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At least 181 records · Page 10

The electronic Raman scattering spectrum of PuO 2

Here the Raman spectrum of PuO 2 was measured up to 13,000 cm –1 with three different laser excitation wavelengths spanning the resonance (405 nm), near-resonance (457 nm), and preresonance (514 nm) energy range. Approximately 26 never-before-seen bands were observed between 3500 and 13,000 cm –1 . Given the very high energy of the Raman shifts of these bands and the relative insensitivity of their spectral position to the interrogating laser wavelength, they are believed to arise from an electronic origin. These bands are present in both freshly calcined and radiolytically aged PuO 2 , although a broad luminescence is observed in the aged material, which obscures many of the high frequency features. In situ laser annealing of the material attenuated this luminescence and allowed for clear observation of these never-before-seen spectral features. Discovery of these high-energy bands presents a new way of identifying PuO 2 for nuclear nonproliferation and forensics purposes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

A Closer Look at Tip-Enhanced Raman Chemical Reaction Nanoimages

Tip-enhanced Raman spectroscopy (TERS) is a powerful technique that enables ultrahigh spatial resolution and ultrasensitive chemical imaging. This technique’s ability to track plasmon-induced/enhanced chemical reactions in real space has gained increasing popularity in recent years. Here, in this study, we expose inherent difficulties associated with assigning TERS signatures that accompany chemical transformations. Namely, distinct selection rules as well as the possibility of multiple physical processes/chemical reaction pathways complicate spectral assignments and necessitate caution in assigning the experimental observables. We illustrate the latter using 4,4'-dimercaptostilbene-functionalized plasmonic silver nanocubes, wherein we identify the TERS signatures of product formation, molecular charging, multipolar Raman scattering, and preferred molecular orientations that all lead to distinct and assignable spectral patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multipolar Raman Scattering vs Interfacial Nanochemistry: Case of 4-Mercaptopyridine on Gold

Caution needs to be exercised in associating changes in plasmon-enhanced Raman spectra with chemical transformations. This is demonstrated through a detailed analysis of tip-enhanced Raman (TER) scattering from 4-mercaptopyridine (MPY) on gold. The substrate used consists of gold nanoplates atop a gold surface featuring heterogeneous grooves, all coated with a monolayer of MPY. The brightest spectra across the substrate exhibit features that can only be recovered by considering the generalized polarizability of oriented MPY molecules. Finally, the complex TER spectra we observe do not mark interfacial chemistry, but rather, multipolar TER scattering driven by local field gradients.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-pressure response of vibrational properties of b-As x P 1– x : in situ Raman studies

The structural evolution of black arsenic-phosphorous (b-As x P 1–x ) alloys with varying arsenic concentrations was investigated under hydrostatic pressure using in situ Raman spectroscopy. High-pressure experiments were conducted using a diamond anvil cell, which revealed pressure-induced shifts in vibrational modes associated with P–P bonds (A 1 g , A 2 g , ${B}_{2g}$), As–As bonds (A 1 g , A 2 g , ${{B}}_{2g}$), and As–P bonds in b-As x P 1–x alloys. Two distinct pressure regimes were observed. In the first regime (region I), all vibrational modes exhibited a monotonic upshift, indicating phonon hardening due to hydrostatic pressure. In the second regime (region II), As 0.4 P 0.6 and As 0.6 P 0.4 alloys displayed a linear blueshift (or negligible change in some modes) at a reduced rate, suggesting local structural reorganization with less compression on the bonds. Notably, the alloy with the highest As concentration, As 0.8 P 0.2 , exhibited anomalous behavior in the second pressure regime, with a downward shift observed in all As–As and As–P Raman modes (and some P–P modes). Interestingly, the emergence of new peaks corresponding to the E g mode and A 1g mode of the gray-As phase was observed in this pressure range, indicating compressive strain-induced structural changes. The anomalous change in region II confirms the formation of a new local structure, characterized by elongation of the P–P, As–As, and As–P bonds along the zigzag direction within the b-As x P 1–x phase, possibly near the grain boundary. Additionally, a gray-As phase undergoes compressive structural changes. This study underscores the significance of pressure in inducing structural transformations and exploring novel phases in two-dimensional materials, including b-As x P 1–x alloys.

36 MATERIALS SCIENCE↗

Electrolyte Solvation and Ionic Association. VII. Correlating Raman Spectroscopic Data with Solvate Species

Raman spectroscopy is a widely utilized method for determining information about the solvate species present in electrolyte solutions. Difficulties arise, however, when interpreting the Raman data in terms of correlating the spectroscopic vibrational bands with specific solvate species. Examples are provided to demonstrate how erroneous conclusions may be drawn with regard to the identity and population (distribution) of the solvent-separated ion pair (SSIP), contact ion pair (CIP) and aggregate (AGG) solvate species frequently mentioned in the scientific literature.

contact ion pairs↗

An Optothermal Raman Model Accounting for Convection, Radiation, and Substrate Effects for Evaluation of the Thermal Conductivity of Two‐Dimensional Coatings

Thermal conductivity of two‐dimensional (2D) materials is important to characterize as this will govern thermal transport physics in the various thermal and energy applications benefitting from the unique properties of these materials. Here, analytical and numerical techniques are presented to determine the thermal conductivity and interfacial conductance of a 2D material coating using confocal micro‐Raman spectroscopy as a noncontact diagnostic. While several methods have been proposed for calculating the values of thermal conductivity, interfacial conductance, and spatial temperature profile, these models often do not consider effects of radiation, convection, and substrate resistance on the temperature and heat flux profiles. We present a model to calculate the thermal conductivity and interfacial conductance which accounts for convection, radiation, and substrate effects to characterize a variety of 2D material coatings, which is demonstrated using large area graphene transferred onto copper and nickel substrates. Convection and radiation effects are found to have a negligible effect on the temperature profile of supported coatings, while the substrate effects have a considerable effect and therefore impact the quantification of thermal conductivity and interfacial conductance in addition to limiting the spatial resolution of the technique. These findings will allow for more accurate and reproducible extraction of the thermal conductivity of graphene and other 2D material coatings when employing noncontact optothermal Raman spectroscopy methods.

2D coatings↗

Raman signatures of detonation soot

Soot generated from the detonation of nine explosives was investigated with Raman microspectroscopy and high-resolution transmission electron microscopy (HRTEM). The first order bands, located at approximately 1,580 (G), 1,350 (D1), 1,620 cm –1 (D2), 1,500 (D3), and 1,200 (D4), are used to provide information on the carbon allotropes and defects. The intensity ratios and the full-width at half-maximum provide an indication of the disorder in the material. The Raman spectra of soot acquired from the detonation of nine explosives showed differences which can be used to identify the precursor explosive. Overall, most differences in the spectra were correlated with the presence of amorphous carbon in the soot. In additional to identification of distinct bands in the spectra via deconvolution, principal component analysis was also used to differentiate the different types of soot. HRTEM performed on soot samples with different explosive precursors identified several distinct allotropes of carbon such as nanodiamonds, carbon onions, graphite fibers, and amorphous carbon.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Determining the twist angle of stacked MoS 2 layers using machine learning-assisted low-frequency interlayer Raman fingerprints

The investigation of twisted stacked few-layer MoS 2 has revealed novel electronic, optical, and vibrational properties over an extended period. For the successful integration of twisted stacked few-layer MoS 2 into a wide range of applications, it is crucial to employ a noninvasive, versatile technique for characterizing the layered architecture of these complex structures. Here, in this work, we introduce a machine learning-assisted low-frequency Raman spectroscopy method to characterize the twist angle of few-layer stacked MoS 2 samples. A feedforward neural network (FNN) is utilized to analyze the low-frequency breathing mode as a function of the twist angle. Moreover, using finite difference method (FDM) and density functional theory (DFT) calculations, we show that the low-frequency Raman spectra of MoS 2 are mainly influenced by the effect of the nearest and second nearest layers. A new improved linear chain model (TA-LCM) with taking the twist angle into the consideration is developed to understand the interlayer breathing modes of stacked few-layer MoS 2 . This approach can be extended to other 2D materials systems and provides an intelligent way to investigate naturally stacked and twisted interlayer interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Spatially Resolved Evaluation of Accelerated Environmental Aging on Emerging Polypropylene-Based Photovoltaic Backsheets Using Raman Spectroscopy

For this work, accelerated aging was used to assess environmental degradation in emerging co-extruded polypropylene (PP)-based backsheets under three different environmental conditions (65°C/20% relative humidity (RH), 75°C/20% RH, and 75°C/50% RH). Although differential scanning calorimetry did not measure crystallinity changes with exposure, spatially resolved Raman spectroscopy identified crystallinity increases in the core layer of aged samples, indicating a heterogeneous postcrystallization process. The Raman results were in agreement with synchrotron-based microfocused wide-angle X-ray scattering measurements. Cross-sectional nanoindentation was used to correlate localized crystallinity shifts with changes in Young's modulus. A similar trend was found where increased modulus was measured in the core layer, supporting the relationship between modulus and crystallinity. Finally, dielectric characterization was used to assess the impact of these material property changes on performance. While changes in the backsheet material properties and dielectric performance were observed with accelerated aging, these shifts generally equilibrated with time, indicating overall stability in response to environmental stressors. Additionally, the identified heterogeneous material property changes indicate that spatially resolved crystallinity measurements may be a valuable early failure indicator to be used in the assessment of PV backsheet long-term durability.

36 MATERIALS SCIENCE↗

Ultrafast Early Warning of Heart Attacks through Plasmon‐Enhanced Raman Spectroscopy using Collapsible Nanofingers and Machine Learning

Abstract As the leading cause of death, heart attacks result in millions of deaths annually, with no end in sight. Early intervention is the only strategy for rescuing lives threatened by heart disease. However, the detection time of the fastest heart‐attack detection system is >15 min, which is too long considering the rapid passage of life. In this study, a machine learning (ML)‐driven system with a simple process, low‐cost, short detection time (only 10 s), and high precision is developed. By utilizing a functionalized nanofinger structure, even a trace amount of biomarker leaked before a heart attack can be captured. Additionally, enhanced Raman profiles are constructed for predictive analytics. Five ML models are developed to harness the useful characteristics of each Raman spectrum and provide early warnings of heart attacks with >98% accuracy. Through the strategic combination of nanofingers and ML algorithms, the proposed warning system accurately provides alerts on silent heart‐attack attempts seconds ahead of actual attacks.

60 APPLIED LIFE SCIENCES↗

Mapping the Residual Stress Distribution in Polycrystalline Quartz Tiger's Eye Using Raman Spectroscopy

Stress distribution maps in polycrystalline materials are needed to reveal stress pathways caused by short‐and long‐range interactions of crystallites. Stress induced changes to wavenumbers in Raman spectroscopy is a well‐known phenomenon that occurs when a crystalline material undergoes elastic strain. Using spatially resolved Raman spectroscopy, we have developed a technique to experimentally measure grain‐scale residual stresses across a sample of polycrystal quartz Tiger's Eye. The results of this technique are validated using multiple criteria, including evaluation of the residual stress map itself and the accuracy of the measurements taken. The residual map of Tiger's Eye shows striking similarity to observed characteristics of other polycrystalline residual stress distributions, revealing heterogenous areas of high and low magnitude stresses. The stress magnitudes are consistent with residual stress magnitudes previously measured from polycrystalline quartz. Characterization of Tiger's Eye quartz also revealed the geometric nature of the iron oxide inclusions, not previously observed in Tiger's Eye quartz. With this technique, we present a residual stress map of Tiger's Eye quartz that shows with accuracy a heterogeneous stress state with inter‐ and intra‐granular detail.

36 MATERIALS SCIENCE↗

A high-pressure Raman study of FeTiO 3 ilmenite: Fermi resonance as a manifestation of Fe-Ti charge transfer

In this work, we investigated the 300 K high-pressure behavior of ilmenite using Raman spectroscopy to 54 GPa. Upon compression, we observe a Fermi resonance between the lowest frequency A g symmetry peaks (ν 4 and ν 5 ) between ~ 10 and ~ 30 GPa: bands that involve major components of Ti–O and Fe–O-related displacements, respectively. The peaks’ relative intensities switch at ~ 18 GPa and they also reach their minimum separation at ~ 20 GPa, indicating that their maximum resonance occurs between 18 and 20 GPa. The negative shift of the Ti–O-associated ν 4 vibration under compression is fully consistent with a shift in valence of Ti from 4 + to 3 + under compression. Anomalously small mode shifts of other, more localized vibrations are also consistent with a charge transfer from Fe to Ti under compression. At higher pressures, we have not found definitive evidence for a transition to the perovskite-structure at 300 K, which has been well characterized at high pressures and temperatures. At 40 GPa, we observe an apparent reversible disordering that persists up to our highest pressure. The 300 K mode shifts of the Raman active modes in FeTiO 3 under pressure are notably different from those of other ABO 3 compounds (where A = Mg, Mn and B = Ti, Si); in other ilmenite-structured compounds, the peaks shift at a faster rate and there has not been any observation of Fermi resonance. Thus, iron’s complex electronic structure, and its charge transfer with titanium, appears to play a primary role in the behavior of phonons in FeTiO 3 ilmenite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High pressure raman spectroscopy and X-ray diffraction of K2Ca(CO3)2 bütschliite: multiple pressure-induced phase transitions in a double carbonate

Abstract The crystal structure and bonding environment of K 2 Ca(CO 3 ) 2 bütschliite were probed under isothermal compression via Raman spectroscopy to 95 GPa and single crystal and powder X-ray diffraction to 12 and 68 GPa, respectively. A second order Birch-Murnaghan equation of state fit to the X-ray data yields a bulk modulus, $${K}_{0}=46.9$$ K 0 = 46.9 GPa with an imposed value of $${K}_{0}^{\prime}= 4$$ K 0 ′ = 4 for the ambient pressure phase. Compression of bütschliite is highly anisotropic, with contraction along the c -axis accounting for most of the volume change. Bütschliite undergoes a phase transition to a monoclinic C 2/ m structure at around 6 GPa, mirroring polymorphism within isostructural borates. A fit to the compression data of the monoclinic phase yields $${V}_{0}=322.2$$ V 0 = 322.2 Å 3 $$,$$ , $${K}_{0}=24.8$$ K 0 = 24.8 GPa and $${K}_{0}^{\prime}=4.0$$ K 0 ′ = 4.0 using a third order fit; the ability to access different compression mechanisms gives rise to a more compressible material than the low-pressure phase. In particular, compression of the C 2/ m phase involves interlayer displacement and twisting of the [CO 3 ] units, and an increase in coordination number of the K + ion. Three more phase transitions, at ~ 28, 34, and 37 GPa occur based on the Raman spectra and powder diffraction data: these give rise to new [CO 3 ] bonding environments within the structure.

36 MATERIALS SCIENCE↗

Characterization of SimulCam, a standoff Raman system for scientific support of SuperCam operations on Mars

During the development activities of SuperCam Calibration Target, target intended for one of the two first Raman instruments to be deployed on another planetary body, our group developed a laboratory instrument that could simulate to some extent the Raman capabilities of one of such instruments and could provide data with similar quality. The use of this kind of laboratory instruments has demonstrated its utility in the evaluation of potential calibration targets or anticipating the science outcome that an instrument could provide. The present work describes our laboratory setup to support SuperCam, evaluating similarities between both instruments, despite of differences in the hardware. Evaluation of data gathered by SuperCam on Mars and the availability of one replica of SuperCam’s Calibration Target allowed the comparison on the same set of targets, demonstrating how similar Signal-to-Noise Ratio (SNR) could be achieved from both instruments. The higher energy per pulse on SimulCam is compensated by a greater analytical footprint and the use of smaller collection optics. The results show how spectra obtained at representative distances of SuperCam are comparable. Operational principles are also comparable in terms of time resolution, and close in terms of spectral resolution. This similarity has allowed different science support works using SimulCam data, as well as the support to Mars detections using our setup. We provide examples of this support that will be shared with the community in different papers, as well as examples of possible operations activities that could benefit from experiments performed with SimulCam. We show how this setup can complement the two laboratory replicas in Los Alamos and Toulouse in providing support data to different experiments.

47 OTHER INSTRUMENTATION↗

Raman-probes for monitoring metabolites and nutrient fate in Yarrowia lipolytica using deuterated glucose

The aim of this study was to explore the application of deuterium (D) labeled glucose-D 7 as Raman-tag in Yarrowia lipolytica to assess triacyl glycerides (TAG) biosynthesis. Cells were grown in N depleted media in: (i) glucose in H 2 O (control), (ii) glucose-D 7 in H 2 O and (iii) glucose-D 7 in D 2 O, and the resulting biomass and lipids quantified. Infrared and Raman spectroscopies showed the incorporation of D with the presence of a C-D stretching bands in the silent region (1800–2600 cm -1 ) for cells grown in glucose-D 7 in H 2 O and glucose-D 7 in D 2 O as compared to the control. Fatty acid methyl ester analysis of cells grown in the three media showed significant differences in lipid profiles. Cells grown on glucose-D 7 in H 2 O and glucose-D 7 in D 2 O showed unequivocally D incorporation in fatty acids and TAG by mass spectrometry. Higher D incorporation was observed when cells were grown in D 2 O than H 2 O. Deuterium was also incorporated into the cell wall polysaccharides.

59 BASIC BIOLOGICAL SCIENCES↗

Resonant Raman in armchair graphene nanoribbons from first-principles

Resonant Raman spectra of armchair graphene nanoribbons (AGNRs) are computed using Density Functional Theory (DFT) and third-order perturbation theory. Results are benchmarked against available experimental data and compared to previously used theoretical approaches based on the Placzek approximation. Comparable agreement with experiments is found for both previously and presently used methods. In addition, a numerical analysis is carried out to provide a justification for the resonant modeling method based on the use of the frequency-dependent dielectric tensor in the Placzek approximation. Finally, this work also provides additional predictions and references for wide AGNRs that might be investigated with Raman scattering experiments in the future.

42 ENGINEERING↗

Quantification of the REE 3+ aqua ions and chloride species in aqueous fluids by in situ Raman spectroscopy using perturbations of the water band

Acidic NaCl-rich aqueous fluids play a crucial role in forming hydrothermal rare earth elements (REE) mineral deposits. Aqueous REE mobility is mostly controlled by the stabilities of REE 3+ and REE chloride species. Our current knowledge of REE speciation is based on solubility data, thermodynamic models and in situ spectroscopic measurements, sometimes coupled with molecular simulations. Here, in this study, we investigate Nd and Yb speciation in pH2 Cl-bearing solutions at 25 °C and 0.1 MPa with variable Cl/REE ratios using Raman Spectroscopy in solutions with 0.1 to 0.6 mol/kg NdCl 3 or YbCl 3 and 0.2 to 3.2 mol/kg NaCl. Due to the challenges in resolving the REE-Cl band, we developed a new method using the water vibrational mode and multivariate curve resolution (MCR) analysis. The Raman spectra for the vibrational band of water (2700 to 3900 cm –1 ) were collected at 25 °C and fitted by three Gaussian sub-peaks, then quantified using MCR analysis to de-convolute the water band into bulk H 2 O and the perturbations caused by of Cl – , REE 3+ , and REE chloride species. REE speciation based on the perturbations of the water band indicates that REE 3+ aqua ions dominate acidic solutions at 25 °C, but up to ~20 mol% YbCl 2+ forms at high YbCl 3 concentrations. The new method is promising for quantifying in situ speciation of the REE 3+ aqua ions and REE chloride species in aqueous fluids while providing information on the hydration of ions. This method improves our molecular level understanding of REE aqueous species stability and their role in REE mobilization during fluid-rock interaction.

58 GEOSCIENCES↗

Time-domain modelling and thermometry of the CH 4 v 1 Q-branch using hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering

Here, we present time-domain measurements and modelling of the CH 4 v 1 vibrational Q-branch, as well as simultaneous temperature acquisition from the CH 4 and N 2 vibrational Q-branches using broadband hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS). Accurate measurements with fs/ps CARS require knowledge of the time-domain response of the probed molecule at different temperatures and pressures. In this work, a fs/ps CARS model was developed for theCH 4 v 1 Q-branch and validated using time-resolved probe delay scans at pressures between 70 and 600 Torr and temperatures between 295 and 1000 K. A simplified modified exponential energy gap model was used to determine the linewidths of the Raman transitions within the Q-branch. Total Q-branch linewidths for the entire explored parameter space were also determined from the probe delay scans. This enabled quantitative measurements of CH 4 with fs/ps CARS as well as the temperature through the hot bands of the CH 4 v 1 Q-branch. With a broadband fs laser pulse in a two-beam phase matching scheme, the N 2 Q-branch and CH 4 v 1 Q-branch were simultaneously measured in a heated cell, and the temperatures from each molecule's spectra was evaluated. Here, the fitted temperatures corresponded well with differences ranging from 4 to 17%. It was also shown that exchanging 90% of CH 4 for N 2 or Ar at 295 K and 500 Torr did not significantly impact the normalized time-domain signal prior to a 100 picosecond probe delay. Spatially resolved one-dimensional (1-D) thermometry using the CH 4 Q-branch was also demonstrated with an imaged spatial resolution of 40 µm. With the developed model, 1-D quantitative measurements of CH 4 concentration and temperature can be measured with time resolution of tens of picoseconds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗