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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 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Tracking the first electron transfer step at the donor side of oxygen-evolving photosystem II by time-resolved infrared spectroscopy

In oxygen-evolving photosystem II (PSII), the multi-phasic electron transfer from a redox-active tyrosine residue (TyrZ) to a chlorophyll cation radical (P680 + ) precedes the water-oxidation chemistry of the S-state cycle of the Mn 4 Ca cluster. Here we investigate these early events, observable within about 10 ns to 10 ms after laser-flash excitation, by time-resolved single-frequency infrared (IR) spectroscopy in the spectral range of 1310–1890 cm -1 for oxygen-evolving PSII membrane particles from spinach. Comparing the IR difference spectra at 80 ns, 500 ns, and 10 µs allowed for the identification of quinone, P680 and TyrZ contributions. A broad electronic absorption band assignable P680 + was used to trace largely specifically the P680 + reduction kinetics. The experimental time resolution was taken into account in least-square fits of P680 + transients with a sum of four exponentials, revealing two nanosecond phases (30–46 ns and 690–1110 ns) and two microsecond phases (4.5–8.3 µs and 42 µs), which mostly exhibit a clear S-state dependence, in agreement with results obtained by other methods. Our investigation paves the road for further insight in the early events associated with TyrZ oxidation and their role in the preparing the PSII donor side for the subsequent water oxidation chemistry.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1972

The Nimbus 4 infrared spectroscopy experiment. I - Calibrated thermal emission spectra.

Measurement of the infrared spectrum of the earth and atmosphere between 400 and 1600/cm. In an effort to obtain spectra with high absolute accuracy, it was necessary to incorporate many factors into the calibration, including small departures from unity in the emissivity of the on-board calibration source, imbalance between cold and warm calibration ports, and effects due to orbital variations in instrument temperature. The inclusion of such higher order corrections, along with careful data screening processes, has ensured a high quality data set that can be used in a variety of geophysical and meteorological investigations. Representative samples of data are presented that illustrate the behavior of the thermal emission spectra under a variety of conditions encountered in a typical orbit, including extremes in temperature, surface reststrahlung (or residual ray) effects, and various types of cloud conditions.

Hanel, R. A.↗
NASA NTRS1974

High pressure far infrared spectroscopy of ionic solids

A high-pressure far-infrared cell operating at up to truly hydrostatic pressures of 8 kbar is described and used to determine the anharmonic self-energies associated with the transverse optic modes of ionic solids in which q approximately equals zero. The cell allows far-infrared studies in the spectral range below 120 reciprocal cm. The transverse optic modes were investigated to determine their mode Gruneisen constants and the pressure dependence of their inverse lifetimes in RbI, CsI, and TlCl.

Lowndes, R. P.↗
NASA NTRS1992

Lunar Resources Using Moderate Spectral Resolution Visible and Near-infrared Spectroscopy: Al/si and Soil Maturity

Modern visible and near-infrared detectors are critically important for the accurate identification and relative abundance measurement of lunar minerals; however, even a very small number of well-placed visible and near-infrared bandpass channels provide a significant amount of general information about crucial lunar resources. The Galileo Solid State Imaging system (SSI) multispectral data are an important example of this. Al/Si and soil maturity will be discussed as examples of significant general lunar resource information that can be gleaned from moderate spectral resolution visible and near-infrared data with relative ease. Because quantitative-albedo data are necessary for these kinds of analyses, data such as those obtained by Galileo SSI are critical. SSI obtained synoptic digital multispectral image data for both the nearside and farside of the Moon during the first Galileo Earth-Moon encounter in December 1990. The data consist of images through seven filters with bandpasses ranging from 0.40 microns in the ultraviolet to 0.99 microns in the near-infrared. Although these data are of moderate spectral resolution, they still provide information for the following lunar resources: (1) titanium content of mature mare soils based upon the 0.40/0.56-micron (UV/VIS) ratio; (2) mafic mineral abundance based upon the 0.76/0.99-micron ratio; and (3) the maturity or exposure age of the soils based upon the 0.56-0.76-micron continuum and the 0.76/0.99-micron ratio. Within constraints, these moderate spectral resolution visible and near-infrared reflectance data can also provide elemental information such as Al/Si for mature highland soils.

Fischer, Erich M.↗
DOE OSTI2022

In vitro investigation of protein assembly by combined microscopy and infrared spectroscopy at the nanometer scale

The nanoscale structure and dynamics of proteins on surfaces has been extensively studied using various imaging techniques, such as transmission electron microscopy and atomic force microscopy (AFM) in liquid environments. These powerful imaging techniques, however, can potentially damage or perturb delicate biological material and do not provide chemical information, which prevents a fundamental understanding of the dynamic processes underlying their evolution under physiological conditions. Here, we use a platform developed in our laboratory that enables acquisition of infrared (IR) spectroscopy and AFM images of biological material in physiological liquids with nanometer resolution in a cell closed by atomically thin graphene membranes transparent to IR photons. In this work, we studied the self-assembly process of S-layer proteins at the graphene-aqueous solution interface. The graphene acts also as the membrane separating the solution containing the proteins and Ca 2+ ions from the AFM tip, thus eliminating sample damage and contamination effects. The formation of S-layer protein lattices and their structural evolution was monitored by AFM and by recording the amide I and II IR absorption bands, which reveal the noncovalent interaction between proteins and their response to the environment, including ionic strength and solvation. Our measurement platform opens unique opportunities to study biological material and soft materials in general.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Can Agricultural Management Induced Changes in Soil Organic Carbon Be Detected Using Mid-Infrared Spectroscopy?

A major limitation to building credible soil carbon sequestration programs is the cost of measuring soil carbon change. Diffuse reflectance spectroscopy (DRS) is considered a viable low-cost alternative to traditional laboratory analysis of soil organic carbon (SOC). While numerous studies have shown that DRS can produce accurate and precise estimates of SOC across landscapes, whether DRS can detect subtle management induced changes in SOC at a given site has not been resolved. Here, we leverage archived soil samples from seven long-term research trials in the U.S. to test this question using mid infrared (MIR) spectroscopy coupled with the USDA-NRCS Kellogg Soil Survey Laboratory MIR spectral library. Overall, MIR-based estimates of SOC%, with samples scanned on a secondary instrument, were excellent with the root mean square error ranging from 0.10 to 0.33% across the seven sites. In all but two instances, the same statistically significant (p < 0.10) management effect was found using both the lab-based SOC% and MIR estimated SOC% data. Despite some additional uncertainty, primarily in the form of bias, these results suggest that large existing MIR spectral libraries can be operationalized in other laboratories for successful carbon monitoring.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Chemometrics and Experimental Design for the Quantification of Nitrate Salts in Nitric Acid: Near-Infrared Spectroscopy Absorption Analysis

Implementing remote, real-time spectroscopic monitoring of radiochemical processing streams in hot cell environments requires efficiency and simplicity. The success of optical spectroscopy for the quantification of species in chemical systems highly depends on representative training sets and suitable validation sets. Selecting a training set (i.e., calibration standards) to build multivariate regression models is both time- and resource-consuming using standard one-factor-at-a-time approaches. This study describes the use of experimental design to generate spectral training sets and a validation set for the quantification of sodium nitrate (0–1 M) and nitric acid (0.1–10 M) using the near-infrared water band centered at 1440 nm. Partial least squares regression models were built from training sets generated by both D- and I-optimal experimental designs and a one-factor-at-a-time approach. The prediction performance of each model was evaluated by comparing the bias and standard error of prediction for statistical significance. D- and I-optimal designs reduced the number of samples required to build regression models compared with one-factor-at-a-time while also improving performance. Models must be confirmed against a validation sample set when minimizing the number of samples in the training set. The D-optimal design performed the best when considering both performance and efficiency by improving predictive capability and reducing number of samples in the training set by 64% compared with the one-factor-at-a-time approach. The experimental design approach objectively selects calibration and validation spectral data sets based on statistical criterion to optimize performance and minimize resources.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1998

In situ CF3 Detection in Low Pressure Inductive Discharges by Fourier Transform Infrared Spectroscopy

The detection of CF(x) (x=1-3) radicals in low pressure discharges using source gases such as CF4 and CHF3 is of importance to the understanding of their chemical structure and relevance in plasma based etching processes. These radicals are known to contribute to the formation of fluorocarbon polymer films, which affect the selectivity and anisotropy of etching. In this study, we present preliminary results of the quantitative measurement of trifluoromethyl radicals, CF3, in low pressure discharges. The discharge studied here is an inductively (transformer) coupled plasma (ICP) source in the GEC reference cell, operating on pure CF4 at pressures ranging from 10 - 100 mTorr, This plasma source generates higher electron number densities at lower operating pressures than obtainable with the parallel-plate capacitively coupled version of the GEC reference cell. Also, this expanded operating regime is more relevant to new generations of industrial plasma reactors being used by the microelectronics industry. Fourier transform infrared (FTIR) spectroscopy is employed to observe the absorption band of CF3 radicals in the electronic ground state X2Al in the region of 1233-1270/cm. The spectrometer is equipped with a high sensitivity HgCdTe (MCT) detector and has a fixed resolution of 0.125/cm. The CF3 concentrations are measured for a range of operating pressures and discharge power levels.

Kim, J. S.↗
NASA NTRS1975

Composition of the Martian dust as derived by infrared spectroscopy from Mariner 9

The Martian dust spectra obtained by the infrared interferometer spectrometer (Iris) experiment on Mariner 9 have been compared with modeling computations for various minerals and rocks. The model used was based upon a recently developed theory of absorption and scattering by particulate materials. The results indicate that the composition of Martian dust is biased toward silicate structures which involve a high degree of silicate oxygen sharing. A feldspar-rich dust of approximately 1-micron particle size appears to be the best candidate, although sheet-structure silicates cannot be ruled out.

Aronson, J. R.↗
NASA NTRS1994

Near-infrared spectroscopy of primitive solar system objects

We have obtained near-infrared (H and K band at lambda/Delta(lambda) is approximately 480 to 600) spectra of a sample of primitive objects including 2 Centaur objects (2060 Chiron and 5145 Pholus) and 16 P- and D-type asteroids. The spectra were obtained at the United Kingdom Infrared Telescope using the cooled grating spectrometer CGS4, and were used to search for chemically diagnostic vibrational features in these primitive objects. Pholus exhibits broad adsorption features at 2.07 and 2.27 micrometers, as well as a weak feature at 1.72 micrometers. The 1.72- and 2.27-micrometer features are similar to those seen in a laboratory tar sand sample. No distinct absorption features are found in other objects, including Chiron, which displays a spectrally neutral continuum. A comparison of the P- and D-type asteroid spectra with laboratory measurements of organic solids shows no compelling evidence for hydrocarbon overtones seen in terrestrial bituminous tar sands.

Luu, Jane↗
DOE OSTI2022

High-resolution infrared spectroscopy of supersonically cooled singlet carbenes: Bromomethylene (HCBr) in the CH stretch region

First high-resolution spectra of cold (~35 K) singlet bromomethylene HCBr in the CH stretching (v 1 ) region from 2770 to 2850 cm-1 are reported using near quantum shot-noise limited laser absorption methods in a slit jet supersonic discharge expansion source. Three rovibrational bands are identified at high S/N (20:1 - 40:1) and rotationally assigned to i) the CH stretch fundamental (v 1 ) band $\tilde{X}$(1,0,0) ← $\tilde{X}$ (0,0,0) and ii) vibrational hot bands ($\tilde{X}$(1,1,0) ← $\tilde{X}$(0,1,0) and $\tilde{X}$(1,0,1) ← $\tilde{X}$(0,0,1)) arising from vibrationally excited HCBr populated in the discharge with single quanta in either the H–C–Br bend (v 2 ) or C–Br stretch (v 3 ) modes. Precision rotational constants are reported for a total of six states, with an experimentally determined CH stretch vibrational frequency (2799.38 cm -1 ) in good agreement with previous low-resolution fluorescence studies. Detailed analysis of the fundamental v 1 band highlights the presence of perturbations in the $\tilde{X}$(1,0,0) level, which we tentatively attribute to arise from the nearby triplet state $\tilde{a}$(0,0,1) through spin-orbit interaction or the multiple quanta $\tilde{X}$(0,2,1) singlet state via c-type Coriolis coupling. Reduced-Doppler resolution (60 MHz) in the slit-jet IR spectrometer permits clear observation of nuclear spin hyperfine structure, with experimental line shapes well reproduced by nuclear quadrupole/spin-rotation coupling constants from microwave studies. Lastly, the a-type to b-type transition intensity ratio for the fundamental CH stretch band is notably larger than predicted by a bond-dipole model, which from high level ab initio quantum calculations (CCSD(T)/PVQZ) can be attributed to vibrationally induced “charge-sloshing” of electron density along the polar C–Br bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2013

HST-WFC3 Near-Infrared Spectroscopy of Quenched Galaxies at zeta approx 1.5 from the WISP Survey: Stellar Populations Properties

We combine Hubble Space Telescope (HST) G102 and G141 near-IR (NIR) grism spectroscopy with HST/WFC3- UVIS, HST/WFC3-IR, and Spitzer/IRAC [3.6 microns] photometry to assemble a sample of massive (log(Mstar/M solar mass) at approx 11.0) and quenched (specific star formation rate < 0.01 G/yr(exp −1) galaxies at zeta approx 1.5. Our sample of 41 galaxies is the largest with G102+G141 NIR spectroscopy for quenched sources at these redshifts. In contrast to the local universe, zeta approx 1.5 quenched galaxies in the high-mass range have a wide range of stellar population properties. We find that their spectral energy distributions (SEDs) are well fitted with exponentially decreasing star formation histories and short star formation timescales (τau less than or equal to 100 M/yr). Quenched galaxies also show a wide distribution in ages, between 1 and 4 G/yr. In the (u − r)0-versus-mass space quenched galaxies have a large spread in rest-frame color at a given mass. Most quenched galaxies populate the zeta appro. 1.5 red sequence (RS), but an important fraction of them (32%) have substantially bluer colors. Although with a large spread, we find that the quenched galaxies on the RS have older median ages (3.1 G/yr) than the quenched galaxies off the RS (1.5 G/yr). We also show that a rejuvenated SED cannot reproduce the observed stacked spectra of (the bluer) quenched galaxies off the RS. We derive the upper limit on the fraction of massive galaxies on the RS at zeta approx 1.5 to be <43%.We speculate that the young quenched galaxies off the RS are in a transition phase between vigorous star formation at zeta > 2 and the zeta approx 1.5 RS. According to their estimated ages, the time required for quenched galaxies off the RS to join their counterparts on the z approx. 1.5 RS is of the order of approx. 1G/yr.

HST WFC#↗
DOE OSTI2021

Ultraviolet photodissociation of gas-phase iron pentacarbonyl probed with ultrafast infrared spectroscopy

It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. Here we employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO) 3 within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).

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

Mixed Molecular and Dissociative Water Adsorption on Hydroxylated TiO 2 (110): An Infrared Spectroscopy and Ab Initio Molecular Dynamics Study

For this work, we have investigated the structure and dynamics of water (D 2 O) adsorbed on TiO 2 (110) for coverages between 0 and 1 monolayer with infrared reflection absorption spectroscopy (IRAS) and ab initio molecular dynamics (AIMD) simulations. For D 2 O coverages as low as 0.4 monolayers (ML) on a hydroxylated surface, IR spectra typical of hydrogen-bonded chains of water molecules are observed. However, for D 2 O coverages ≥ 0.3 ML, a sharp, high frequency peak is also observed in the p-polarized spectra that is red-shifted relative to the bridging hydroxyl peak. This new peak is not observed for water adsorbed on an oxidized surface. Based on the AIMD simulations and comparisons with previous IR spectra for TiO 2 nanoparticles, the new peak is assigned to terminal hydroxyl groups produced by dissociative adsorption of some of the water on TiO 2 (110). The simulations indicate that water dissociation is related to the presence of defect electrons in the system, but not due to direct interactions between adsorbed water and bridging hydroxyls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

Temperature gradients through EHD films and molecular alignment evidenced by infrared spectroscopy

Partial and complete emission band reversals have been observed in the infrared emission spectra from portions of operating sliding contacts. An elementary analysis has been carried out to show that partial reversals are due to temperature gradients in the fluid film - the film acts both as a radiation-emitter and absorber, and that total reversals - an emission spectrum appears as an absorption spectrum are likely to be due to a continuum source, such as hot solid asperities. The total energy radiated under the latter conditions exceeds that under the others. A decrease in gap width with increased load was accompanied by a dramatic spectral change in the case of 5P4E polyphenyl ether, which is indicative of molecular alignment.

King, V. W.↗