranium exploration. Recently, we surveyed all published Raman spectra for uranium minerals and found significantly less easily accessible data available for uranyl sulfates relative to other groups of uranium minerals (Spano et al. 2023). In that work, we described average spectra for groups of uranyl minerals to understand common vibrational spectroscopic features attributable to similarities in oxyanion chemistry among U(VI) minerals, but only data for three uranyl sulfate minerals were included in the study. The present work reports on Raman spectra collected for 18 additional uranyl sulfate minerals. In conclusion, to better understand underlying structural and chemical features that give rise to spectroscopic observables, we relate differences in structural topology, charge-balancing cations, and locality of origin to features observed in the Raman spectra of selected natural uranyl sulfates.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗