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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 829 records · Page 46
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Multidimensional Coherent Spectroscopy of Molecular Polaritons: Langevin Approach

We present a microscopic theory for nonlinear optical spectroscopy of N molecules in an optical cavity. Using the Heisenberg-Langevin equation, an analytical expression is derived for the time- and frequency-resolved signals accounting for arbitrary numbers of vibrational excitations. We identify clear signatures of the polariton-polaron interaction from multidimensional projections of the signal, e.g., pathways and timescales. Cooperative dynamics of cavity polaritons against intramolecular vibrations is revealed, along with a crosstalk between long-range coherence and vibronic coupling that may lead to localization effects. Our results further characterize the polaritonic coherence and the population transfer that is slower.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1997

Liquid water in the domain of cubic crystalline ice Ic

Vapor-deposited amorphous water ice when warmed above the glass transition temperature (120-140 K), is a viscous liquid which exhibits a viscosity vs temperature relationship different from that of liquid water at room temperature. New studies of thin water ice films now demonstrate that viscous liquid water persists in the temperature range 140-210 K. where it coexists with cubic crystalline ice. The liquid character of amorphous water above the glass transition is demonstrated by (1) changes in the morphology of water ice films on a nonwetting surface observed in transmission electron microscopy (TEM) at around 175 K during slow warming, (2) changes in the binding energy of water molecules measured in temperature programmed desorption (TPD) studies, and (3) changes in the shape of the 3.07 micrometers absorption band observed in grazing angle reflection-absorption infrared spectroscopy (RAIRS) during annealing at high temperature. whereby the decreased roughness of the water surface is thought to cause changes in the selection rules for the excitation of O-H stretch vibrations. Because it is present over such a wide range of temperatures, we propose that this form of liquid water is a common material in nature. where it is expected to exist in the subsurface layers of comets and on the surfaces of some planets and satellites.

NASA Center ARC↗
DOE OSTI2021

Transparent window 2D IR spectroscopy of proteins

Proteins are complex, heterogeneous macromolecules that exist as ensembles of interconverting states on a complex energy landscape. A complete, molecular-level understanding of their function requires experimental tools to characterize them with high spatial and temporal precision. Infrared (IR) spectroscopy has an inherently fast time scale that can capture all states and their dynamics with, in principle, bond-specific spatial resolution. Two-dimensional (2D) IR methods that provide richer information are becoming more routine but remain challenging to apply to proteins. Spectral congestion typically prevents selective investigation of native vibrations; however, the problem can be overcome by site-specific introduction of amino acid side chains that have vibrational groups with frequencies in the “transparent window” of protein spectra. This Perspective provides an overview of the history and recent progress in the development of transparent window 2D IR of proteins.

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

Anion Photoelectron Spectroscopy and Ab Initio Studies of the UF – Anion

A synergistic anion photoelectron spectroscopic and ab initio computational study of photodetachment of UF – is reported. The measurement determined a vertical detachment energy of 0.63(03) eV, which is consistent with a spinor-based relativistic coupled-cluster CCSD(T) value of 0.61 eV. The complex spectral features due to excited electronic states and vibrational progressions of UF are analyzed and assigned with the help of spin–orbit-coupled multireference perturbation theory and spinor-based relativistic coupled-cluster calculations. UF and UF – are confirmed to be dominated by ionic bonding. Furthermore, the usefulness of the spinor CCSD(T) approach is demonstrated.

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

Selective photo-excitation of molecules enabled by stimulated Raman pre-excitation

Double resonance excitation, where the energies of vibrational and electronic molecular transitions are combined in a single, sequential excitation process, was introduced in the 1970s but has only been recently applied to microscopy due to the immense progress in Raman spectroscopy. The value of the technique is in combining the chemical selectivity of IR or Raman excitation with the much larger cross-sections of electronic transitions. Recently, it has been shown to be particularly suited for the detection and identification of chromophores at low concentrations and in the presence of spectral crosstalk. However, despite its low quantum yield per pulse sequence, we believe the technique has potential for selective photochemical transformations. There are some cases (e.g., the selective excitation of optogenetic switches) where the low yield may be overcome by repeated excitations to build up biochemically relevant concentrations. Here we show that double resonance excitation using general, non-resonant Raman pre-excitation is a viable candidate for selectively promoting molecules to chemically active energy levels. Further, the use of non-resonant Raman pre-excitation is less constraining than resonant Raman (used in previous double resonance microscopy works) since the choice of Raman pump-Stokes frequencies may be rather freely chosen.

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

X-ray dichroism as a probe of orbital quenching and unquenching induced by optically excited Jahn-Teller modes

The use of soft-X-ray spectroscopy to probe changes in the ground-state due to vibronic excitations is studied. The changes in L-edge X-ray absorption on divalent cobalt in the presence of a vibrating Jahn-Teller distortion are calculated. For linear dichroism, a strong dependence on the distortion is obtained reflecting the change in the local quadrupole moment due to the changes in the xy versus yz/zx hole densities during the oscillation. Here, in the presence of a magnetic moment, significant variations in the circular dichroic signal are obtained related to the quenching and unquenching of the orbital angular momentum.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1994

Superfluid helium sloshing dynamics induced oscillations and fluctuations of angular momentum, force and moment actuated on spacecraft driven by gravity gradient or jitter acceleration associated with slew motion

The generalized mathematical formulation of sloshing dynamics for partially filled liquid of cryogenic superfluid helium II in dewar containers driven by the gravity gradient and jitter accelerations associated with slew motion for the purpose to perform scientific observation during the normal spacecraft operation are investigated. An example is given with the Advanced X-Ray Astrophysics Facility-Spectroscopy (AXAF-S) for slew motion which is responsible for the sloshing dynamics. The jitter accelerations include slew motion, spinning motion, atmospheric drag on the spacecraft, spacecraft attitude motions arising from machinery vibrations, thruster firing, pointing control of spacecraft, crew motion, etc. Explicit mathematical expressions to cover these forces acting on the spacecraft fluid systems are derived. The numerical computation of sloshing dynamics is based on the non-inertia frame spacecraft bound coordinate, and solve time-dependent, three-dimensional formulations of partial differential equations subject to initial and boundary conditions. The explicit mathematical expressions of boundary conditions to cover capillary force effect on the liquid-vapor interface in microgravity environments are also derived. The formulations of fluid moment and angular moment fluctuations in fluid profiles induced by the sloshing dynamics, together with fluid stress and moment fluctuations exerted on the spacecraft dewar containers have also been derived. Examples are also given for cases applicable to the AXAF-S spacecraft sloshing dynamics associated with slew motion.

Hung, R. J.↗
NASA NTRS2000

Experimental and Ab Initio Studies of the HDO Absorption Spectrum in the 13165-13500 1/cm Spectral Region

The HDO absorption spectrum has been recorded in the 13165 - 13500 cm(exp-1) spectral region by Intracavity Laser Absorption Spectroscopy. The spectrum (615 lines), dominated by the 2n2 + 3n3 and n1+3n3 bands was assigned and modeled leading to the derivation of 196 accurate energy levels of the (103) and (023) vibrational states. Finally, 150 of these levels have been reproduced by an effective Hamiltonian involving two vibrational dark states interacting with the (023) and ( 103) bright states. The rms deviation achieved by variation of 28 parameters is 0.05-1 cm, compared to an averaged experimental uncertainty of 0.007-1 cm, indicating the limit of validity of the effective Hamiltonian approach for HDO at high vibrational excitation. The predictions of previous ab initio calculations of the HDO spectrum were extensively used in the assignment process. The particular spectral region under consideration has been used to test and discuss the improvements of new ab initio calculations recently performed on the basis of the same potential energy surface but with an improved dipole moment surface. The improvements concern both the energy levels and the line intensities. In particular, the strong hybrid character of the n1+3n3 band is very well accounted for by the the new ab initio calculations.

Schwenke, David↗
NASA NTRS1996

The High Resolution Infrared Spectrum of CH(sub 3)D in the Region 900-1700 cm(sup -1)

The high resolution absorption spectrum of CH(sub 3)D in the region of 900-1700 cm(sup -1) has been revisited on the basis of new long path experimental data recorded with the Fourier transform spectrometer at Kitt Peak. A theoretical model used previously for spherical rotors has been adapted for polyatomic molecules in order to analyze the vibrational polyads of CH(sub 3)D simultaneously.

methane atmosphere study spectroscopy↗
NASA NTRS2016

Mid and Thermal Infrared Remote Sensing at the Jet Propulsion Laboratory

The mid and thermal infrared (MTIR) for the Earth surface is defined between 3 and 14µm. In the outer solar system, objects are colder and their Planck response shifts towards longer wavelengths. Hence for these objects (e.g. icy moons, polar caps, comets, Europa), the thermal IR definition usually stretches out to 50µm and beyond. Spectroscopy has been a key part of this scientific exploration because of its ability to remotely determine elemental and mineralogical composition. Many key gas species such as methane, ammonia, sulfur, etc. also have vibrational bands which show up in the thermal infrared spectrum above the background response. Over the past few decades, the Jet Propulsion Laboratory has been building up a portfolio of technology to capture the MTIR for various scientific applications. Three recent sensors are briefly reviewed: The airborne Hyperspectral thermal emission spectrometer (HyTES), the ECOsystem Spaceborne Thermal Radiometer Experiment on Space Station (ECOSTRESS) and Mars Climate Sounder (MCS)/DIVINER. Each of these sensors utilize a different technology to provide a remote sensing product based on MTIR science. For example, HyTES is a push-brooming hyperspectral imager which utilizes a large format quantum well infrared photodetector (QWIP). The goal is to transition this to a new complementary barrier infrared photodetector (CBIRD) with a similar long wave cut-off and increased sensitivity. ECOSTRESS is a push-whisk Mercury Cadmium Telluride (MCT) based high speed, multi-band, imager which will eventually observe and characterize plant/vegetation functionality and stress index from the International Space Station (ISS) across the contiguous United States (CONUS). MCS/DIVINER utilizes thermopile technology to capture the thermal emission from the polar caps and shadow regions of the moon. Each sensor utilizes specific JPL technology to capture unique science. similar long wave cut-off and increased sensitivity. ECOSTRESS is a push-whisk Mercury Cadmium Telluride (MCT) based high speed, multi-band, imager which will eventually observe and characterize plant/vegetation functionality and stress index from the International Space Station (ISS) across the contiguous United States (CONUS). MCS/DIVINER utilizes thermopile technology to capture the thermal emission from the polar caps and shadow regions of the moon. Each sensor utilizes specific JPL technology to capture unique science.

Johnson, William R.↗
DOE OSTI2022

Formation and detection of metastable formic acid in a supersonic expansion: High resolution infrared spectroscopy of the jet-cooled cis -HCOOH conformer

High-resolution direct absorption infrared spectra of metastable cis-formic acid (HCOOH) trapped in a cis-well resonance behind a 15 kcal/mol barrier are reported for the first time, with the energetically unstable conformer produced in a supersonic slit plasma expansion of trans-formic acid/H 2 mixtures. We present a detailed high-resolution rovibrational analysis for cis-formic acid species in the OH stretch (ν 1 ) fundamental, providing first precision vibrational band origin, rotational constants, and term values, which in conjunction with ab initio calculations at the couple-cluster with single, double, and perturbative triple [CCSD(T)]/ANOn (n = 0, 1, 2) level support the experimental assignments and establish critical points on the potential energy surface for internal rotor trans-to-cis isomerization. Relative intensities for a- and b-type transitions observed in the spectra permit the transition dipole moment components to be determined in the body fixed frame and prove to be in good agreement with ab initio CCSD(T) theoretical estimates but in poor agreement with simple bond-dipole predictions. As a result, the observed signal dependence on H 2 in the discharge suggests the presence of a novel H atom radical chemical mechanism for strongly endothermic “up-hill” internal rotor isomerization between trans- and cis-formic acid conformers.

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

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↗
DOE OSTI2021

Vibrational Sum-Frequency Generation Hyperspectral Microscopy for Molecular Self-Assembled Systems

In this review, we discuss the recent developments and applications of vibrational sum-frequency generation (VSFG) microscopy. This hyperspectral imaging technique can resolve systems without inversion symmetry, such as surfaces, interfaces and noncentrosymmetric self-assembled materials, in the spatial, temporal, and spectral domains. We discuss two common VSFG microscopy geometries: wide-field and confocal point-scanning. We then introduce the principle of VSFG and the relationships between hyperspectral imaging with traditional spectroscopy, microscopy, and time-resolved measurements. We further highlight crucial applications of VSFG microscopy in self-assembled monolayers, cellulose in plants, collagen fibers, and lattice self-assembled biomimetic materials. In these systems, VSFG microscopy reveals relationships between physical properties that would otherwise be hidden without being spectrally, spatially, and temporally resolved. Lastly, we discuss the recent development of ultrafast transient VSFG microscopy, which can spatially measure the ultrafast vibrational dynamics of self-assembled materials. The review ends with an outlook on the technical challenges of and scientific potential for VSFG microscopy.

Chemistry↗
DOE OSTI2025

Anisotropic Raman Scattering and Lattice Orientation Identification of 2M-WS 2

Anisotropic materials with low symmetries hold significant promise for next-generation electronic and quantum devices. 2M-WS 2 , which is a candidate for topological superconductivity, has garnered considerable interest. However, a comprehensive understanding of how its anisotropic features contribute to unconventional superconductivity, along with a simple, reliable method to identify its crystal orientation, remains elusive. Here, we combine theoretical and experimental approaches to investigate angle- and polarization-dependent anisotropic Raman modes of 2M-WS 2 . Through first-principles calculations, we predict and analyze the phonon dispersion and lattice vibrations of all Raman modes in 2M-WS 2 . We establish a direct correlation between their anisotropic Raman spectra and high-resolution transmission electron microscopy images. Finally, we demonstrate that anisotropic Raman spectroscopy can accurately determine the crystal orientation and twist angle between two stacked 2M-WS 2 layers. Furthermore, our findings provide insights into the electron–phonon coupling and anisotropic properties of 2M-WS 2 , paving the way for the use of anisotropic materials in advanced electronic and quantum devices.

2M-WS2↗
NASA NTRS1984

Molecular velocimetry using stimulated Raman spectroscopy

Molecular flow velocity of N2 was measured in a supersonic wind tunnel using inverse Raman spectroscopy. This technique employs the large Doppler shift exhibited by the molecules when the pump and probe laser beams are counter-propagating (backward scattering). A retrometer system is employed to yield a vibration-free optical configuration which has the additional advantage of obtaining both the forward and backward scattered spectra simultaneously. The linebreadths and their relative Doppler shift can be used to determine the static pressure, translational temperature, and molecular flow velocity. A demonstration of the concept was performed in a supersonic wind tunnel and included: (1) measurements over the Mach number range 2.50 to 4.63; (2) static pressure measurements (at Mach 2.50) corresponding to a Reynolds number per foot range of 1 to 5 x 10 to the 6th power; and (3) measurements behind the shock wave of a flat plate model.

Exton, R. J.↗
NASA NTRS1985

Shock effects on hydrous minerals and implications for carbonaceous meteorites

The effect of shock loading over the pressure range of 29-59 GPa on the shock-recovered specimens of antigorite serpentine, Mg3Si2O5(OH)4, were investigated employing infrared (IR) spectroscopy, thermogravimetric analysis, and optical and scanning electron microscopy. With increasing shock pressure, there was an increase in H2O IR absorption peaks at the expense of OH peaks, while the changes in SiO bond vibration modes were identical to those seen for other, nonhydrous minerals. Thermogravimetric results on vented assembly samples showed linear relationships between the shock pressure and both the length of dehydration interval and the effective activation energy for releasing post-shock structural water. Optical and scanning electron microscopy revealed gas bubbles, which appeared to be injected into zones of partial melting, and vesicular dark veins distributed throughout the shocked samples. It is suggested that shock loading of hydrous minerals would release and redistribute free water in the regoliths of carbonaceous chondrite parent bodies, giving rise to observed hydrous alterations.

Lange, M. A.↗
NASA NTRS1986

Raman spectroscopy of gases with a Fourier transform spectrometer - The spectrum of D2

Fourier transform spectrometry (FTS) is presently used to record the spontaneous incoherent laser Raman spectra of gases. The high resolution, sensitivity, calibration accuracy and spectral coverage achieved demonstrate the viability of FTS for Raman spectroscopy. Attention is given to the coefficients obtained by fitting measurements obtained from the spectrum of D2, containing both v = 0-0 and 1-0 transitions, to the Dunham (1932) expansion of the vibration-rotation energy levels.

Jennings, D. E.↗