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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 OSTI2016

High resolution spectroscopy of jet cooled phenyl radical: The ν{sub 1} and ν{sub 2} a{sub 1} symmetry C–H stretching modes

A series of CH stretch modes in phenyl radical (C{sub 6}H{sub 5}) has been investigated via high resolution infrared spectroscopy at sub-Doppler resolution (∼60 MHz) in a supersonic discharge slit jet expansion. Two fundamental vibrations of a{sub 1} symmetry, ν{sub 1} and ν{sub 2}, are observed and rotationally analyzed for the first time, corresponding to in-phase and out-of-phase symmetric CH stretch excitation at the ortho/meta/para and ortho/para C atoms with respect to the radical center. The ν{sub 1} and ν{sub 2} band origins are determined to be 3073.968 50(8) cm{sup −1} and 3062.264 80(7) cm{sup −1}, respectively, which both agree within 5 cm{sup −1} with theoretical anharmonic scaling predictions based on density functional B3LYP/6-311g++(3df,3dp) calculations. Integrated band strengths for each of the CH stretch bands are analyzed, with the relative intensities agreeing remarkably well with theoretical predictions. Frequency comparison with previous low resolution Ar-matrix spectroscopy [A. V. Friderichsen et al., J. Am. Chem. Soc. 123, 1977 (2001)] reveals a nearly uniform Δν ≈ + 10-12 cm{sup −1} blue shift between gas phase and Ar matrix values for ν{sub 1} and ν{sub 2}. This differs substantially from the much smaller red shift (Δν ≈ − 1 cm{sup −1}) reported for the ν{sub 19} mode, and suggests a simple physical model in terms of vibrational mode symmetry and crowding due to the matrix environment. Finally, the infrared phenyl spectra are well described by a simple asymmetric rigid rotor Hamiltonian and show no evidence for spectral congestion due to intramolecular vibrational coupling, which bodes well for high resolution studies of other ring radicals and polycyclic aromatic hydrocarbons. In summary, the combination of slit jet discharge methods with high resolution infrared lasers enables spectroscopic investigation of even highly reactive combustion and interstellar radical intermediates under gas phase, jet-cooled (T{sub rot} ≈ 11 K) conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hyperfine structures and isotopic shifts of uranium transitions using tunable laser spectroscopy of laser ablation plumes

We report isotopic shifts and hyperfine structures of selected U transitions employing tunable spectroscopy viz: laser-induced fluorescence and laser absorption spectroscopy of laser ablation plumes. The laser-produced plasmas were produced during ns laser ablation on a natural U metal which contains 0.7% 235U. Our results show that isotopic shifts between 238U and 235U are entangled with hyperfine structures of 235U. The isotopic ratio obtained using laser-induced fluorescence is affected by optical saturation effect. Time-resolved laser absorption spectroscopy is carried out for evaluating the optical absorption and estimating the hyperfine constants.

(020.3260) Isotope shifts↗
DOE OSTI2015

Reactive intermediates in {sup 4}He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Singlet dihydroxycarbene (HOC{sup ¨}OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans,trans- or trans,cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans- and trans, cis-rotamers are (μ{sub a}, μ{sub b}) = (0.00, 0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HOC{sup ¨}OH torsional interconversion and tautomerization barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Synchrotron-based double imaging photoelectron/photoion coincidence spectroscopy of radicals produced in a flow tube: OH and OD

We present a microwave discharge flow tube coupled with a double imaging electron/ion coincidence device and vacuum ultraviolet (VUV) synchrotron radiation. The system has been applied to the study of the photoelectron spectroscopy of the well-known radicals OH and OD. The coincidence imaging scheme provides a high selectivity and yields the spectra of the pure radicals, removing the ever-present contributions from excess reactants, background, or secondary products, and therefore obviating the need for a prior knowledge of all possible byproducts. The photoelectron spectra encompassing the X{sup 3}Σ{sup −} ground state of the OH{sup +} and OD{sup +} cations have been extracted and the vibrational constants compared satisfactorily to existing literature values. Future advantages of this approach include measurement of high resolution VUV spectroscopy of radicals, their absolute photoionization cross section, and species/isomer identification in chemical reactions as a function of time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Optical spectroscopy of molecular junctions: Nonequilibrium Green’s functions perspective

We consider optical spectroscopy of molecular junctions from the quantum transport perspective when radiation field is quantized and optical response of the system is simulated as photon flux. Using exact expressions for photon and electronic fluxes derived within the nonequilibrium Green function (NEGF) methodology and utilizing fourth order diagrammatic perturbation theory (PT) in molecular coupling to radiation field, we perform simulations employing realistic parameters. Results of the simulations are compared to the bare PT which is usually employed in studies on nonlinear optical spectroscopy to classify optical processes. We show that the bare PT violates conservation laws, while flux conserving NEGF formulation mixes optical processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Applications of Doppler-free saturation spectroscopy for edge physics studies (invited)

Doppler-free saturation spectroscopy provides a very powerful method to obtain detailed information about the electronic structure of the atom through measurement of the spectral line profile. This is achieved through a significant decrease in the Doppler broadening and essentially an elimination of the instrument broadening inherent to passive spectroscopic techniques. In this paper we present the technique and associated physics of Doppler-free saturation spectroscopy in addition to how one selects the appropriate transition. Simulations of H{sub δ} spectra are presented to illustrate the increased sensitivity to both electric field and electron density measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2018

The charge exchange recombination spectroscopy diagnostic on the upgraded Lithium Tokamak eXperiment (LTX-β)

The Lithium Tokamak eXperiment has undergone an upgrade to LTX-β, a major part of which is the addition of neutral beam injection (NBI). NBI has allowed for a new charge exchange recombination spectroscopy (CHERS) system to be installed in order to measure impurity concentrations, ion temperature, and toroidal velocity. Previously on LTX measuring these parameters relied on passive spectroscopy and inversion techniques and had large uncertainty. The CHERS system has 52 total views, split into four groups of 13, half facing toward the beam and half symmetrically facing away from the beam, so the background non-beam related emission can be simultaneously subtracted. Both sets of views sample a major radius of 27-59 cm, with resolution through the beam of 1.5-2.5 cm. LTX-β is expected to have its magnetic axis near 35 cm, with minor radii of 18-23 cm. Three separate spectrometers will be used for the diagnostic, giving the system great flexibility to simultaneously measure emission from multiple impurity lines. The viewing optics are f/1.8, allowing all of the spectrometers to be fully illuminated. Design and calibration of the system as well as the advantages of various configurations of the spectrometers will be highlighted.

Elliott, Drew↗
DOE OSTI2015

NEAR-ULTRAVIOLET SPECTROSCOPY OF STAR-FORMING GALAXIES FROM eBOSS: SIGNATURES OF UBIQUITOUS GALACTIC-SCALE OUTFLOWS

We present rest-frame near-ultraviolet (NUV) spectroscopy of star-forming galaxies (SFGs) at 0.6 < z < 1.2 from the Extended Baryon Oscillation Spectroscopic Survey (eBOSS) in SDSS-IV. One of the eBOSS programs is to obtain 2″ (about 15 kpc) fiber spectra of about 200,000 emission-line galaxies (ELGs) at redshift z ≳ 0.6. We use the data from the pilot observations of this program, including 8620 spectra of SFGs at 0.6 < z < 1.2. The median composite spectra of these SFGs at 2200 Å < λ < 4000 Å feature asymmetric, preferentially blueshifted non-resonant emission, Fe ii*, and blueshifted resonant absorption, e.g., Fe ii and Mg ii, indicating ubiquitous outflows driven by star formation at these redshifts. For the absorption lines, we find a variety of velocity profiles with different degrees of blueshift. Comparing our new observations with the literature, we do not observe the non-resonant emission in the small-aperture (<40 pc) spectra of local star-forming regions with the Hubble Space Telescope, and find the observed line ratios in the SFG spectra to be different from those in the spectra of local star-forming regions, as well as those of quasar absorption-line systems in the same redshift range. We introduce an outflow model that can simultaneously explain the multiple observed properties and suggest that the variety of absorption velocity profiles and the line ratio differences are caused by scattered fluorescent emission filling in on top of the absorption in the large-aperture eBOSS spectra. We develop an observation-driven, model-independent method to correct the emission infill to reveal the true absorption profiles. Finally, we show that the strengths of both the non-resonant emission and the emission-corrected resonant absorption increase with [O ii] λλ3727, 3730 rest equivalent width and luminosity, with a slightly larger dependence on the former. Our results show that the eBOSS and future dark-energy surveys (e.g., Dark Energy Spectroscopic Instrument survey and Prime Focus Spectrograph survey) will provide rich data sets of rest-frame NUV spectroscopy for astrophysical applications.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2016

FLASH SPECTROSCOPY: EMISSION LINES FROM THE IONIZED CIRCUMSTELLAR MATERIAL AROUND <10-DAY-OLD TYPE II SUPERNOVAE

Supernovae (SNe) embedded in dense circumstellar material (CSM) may show prominent emission lines in their early-time spectra (≤10 days after the explosion), owing to recombination of the CSM ionized by the shock-breakout flash. From such spectra (“flash spectroscopy”), we can measure various physical properties of the CSM, as well as the mass-loss rate of the progenitor during the year prior to its explosion. Searching through the Palomar Transient Factory (PTF and iPTF) SN spectroscopy databases from 2009 through 2014, we found 12 SNe II showing flash-ionized (FI) signatures in their first spectra. All are younger than 10 days. These events constitute 14% of all 84 SNe in our sample having a spectrum within 10 days from explosion, and 18% of SNe II observed at ages <5 days, thereby setting lower limits on the fraction of FI events. We classified as “blue/featureless” (BF) those events having a first spectrum that is similar to that of a blackbody, without any emission or absorption signatures. It is possible that some BF events had FI signatures at an earlier phase than observed, or that they lack dense CSM around the progenitor. Within 2 days after explosion, 8 out of 11 SNe in our sample are either BF events or show FI signatures. Interestingly, we found that 19 out of 21 SNe brighter than an absolute magnitude M{sub R} = −18.2 belong to the FI or BF groups, and that all FI events peaked above M{sub R} = −17.6 mag, significantly brighter than average SNe II.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Photoelectron spectroscopy and theoretical studies of PCSe-, AsCS-, AsCSe-, and NCSe-: Insights into the electronic structures of the whole family of ECX- anions (E = N, P, and As; X = O, S, and Se)

The newly synthesized, phosphorus- and arsenic-containing analogues of the thio- and seleno-cyanate anions, PCSe-, AsCS-, and AsCSe-, as well as the known ion NCSe-, were investigated in the gas phase by negative ion photoelectron spectroscopy (NIPES), velocity-map imaging (VMI) spectroscopy, and quantum chemical computations. The electron affinities (EA), spin-orbit (SO) splittings, and “symmetric” / “antisymmetric” stretching frequencies (?1 and ?2) of the neutral radicals ECX• (E = N, P and As, X = S and Se), generated by electron detachment from the corresponding anions, were obtained from the spectra. The calculated EAs, SO splittings, and vibrational frequencies are in excellent agreement with the measured values. These newly obtained values, when combined with those previously determined for the lighter analogues, show interesting trends on descending the pnictogen and chalcogen series. These trends are rationalized on the basis of electronegativity arguments, the electron distribution in the HOMO, and NBO/NRT analyses.

Yuan, Qinqin↗
DOE OSTI2015

Evidence of Cu I /Cu II Redox Process by X‐ray Absorption and EPR Spectroscopy: Direct Synthesis of Dihydrofurans from β‐Ketocarbonyl Derivatives and Olefins

Abstract The Cu I /Cu II and Cu I /Cu III catalytic cycles have been subject to intense debate in the field of copper‐catalyzed oxidative coupling reactions. A mechanistic study on the Cu I /Cu II redox process, by X‐ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopies, has elucidated the reduction mechanism of Cu II to Cu I by 1,3‐diketone and detailed investigation revealed that the halide ion is important for the reduction process. The oxidative nature of the thereby‐formed Cu I has also been studied by XAS and EPR spectroscopy. This mechanistic information is applicable to the copper‐catalyzed oxidative cyclization of β‐ketocarbonyl derivatives to dihydrofurans. This protocol provides an ideal route to highly substituted dihydrofuran rings from easily available 1,3‐dicarbonyls and olefins.

Yi, Hong↗
DOE OSTI2021

Probing the Dipole-Bound State in the 9-Phenanthrolate Anion by Photodetachment Spectroscopy, Resonant Two-Photon Photoelectron Imaging, and Resonant Photoelectron Spectroscopy

Valence-bound anions with a dipolar core can support dipole-bound states (DBSs) below the electron detachment threshold. The highly diffuse DBS observed is usually of σ symmetry with an s-like orbital. Recently, a π-type DBS was observed experimentally in the 9-anthrolate anion (9AT – ) and it was shown to be stabilized due to the large anisotropic polarizability of the 9AT core. To confirm the general existence of π-DBS and its structural dependence, here we report an investigation of the 9-phenanthrolate anion (9PT – ), which has a different structure and lower symmetry than 9AT – . Photodetachment spectroscopy revealed a DBS 257 cm -1 below the detachment threshold of 9PT – at 19,627 cm -1 (2.4334 eV). Resonant two-photon photoelectron imaging indeed showed a π symmetry for the DBS. Similar to that observed in 9AT – , the π-DBS in 9PT – is also stabilized by the anisotropic polarizability of the 9PT core and accessed via non-adiabatic population transfer from the initially populated σ-DBS. Photodetachment spectroscopy unveiled nine above-threshold vibrational resonances of the DBS, resulting in nine highly non-Franck-Condon resonant photoelectron spectra by tuning the detachment laser to the vibrational resonances. In conclusion, the combination of photodetachment spectroscopy and resonant photoelectron spectroscopy allowed frequencies for nine vibrational modes of the 9-phenathroxy radical to be measured, including the six lowest frequency bending modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Interaction of Hydrocarbons with Clays under Reservoir Conditions: In Situ Infrared and Nuclear Magnetic Resonance Spectroscopy and X-ray Diffraction for Expandable Clays with Variably Wet Supercritical Methane

The results from novel in situ high-pressure nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and X-ray diffraction (XRD) investigation of the interaction of the smectite hectorite with variably wet supercritical methane (scCH4) at 90 bar and 323 K (hydrostatic conditions equivalent to ~1 km depth) show that CH4 occurs in the clay interlayers, in pores external to the individual clay particles, and as bulk fluid. The occupancy of each environment depends on the relative humidity (RH) of the CH4-rich fluid and the hydration energy and size of the charge-balancing cation. As RH increases, the fraction of interlayer and interparticle CH4 decreases, although with Cs+, addition of a small amount of H2O initially increases CH4 uptake. Maximum interlayer CH4 adsorption occurs when the mean basal spacing just permits methane intercalation (~11.5 Å) and never below this basal spacing. It is also higher with divalent cations than with monovalent cations. The data show that CH4 adsorption occurs predominantly via a weak dispersion interaction with the clay and that its intercalation occurs via a passive space-filling hydrophobic mechanism. The results suggest that, under reservoir conditions, smectite interlayers may provide a reservoir for CH4 under low-water conditions.

Bowers, Geoffrey M.↗
DOE OSTI2015

Synthesis, Structure, and Spectroscopy of Epitaxial EuFeO 3 Thin Films

Rare earth iron perovskites RFeO3, where R is a rare earth cation, exhibit an array of magnetic, catalytic, optical, and electrochemical properties. Here we study EuFeO3 films synthesized by molecular beam epitaxy to improve our understanding of the optical properties of ferrites. A combination of X-ray diffraction, X-ray reflectivity, Rutherford backscattering spectroscopy, and scanning transmission electron microscopy was used to characterize the film structure and cation composition. X-ray absorption spectroscopy confirms the nominal 3+ valence states of Eu and Fe. The optical properties of EuFeO3 were investigated using variable-angle spectroscopic ellipsometry between the photon energies of 1.25 and 5 eV. We find that EuFeO3 is a semiconductor with an onset of optical absorption near 2.5 eV. The absorption spectrum of EuFeO3 is blue-shifted with respect to LaFeO3 films, a result that is attributed to the structural differences between the two materials.

Choquette, Amber K.↗
DOE OSTI2017

Spiers Memorial Lecture : Surface-enhanced Raman spectroscopy: from single particle/molecule spectroscopy to ångstrom-scale spatial resolution and femtosecond time resolution

Four decades on, surface-enhanced Raman spectroscopy (SERS) continues to be a vibrant field of research that is growing (approximately) exponentially in scope and applicability while pushing at the ultimate limits of sensitivity, spatial resolution, and time resolution. This introductory paper discusses some aspects related to all four of the themes for this Faraday Discussion. First, the wavelength-scanned SERS excitation spectroscopy (WS-SERES) of single nanosphere oligomers ( viz. , dimers, trimers, etc. ), the distance dependence of SERS, the magnitude of the chemical enhancement mechanism, and the progress toward developing surface-enhanced femtosecond stimulated Raman spectroscopy (SE-FSRS) are discussed. Second, our efforts to develop a continuous, minimally invasive, in vivo glucose sensor based on SERS are highlighted. Third, some aspects of our recent work in single molecule SERS and the translation of that effort to ångstrom-scale spatial resolution in ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) and single molecule electrochemistry using electrochemical (EC)-TERS will be presented. Finally, we provide an overview of analytical SERS with our viewpoints on SERS substrates, approaches to address the analyte generality problem ( i.e. target molecules that do not spontaneously adsorb and/or have Raman cross sections <10 -29 cm 2 sr -1 ), SERS for catalysis, and deep UV-SERS.

Chemistry↗
DOE OSTI2015

Low-loss electron energy loss spectroscopy: An atomic-resolution complement to optical spectroscopies and application to graphene

Photon-based spectroscopies previously played a central role in exploring the electronic properties of crystalline solids and thin films. They are a powerful tool for probing the electronic properties of nanostructures, but they are limited by lack of spatial resolution. On the other hand, electron-based spectroscopies, e.g., electron energy loss spectroscopy (EELS), are now capable of subangstrom spatial resolution. Core-loss EELS, a spatially resolved analog of x-ray absorption, has been used extensively in the study of inhomogeneous complex systems. In this paper, we demonstrate that low-loss EELS in an aberration-corrected scanning transmission electron microscope, which probes low-energy excitations, combined with a theoretical framework for simulating and analyzing the spectra, is a powerful tool to probe low-energy electron excitations with atomic-scale resolution. The theoretical component of the method combines density functional theory–based calculations of the excitations with dynamical scattering theory for the electron beam. We apply the method to monolayer graphene in order to demonstrate that atomic-scale contrast is inherent in low-loss EELS even in a perfectly periodic structure. The method is a complement to optical spectroscopy as it probes transitions entailing momentum transfer. The theoretical analysis identifies the spatial and orbital origins of excitations, holding the promise of ultimately becoming a powerful probe of the structure and electronic properties of individual point and extended defects in both crystals and inhomogeneous complex nanostructures. The approach can be extended to probe magnetic and vibrational properties with atomic resolution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗