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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Protein Dynamics by Two-Dimensional Infrared Spectroscopy

Proteins function as ensembles of interconverting structures. The motions span from picosecond bond rotations to millisecond and longer subunit displacements. Characterization of functional dynamics on all spatial and temporal scales remains challenging experimentally. Two-dimensional infrared spectroscopy (2D IR) is maturing as a powerful approach for investigating proteins and their dynamics. We outline the advantages of IR spectroscopy, describe 2D IR and the information it provides, and introduce vibrational groups for protein analysis. We highlight example studies that illustrate the power and versatility of 2D IR for characterizing protein dynamics and conclude with a brief discussion of the outlook for biomolecular 2D IR.

Chemistry↗
DOE OSTI2021

Infrared spectroscopy of RG–Co + (H 2 O) complexes (RG = Ar, Ne, He): The role of rare gas “tag” atoms

RG n –Co + (H 2 O) cation complexes (RG = Ar, Ne, He) are generated in a supersonic expansion by pulsed laser vaporization. Here, complexes are mass-selected using a time-of-flight spectrometer and studied with infrared laser photodissociation spectroscopy, measuring the respective mass channels corresponding to the elimination of the rare gas “tag” atom. Spectral patterns and theory indicate that the structures of the ions with a single rare gas atom have this bound to the cobalt cation opposite the water moiety in a near-C 2v arrangement. The O–H stretch vibrations of the complex are shifted compared to those of water because of the metal cation charge-transfer interaction; these frequencies also vary systematically with the rare gas atom attached. The efficiencies of photodissociation also vary with the rare gas atoms because of their widely different binding energies to the cobalt cation. The spectrum of the argon complex could only be measured when at least three argon atoms were attached. In the case of the helium complex, the low binding energy allows the spectra to be measured for the low-frequency H–O–H scissors bending mode and for the O–D stretches of the deuterated analog. The partially resolved rotational structure for the antisymmetric O–H and O–D stretches reveals the temperature of these complexes (6 K) and establishes the electronic ground state. The helium complex has the same 3 B 1 ground state as the tag-free complex studied previously by Metz and co-workers (2013), but the A rotational constant is contaminated by vibrational averaging from the bending motion of the helium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Signature of magnetoelectric coupling driven finite momentum pairing in 3D ising superconductor

The finite momentum superconducting paring states (FMPs) represent a forefront of condensed matter physics. Here we report experimental evidence of FMP in a locally noncentrosymmetric bulk superconductor 4H b -TaS 2 . Using hard X-ray diffraction and angle-resolved photoemission spectroscopy, we reveal unusual 2D ferro-rotational charge density wave (CDW) and weak interlayer hopping in 4H b -TaS 2 . The superconducting upper critical field, H c2 , linearly increases via decreasing temperature, and well exceeds the Pauli limit, suggesting the dominant orbital pair-breaking mechanism. Remarkably, we observed evidence of field-induced superconductivity-to-superconductivity transition that breaks continuous rotational symmetry of the s-wave uniform pairing in the Bardeen-Cooper-Schrieffer theory down to the six-fold rotation symmetry. Ginzburg-Landau free energy analysis shows that magnetoelectric coupling, induced by 2D ferro-rotational CDW, stabilizes FMP that provides an explanation of the lowering rotation symmetry. Our results provide a new understanding of unconventional superconducting behaviors of the bulk quantum heterostructure 4H b -TaS 2 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Tendencies of enhanced electronic nematicity in the Hubbard model and a comparison with Raman scattering on high-temperature superconductors

The pseudogap regime of the cuprate high-temperature superconductors is characterized by a variety of competing orders, the nature of which are still widely debated. Recent experiments have provided evidence for electron nematic order, in which the electron fluid breaks rotational symmetry while preserving translational invariance. Raman spectroscopy, with its ability to symmetry resolve low energy excitations, is a unique tool that can be used to assess nematic fluctuations and nematic ordering tendencies. Here we compare results from determinant quantum Monte Carlo simulations of the Hubbard model to experimental results from Raman spectroscopy in La 2-x Sr x CuO 4 , which show a prominent increase in the B 1g response around 10% hole doping as the temperature decreases, indicative of a rise in nematic fluctuations at low energy. Finally, our results support a picture of nematic fluctuations with B 1g symmetry occurring in underdoped cuprates, which may arise from melted stripes at elevated temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Decay spectroscopy of an isomeric state in Md251

Excited states in Md251 have been populated by decay of an isomeric state at Ex≈1174 keV and studied via delayed γ-ray spectroscopy. We observe the population of two rotational bands, one of which we identify as the Nilsson π72[514] ground-state band and the other we propose is based on the π92[624] configuration. From the observed decay pattern, we suggest that the isomer spin parity is 232+, with the three-quasiparticle configuration π72[514]⊗{ν72[624]⊗ν92[734]}Kπ=8−. We compare our results to theoretical predictions of the single- and multi-quasiparticle structure of Md251.

Morse, C↗
DOE OSTI2023

Kramers–Kronig relation in attosecond transient absorption spectroscopy

The Kramers–Kronig relation (KKR) has a wide range of applications in extreme ultraviolet (XUV) and x-ray spectroscopy. However, the validity of KKR for many of these applications has not been systematically studied, while it is known to require careful attention in nonlinear and pump–probe experiments in optical domain spectroscopy. Here, we study the validity of KKR in XUV attosecond transient absorption spectroscopy pump–probe measurements both experimentally and theoretically using argon Fano resonances as a case study. Experiments are enabled by a phase-resolved method dubbed Complex Attosecond Transient-absorption Spectroscopy (CATS). Although the estimations based on the rotating-wave approximation suggest that KKR violation could be expected in the studied case, our results validate KKR and provide a solid basis for its application in a broad range of attosecond spectroscopy experiments.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Hyperspectral imaging of exciton confinement within a moiré unit cell with a subnanometer electron probe

Electronic and optical excitations in two-dimensional systems are distinctly sensitive to the presence of a moiré superlattice. Here we used cryogenic transmission electron microscopy and spectroscopy to simultaneously image the structural reconstruction and associated localization of the lowest-energy intralayer exciton in a rotationally aligned WS 2 -WSe 2 moiré superlattice. In conjunction with optical spectroscopy and ab initio calculations, we determined that the exciton center-of-mass wave function is confined to a radius of approximately 2 nanometers around the highest-energy stacking site in the moiré unit cell. Our results provide direct evidence that atomic reconstructions lead to the strongly confining moiré potentials and that engineering strain at the nanoscale will enable new types of excitonic lattices.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Determination of single crystal elastic moduli of KTb3F10 by resonant ultrasound spectroscopy

KTb3F10 (KTF) has been developed in recent years as a candidate Faraday rotator material because of its cubic symmetry, high figures of merit, and low absorption coefficient. While considerable efforts have focused on crystal growth and optical properties, investigations of fundamental thermodynamic behavior of KTF have been limited. Here, we report elastic moduli C11, C12, and C44 of single crystalline KTF measured by resonant ultrasound spectroscopy from 280 K up to 300 K and the obtained temperature derivatives of each modulus. We additionally report the single crystal elastic moduli of the rare-earth garnet Y3Al5O12 (YAG), yielding results that agree well with the prior literature. We found C11=135.62 GPa, C12=58.11 GPa, and C44=44.81 GPa for KTF and C11=332.43 GPa, C12=109.58 GPa, and C44=114.81 GPa for YAG at room temperature. The present results have been compared with previous experimental and theoretical results and with common oxide and fluoride optical materials, revealing the relative softness of KTF. The low elastic moduli of KTF are, in turn, responsible for its low thermal conductivity and low Debye frequency compared to other laser host materials.

Balodhi, Ashiwini (ORCID:0000000290496382)↗
DOE OSTI2023

Ultrafast relaxation of lattice distortion in two-dimensional perovskites

Direct visualization of ultrafast coupling between charge carriers and lattice degrees of freedom in photoexcited semiconductors has remained a long-standing challenge and is critical for understanding the light-induced physical behaviour of materials under extreme non-equilibrium conditions. Here we obtain a direct visualization of the structural dynamics in monocrystalline 2D perovskites. We achieve this by monitoring the evolution of wavevector-resolved ultrafast electron diffraction intensity following above-bandgap high-density photoexcitation. Our analysis reveals a light-induced ultrafast reduction in antiferro-distortion resulting from a strong interaction between the electron–hole plasma and perovskite lattice, which induces an in-plane octahedra rotation towards a more symmetric phase. Correlated ultrafast spectroscopy performed at the same carrier density as ultrafast electron diffraction reveals that the creation of a dense electron–hole plasma triggers the relaxation of lattice distortion at shorter timescales by modulating the crystal cohesive energy. Then we show that the interaction between carrier gas and lattice can be altered by tailoring the rigidity of the 2D perovskite by choosing an appropriate organic spacer layer.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Contrasting the characteristics of atmospheric pressure plasma jets operated with single and double dielectric material: physicochemical characteristics and application to bacterial killing

Abstract This study reports an experimental comparison of two types of atmospheric pressure plasma jets in terms of their fundamental plasma characteristics and efficacy in bacterial sterilization. The plasma jets are fabricated by inserting a high voltage electrode inside a one-end closed (double DBD plasma jet) or both ends open (single DBD plasma jet) quartz tubes which are further enclosed inside a second quartz tube containing a ground electrode. Both plasma jets are operated in contact with water surface by using a unipolar pulsed DC power supply with helium as the working gas. Results from electrical and time-resolved imaging show that the single DBD configuration induces 3–4 times higher accumulation of charges onto the water surface with significantly faster propagation of plasma bullets. These results are accompanied by the higher discharge intensity as well as stronger emissions from short-lived reactive species which were analyzed through optical emission spectroscopy at the plasma-water interface. The rotational temperature for the single DBD configuration was observed to be higher making it unsafe for direct treatments of sensitive biological targets. These characteristics of the single DBD configuration result in the production of more than two times higher concentration of H 2 O 2 in plasma activated water. Shielding of the HV electrode reduces the plasma potential which in turn reduces the electric field & electron energy at the plasma-water interface. The reduced electric field for the double DBD configuration was lower by ≈463 Td than the single DBD configuration. The bactericidal efficacy of the two configurations of the plasma jets were tested against Escherichia coli , a well studied Gram-negative bacterium that can be commensal and pathogenic in human body. Our results demonstrate that although single DBD plasma jet result in stronger antibacterial effects, the double DBD configuration could be safer.

Physics↗
DOE OSTI2025

Polarization-separated double-imaging spectroscopy for weakly-ionized plasma diagnostics

Laser Thomson scattering, which provides thermal properties of electrons, has been extensively utilized in plasma diagnostics. However, being a non-resonant linear light scattering technique, it often encounters several challenges in weakly-ionized plasma diagnostics due to spectral overlap with different scatterings induced from other existing species, including Mie, Rayleigh, and rotational Raman scatterings. To address this challenge, we propose an imaging spectroscopy technique, polarization-separated double-imaging spectroscopy (PoDIS), which selectively separates specific scatterings based on their polarization characteristics. Using an atmospheric plasma jet as a plasma source for demonstration, we show that PoDIS can effectively separate rotational Raman and Thomson scatterings from a superimposed spectrum without prior knowledge or assumptions about the thermal properties of neutrals or electrons. This separation enables independent fitting of the rotational Raman and Thomson scattering spectra, allowing for precise determination of the thermal properties of neutral particles and electrons separately.

Bak, Junhwi [Texas A&M University, College Station↗
DOE OSTI2025

In Situ Atmospheric Plume Thermometry via Carbon Monoxide Spectral Profile: Laboratory and Field Validation

For small molecules with large rotational constants, knowing the relative intensities of the ro-vibrational transitions can be used to determine the temperature within a gas plume. We demonstrate the use of carbon monoxide (CO) as an in situ spectroscopic probe of gas plume temperature by application of both laboratory and standoff Fourier transform infrared spectroscopy to monitor the CO spectral response at different temperatures. Here, the measured CO rotational contours were analyzed using a simple Boltzmann model to deduce the population distribution of the J-levels, from which the in-plume temperature is deduced. The method was vetted by comparing deduced temperatures in both static laboratory measurements of known temperatures, as well as field measurements using a simulated smokestack release. For the smokestack experiments, spectroscopically deduced temperatures were compared to readings from a series of thermocouples placed at strategically sampled distances along the plume trajectory. Both the spectroscopically-derived and thermocouple-measured temperatures revealed an expansion-induced (mixing) rapid cooling of the plume, with the infrared thermometry values displaying greater temperature values which are believed to better represent the actual plume temperatures.

Analysis of rotational structure↗
DOE OSTI2020

Ro-vibrational Spectroscopy of 2,5-Norbornadiene between 400 and 850 cm-1

Rotationally-resolved infrared absorption spectra of the two lowest-energy fundamental bands for each of the three infrared active symmetry species of 2,5-norbornadiene (C2v point group symmetry; asymmetry parameter ? = -0.2203), ?11 (a1), ?12(a1), ?28(b1), ?29(b1), ?38(b2), and ?39(b2), have been measured, assigned and fit to a semi-rigid rotor Hamiltonian to produce a set of spectroscopic constants for each band. The fit band centers are ?11 (a1), c-type transitions, 728.852357(3) cm-1; ?12 (a1), c-type transitions, 417.31604(1) cm-1; ?28 (b1), a-type transitions, 656.719741(3) cm-1; ?29 (b1), a-type transitions, 500.31425(1) cm-1; ?38 (b2), b-type transitions, 800.82243(2) cm-1; and ?39 (b2), b-type transitions, 539.23110(6) cm-1. Using ground state combination differences from the ?11 and ?28 bands and previously published microwave data, an improved set of ground state spectroscopic constants were fit for the parent isotopologue of the molecule. This research was conducted at the Pacific Northwest National Laboratory (PNNL), which is operated by Battelle Memorial Institute for the Department of Energy (DOE) under Contract No. DE-AC05-76RL01830.

Sams, R L.↗
DOE OSTI2022

Geometry optimizations with spinor-based relativistic coupled-cluster theory

Development of analytic gradients for relativistic coupled-cluster singles and doubles augmented with a non-iterative triples [CCSD(T)] method using an all-electron exact two-component Hamiltonian with atomic mean-field spin–orbit integrals (X2CAMF) is reported. This enables efficient CC geometry optimizations with spin–orbit coupling included in orbitals. Here, the applicability of the implementation is demonstrated using benchmark X2CAMF-CCSD(T) calculations of equilibrium structures and harmonic vibrational frequencies for methyl halides, CH 3 X (X = Br, I, and At), as well as calculations of rotational constants and infrared spectrum for RaSH+, a radioactive molecular ion of interest to spectroscopic study.

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

High-resolution vibrational predissociation spectroscopy of I - ·H 2 O by single-mode CW infrared excitation in a 3D cryogenic ion trap

We describe the integration of a tunable, single-mode, continuous wave infrared laser into a cryogenic ion spectroscopy experiment to measure the rovibrational spectrum of the I - ∙H 2 O complex in the OH stretching region. These upper levels lie about 300 cm -1 above the dissociation threshold. The measurements are carried out by loading the ions in a radiofrequency ion trap at 10 Hz and cooling them to 5 K with pulsed He buffer gas. IR photodissociation (PD) of the I - ∙H 2 O complex is monitored by recording the I - product yield by time-of-flight mass spectrometry as a function of laser wavelength. Very narrow (Δν~75 MHz) rotational lines are observed throughout the spectrum, indicating long (ca. 2 ns) lifetimes for the excited metastable rovibrational levels. Rotational analysis of the band arising from the K”=1 to K’=2 transition of the free OH stretching fundamental yields the structure of the complex for the first time. Over 50% of the trapped ion ensemble in the trap can be photodissociated upon excitation of a single rotational line. This enables very high signal-to-noise in the PD spectrum, and is traced to a mechanism in which the ground state rotational levels are rapidly equilibrated by collisions with the buffer gas.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Structures of glasses created by multiple kinetic arrests

X-ray scattering has been used to characterize glassy itraconazole (ITZ) prepared by cooling at different rates. Faster cooling produces ITZ glasses with lower (or zero) smectic order with more sinusoidal density modulation, larger molecular spacing, and shorter lateral correlation between the rod-like molecules. We find that each glass is characterized by not one, but two fictive temperatures T f (the temperature at which a chosen order parameter is frozen in the equilibrium liquid). The higher T f is associated with the regularity of smectic layers and lateral packing, while the lower T f with the molecular spacings between and within smectic layers. This indicates that different structural features are frozen on different timescales. The two timescales for ITZ correspond to its two relaxation modes observed by dielectric spectroscopy: the slower δ mode (end-over-end rotation) is associated with the freezing of the regularity of molecular packing and the faster α mode (rotation about the long axis) with the freezing of the spacing between molecules. Finally, our finding suggests a way to selectively control the structural features of glasses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗