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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Comparing Calibration Algorithms for the Rapid Characterization of Pretreated Corn Stover Using Near-Infrared Spectroscopy

Rapid characterization of biomass composition is a key enabling technology for biorefineries—the ability to measure the chemical composition of biomass materials entering the biorefinery as well as the composition of key process intermediate streams would allow real-time process control and the development of robust models to predict process performance. The utility of near-infrared (NIR) spectroscopy for rapid characterization requires multivariate algorithms for building calibration models. The most prevalent algorithm used for building calibration models using NIR spectra is the linear modeling algorithm Partial Least Squares Regression (PLS). Nonlinear regression algorithms (which are typically more computationally intensive than linear modeling approaches) have gained popularity in recent years due to their ability to solve a wide variety of classification and regression problems and the dramatic increase in available computational resources. In this work, we demonstrate that a calibration model can predict the composition of corn stover process intermediate samples pretreated with three different treatments—hot water (HW), dilute acid (DA), and deacetylation followed by dilute acid (DDA). We quantitatively compare three different algorithms for building prediction models based on near-infrared spectroscopy—partial least squares (PLS), support vector machines (SVM), and random forests (RF). We demonstrate the utility of improving model performance by accounting for instrument performance variability using repeated measurements of standard materials (e.g., the “repeatability file” strategy) and investigate its performance with nonlinear regression techniques, and we discuss methods for quantifying the uncertainties of specific predictions among the three methods.

09 BIOMASS FUELS↗
DOE OSTI2022

Mechanisms Underlying Plastocyanin-Cytochrome f Electron Transfer Investigated via Site-Specific Linear and Two-dimensional Infrared Spectroscopy

The goal of this research is to further our understanding of biological electron transfer in photosynthesis through the development and application of new methods for studying proteins with high spatial and temporal detail. Biological electron transfer occurs between metal sites imbedded in proteins where the environment and its motions can be very different from those of normal bulk liquids. Moreover, electron transfer between two proteins typically involves short-lived binding interactions within a highly mobile complex. We have directed our studies at photosynthetic electron transfer proteins plastocyanin and cytochrome f. We have labeled two key ligands to the copper ion of plastocyanin with carbon deuterium probe vibrations that enable their selective analysis by infrared spectroscopy. This analysis has shown that association of plastocyanin with cytochrome f leads to large changes in the bonding between the copper ion and ligands. In addition, the probes have been used to assess the contribution of the protein scaffold of plastocyanin in dictating the copper coordination geometry. We also have made progress to extend our experiments from equilibrium to non-equilibrium studies. The studies help to illuminate how proteins are tuned to control biological electron transfer. A better understanding of electron transfer reactions in natural photosynthesis will bolster efforts to develop artificial systems for energy production.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

High-resolution infrared spectroscopy of jet cooled cyclobutyl in the α-CH stretch region: large-amplitude puckering dynamics in a 4-membered ring radical

We report gas-phase cyclobutyl radical (c-C 4 H 7 ) is generated at a rotational temperature of T rot = 26(1) K in a slit-jet discharge mixture of 70% Ne/30% He and 0.5–0.6% cyclobromobutane (c-C 4 H 7 Br). A fully rovibrationally resolved absorption spectrum of the α-CH stretch fundamental band between 3062.9 cm −1 to 3075.7 cm −1 is obtained and analyzed, yielding first precision structural and dynamical information for this novel radical species. The α-CH stretch band origin is determined to be 3068.7887(4) cm −1 , which implies only a modest (≈0.8 cm −1 ) blue shift from rotationally unresolved infrared spectroscopic studies of cyclobutyl radicals in liquid He droplets [ A. R. Brown, P. R. Franke and G. E. Douberly, J. Phys. Chem. A , 2017, 121 , 7576–7587]. Of particular dynamical interest, a one-dimensional potential energy surface with respect to the ring puckering coordinate is computed at CCSD(T)/ANO2 level of theory and reveals a double minimum C s puckered geometry, separated by an exceedingly shallow planar C 2v transition state barrier (E barr ≈ 1 cm −1 ). Numerical solutions on this double minimum potential yield a zero-point energy for the ground state (E zero-point ≈ 27 cm −1 ) greatly in excess of the interconversion barrier. This is indicative of highly delocalized, large amplitude motion of the four-membered ring structure, for which proper vibrationally averaging of the moment of inertia tensor reproduces the experimentally determined inertial defect remarkably well. Finally, intensity alternation in the experimental spectrum due to nuclear spin statistics upon exchange of three indistinguishable H atom pairs (IH = ½) matches K a + K c = even : odd = 36 : 28 predictions, implying that the unpaired electron in the radical center lies in an out-of-plane p π orbital. Thus, high-resolution infrared spectroscopy provides first experimental confirmation of a shallow double minimum ring puckering potential with a highly delocalized ground state wave function peaked at a planar C 2v transition state geometry consistent with a cyclobutyl π radical.

Chemistry↗
DOE OSTI2022

Helium droplet infrared spectroscopy of the butyl radicals

Butyl radicals (n-, s-, i-, and tert-butyl) are formed from the pyrolysis of stable precursors (1-pentyl nitrite, 2-methyl-1-butyl nitrite, isopentyl nitrite, and azo-tert-butane, respectively). The radicals are doped into a beam of liquid helium droplets and probed with infrared action spectroscopy from 2700 to 3125 cm -1 , allowing for a low temperature measurement of the CH stretching region. The presence of anharmonic resonance polyads in the 2800–3000 cm -1 region complicates its interpretation. To facilitate spectral assignment, the anharmonic resonances are modeled with two model Hamiltonian approaches that explicitly couple CH stretch fundamentals to HCH bend overtones and combinations: a VPT2+K normal mode model based on coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)] quartic force fields and a semi-empirical local mode model. Both of these computational methods provide generally good agreement with the experimental spectra.

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

Rapid measurement of soluble xylo-oligomers using near-infrared spectroscopy (NIRS) and multivariate statistics: calibration model development and practical approaches to model optimization

Rapid monitoring of biomass conversion processes using techniques such as near-infrared (NIR) spectroscopy can be substantially quicker and less labor-, resource-, and energy-intensive than conventional measurement techniques such as gas or liquid chromatography (GC or LC) due to the lack of solvents and preparation methods, as well as removing the need to transfer samples to an external lab for analytical evaluation. The purpose of this study was to determine the feasibility of rapid monitoring of a biomass conversion process using NIR spectroscopy combined with multivariate statistical modeling, and to examine the impact of (1) subsetting the samples in the original dataset by process location and (2) reducing the spectral range used in the calibration model on model performance. We develop multivariate calibration models for the concentrations of soluble xylo-oligosaccharides (XOS), monomeric xylose, and total solids at multiple points in a biomass conversion process which produces and then purifies XOS compounds from sugar cane bagasse. A single model using samples from multiple locations in the process stream showed acceptable performance as measured by standard statistical measures. However, compared to the single model, we show that separate models built by segregating the calibration samples according to process location show improved performance. We also show that combining an understanding of the sample spectra with simple multivariate analysis tools can result in a calibration model with a substantially smaller spectral range that provides essentially equal performance to the full-range model. We demonstrate that real-time monitoring of soluble xylo-oligosaccharides (XOS), monomeric xylose, and total solids concentration at multiple points in a process stream using NIR spectroscopy coupled with multivariate statistics is feasible. Segregation of sample populations by process location improves model performance. Models using a reduced spectral range containing the most relevant spectral signatures show very similar performance to the full-range model, reinforcing the importance of performing robust exploratory data analysis before beginning multivariate modeling.

09 BIOMASS FUELS↗
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 OSTI2023

Real-time infrared spectroscopy coupled with blind source separation for nuclear waste process monitoring

On-line infrared absorbance spectroscopy enables rapid measurement of solution-phase molecular species. Many spectra-to-concentration models exist for spectral data, with some models able to handle overlapping spectral bands and nonlinearities. However, model accuracy is limited by the quality of training data used in model fitting. The process spectra of nuclear waste simulants at the Savannah River Site display incongruity between training and process spectra; the glycolate spectral signature in the training data does not match the glycolate signature in Savannah River National Laboratory process data. A novel blind source separation algorithm is proposed that preprocesses spectral data so that process spectra more closely resemble training spectra, thereby improving model quantification accuracy when unexpected sources of variation appear in process spectra. The novel blind source separation preprocessing algorithm is shown to improve nitrate quantification from an R 2 of 0.934 to 0.988 and from 0.267 to 0.978 in two instances analyzing nuclear waste simulants from the Slurry Receipt Adjustment Tank and Slurry Mix Evaporator cycle at the Savannah River Site.

Crouse, Steven H.↗
NASA NTRS1996

Airborne Infrared Spectroscopy of 1994 Western Wildfires

In the summer of 1994, the 0.07cm -1 resolution infrared Airborne Emission Spectrometer (AES) acquired spectral data over two wildfires, one in central Oregon on August 3 and the other near San Luis Obispo, California on August 15. The spectrometer was on board a NASA DC-8 research aircraft, flying at an altitude of 12 km.

Spectroscopy↗
NASA NTRS1988

Infrared spectroscopy of Jupiter and Saturn

High resolution infrared spectoscopy provides unique insights into the chemistry and dynamics of the atmospheres of Jupiter and Saturn. The 5 micrometer spectral region, which is transparent to deep levels, is particularly useful for the identification of molecules that are present at very low (parts per billion) concentrations. These are tracers of convective and strongly non-equilibrium processes in the atmosphere. High resolution ground-based spectroscopy complements Voyager and Galileo measurements. Spectroscopy is sensitive to lower mixing levels for selected molecules, while the on-board mass spectrometers probe molecules that are spectroscopically inaccessible. Analysis and modeling of the 4.7 micrometer carbon monoxide in Jupiter was completed. CO is present at a mole fraction of 1.6 plus or minus 0.3 x 10 to the 9th power and concentrated in the troposphere. At this abundance, it must be convected upward from much deeper levels in Jupiter where the temperature is near 1100 K. Thus CO is a tracer of the deep atmosphere which is otherwise unobservable. The oxygen abundance in Jupiter (as measured by the CO abundance) is near solar. Chemical or physical process must deplete the major oxygen carrier, water. Germane, GeH4, was discovered on Saturn at amole fraction of 4 plus or minus 2 x 10 to the 10th power.

Knacke, Roger↗
NASA NTRS1975

Far Infrared Spectroscopy of H II Regions

The far infrared spectra of H II regions are investigated. A liquid helium cooled grating spectrometer designed to make observations from the NASA Lear Jet is described along with tests of the instrument. The observing procedure on the Lear Jet telescope is described and the method of data analysis is discussed. Results are presented from a search for the (O III) 88.16 micron line. An upper limit on the emission in this line is obtained and line detection is described. Results are compared to theoretical predictions, and future applications of fine structure line observations are discussed. Coarse resolution results are given along with calibration problems. The spectra obtained are compared to models for dust emission.

Ward, D. B.↗
NASA NTRS1984

Mid-infrared Spectroscopy of Planetary Nebulae

The application of infrared spectral lines observed in part of the broadened spectral range (18 to 36 microns) to planetary nebula studies is discussed. Infrared spectral lines in the mid-infrared supply information about planetary nebulae which both supplement and complement optical results. Their utility lies mainly in the insensitivity of the line intensities to temperature variations or uncertainties, in contrast to the behavior of optical emission. This in turn leads to more accurate ionic abundances than presently available from optical lines. Although densities from optical line ratios are not very sensitive to temperature, the lines are weighted toward regions of higher temperatures. A comparison with infrared densities from the same ions therefore provide clues to the density and/or temperature variations within nebulae. Temperatures from OIV and NeV ions show a part of high-excitation nebulae previously inaccessible. They verify the picture of physical processes in the HeIII zone.

Shure, M. A.↗
NASA NTRS1986

Some recent infrared spectroscopy of interstellar processes

The potential which infrared spectroscopic techniques provide for studying interstellar process is demonstrated. Several examples are given. The data were obtained at UKIRT, using its frequency-chopped Fabry-Perot spectrometer and its seven-channel cooled grating spectrometer.

Geballe, T. R.↗
DOE OSTI2022

Probing electrolyte–silica interactions through simulations of the infrared spectroscopy of nanoscale pores

The structural and dynamical properties of nanoconfined solutions can differ dramatically from those of the corresponding bulk systems. Understanding the changes induced by confinement is central to controlling the behavior of synthetic nanostructured materials and predicting the characteristics of biological and geochemical systems. A key outstanding issue is how the molecular-level behavior of nanoconfined electrolyte solutions is reflected in different experimental, particularly spectroscopic, measurements. This is addressed here through molecular dynamics simulations of the OH stretching infrared (IR) spectroscopy of NaCl, NaBr, and NaI solutions in isotopically dilute HOD/D 2 O confined in hydroxylated amorphous silica slit pores of width 1–6 nm and pH ~2. In addition, the water reorientation dynamics and spectral diffusion, accessible by pump–probe anisotropy and two-dimensional IR measurements, are investigated. In this work, the aim is to elucidate the effect of salt identity, confinement, and salt concentration on the vibrational spectra. It is found that the IR spectra of the electrolyte solutions are only modestly blue-shifted upon confinement in amorphous silica slit pores, with both the size of the shift and linewidth increasing with the halide size, but these effects are suppressed as the salt concentration is increased. This indicates the limitations of linear IR spectroscopy as a probe of confined water. However, the OH reorientational and spectral diffusion dynamics are significantly slowed by confinement even at the lowest concentrations. The retardation of the dynamics eases with increasing salt concentration and pore width, but it exhibits a more complex behavior as a function of halide.

Mesoporous material↗
NASA NTRS1979

Study of polyphenyl ether fluid /5P4E/ in operating elastohydrodynamic contacts by infrared emission spectroscopy

Infrared emission spectra of 5P4E polyphenyl ether were obtained from an operating elastohydrodynamic sliding contact at different speeds and loads by Fourier emission microspectrophotometry. The spectra were found to be polarized with respect to the direction of the conjunction line, especially at high shear rates. Film and metal surface temperatures were calculated from the spectra, and film thicknesses were determined under various operating conditions. Changes of polarized band structure above a critical shear rate, at which the slope of the film temperature versus shear curve changes abruptly and at which the film thickness assumes a minimum value, are consistent with a transition of the lubricant from a viscous liquid to a viscoelastic liquid or to an elastic solid.

Lauer, J. L.↗