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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Machine Learning Models for Binary Molecular Classification using VUV Absorption Spectra

Machine learning methods were combined with differential absorption spectroscopy measurements in the vacuum-ultraviolet region (5.167 – 9.920 eV) in order to develop predictive capabilities for inferring molecular structure from the spectra. Several types of species were analyzed and, for modeling purposes, were defined using a single classification: (1) alkane, (2) conjugation with oxygen (e.g. diacetyl, ethyl vinyl ether), (3) non-conjugated alkene (e.g. 1-butene, 1,4-cyclohexadiene), (4) oxygen-containing (e.g. 1-butanol, tetrahydrofuran), or (5) cyclic (e.g. cyclopentane, cyclohexanone). The latter molecular classification excluded cyclic ethers. Several modeling methods were employed in the analysis of 102 absorption spectra, 24 of which were measured for the first time. The primary objective was to identify suitable methods that enable accurate predictions of molecular structure classifications with minimized statistical uncertainties. Rather than identifying a single, unifying method to reliably predict molecular structure contributions to VUV absorption spectra, coordination is required among a particular method, the type of molecular structure detail (e.g. conjugation), and absorption region of interest. The latter is accomplished using a binning approach, wherein absorption regions of ~0.5 eV were utilized rather than the entire ~4.8 eV range. Photon energy binning enabled analysis of region-specific predictions of accuracy, precision, and recall. The outcome from the binning approach is that, rather than utilizing the entire spectrum, optimal determination of molecular structure using machine learning methods depends on the absorption region. Furthermore, the present work provides separate machine learning models for each molecular classification, which enables the identification of multi-functional species relevant to atmospheric chemistry and combustion chemistry, where isomer-resolved speciation is critical to understanding complex reaction networks.

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

Ultraviolet H 2 luminescence in molecular clouds induced by cosmic rays

Context. Galactic cosmic rays (CRs) play a crucial role in ionisation, dissociation, and excitation processes within dense cloud regions where UV radiation is absorbed by dust grains and gas species. CRs regulate the abundance of ions and radicals, leading to the formation of more and more complex molecular species, and determine the charge distribution on dust grains. A quantitative analysis of these effects is essential for understanding the dynamical and chemical evolution of star-forming regions. Aims. The CR-induced photon flux has a significant impact on the evolution of the dense molecular medium in its gas and dust components. This study evaluates the flux of UV photons generated by CRs to calculate the photon-induced dissociation and ionisation rates of a vast number of atomic and molecular species, as well as the integrated UV photon flux. Methods. To achieve these goals, we took advantage of recent developments in the determination of the spectra of secondary electrons, in the calculation of state-resolved excitation cross sections of H 2 by electron impact, and of photodissociation and photoionisation cross sections. Results. We calculated the H 2 level population of each rovibrational level of the X, B, C, B′, D, B″, D′, and a states. We then computed the UV photon spectrum of H 2 in its line and continuum components between 72 and 700 nm, with unprecedented accuracy, as a function of the CR spectrum incident on a molecular cloud, the H 2 column density, the isomeric H 2 composition, and the dust properties. The resulting photodissociation and photoionisation rates are, on average, lower than previous determinations by a factor of about 2, with deviations of up to a factor of 5 for the photodissociation of species such as AlH, C 2 H 2 , C 2 H 3 , C 3 H 3 , LiH, N 2 , NaCl, NaH, O 2 + , S2, SiH, l-C 4 , and l-C 5 H. A special focus is given to the photoionisation rates of H 2 , HF, and N 2 , as well as to the photodissociation of H 2 , which we find to be orders of magnitude higher than previous estimates. We give parameterisations for both the photorates and the integrated UV photon flux as a function of the CR ionisation rate, which implicitly depends on the H 2 column density, as well as the dust properties.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Ultraviolet H 2 luminescence in molecular clouds induced by cosmic rays

Context. Galactic cosmic rays (CRs) play a crucial role in ionisation, dissociation, and excitation processes within dense cloud regions where UV radiation is absorbed by dust grains and gas species. CRs regulate the abundance of ions and radicals, leading to the formation of more and more complex molecular species, and determine the charge distribution on dust grains. A quantitative analysis of these effects is essential for understanding the dynamical and chemical evolution of star-forming regions. Aims. The CR-induced photon flux has a significant impact on the evolution of the dense molecular medium in its gas and dust components. This study evaluates the flux of UV photons generated by CRs to calculate the photon-induced dissociation and ionisation rates of a vast number of atomic and molecular species, as well as the integrated UV photon flux. Methods. To achieve these goals, we took advantage of recent developments in the determination of the spectra of secondary electrons, in the calculation of state-resolved excitation cross sections of H 2 by electron impact, and of photodissociation and photoionisation cross sections. Results. We calculated the H 2 level population of each rovibrational level of the X, B, C, B', D, B", D', and a states. We then computed the UV photon spectrum of H 2 in its line and continuum components between 72 and 700 nm, with unprecedented accuracy, as a function of the CR spectrum incident on a molecular cloud, the H 2 column density, the isomeric H 2 composition, and the dust properties. The resulting photodissociation and photoionisation rates are, on average, lower than previous determinations by a factor of about 2, with deviations of up to a factor of 5 for the photodissociation of species such as AlH, C 2 H 2 , C 2 H 3 , C 3 H 3 , LiH, N 2 , NaCl, NaH, O$^+_2$, S 2 , SiH, l-C 4 , and l-C 5 H. A special focus is given to the photoionisation rates of H 2 , HF, and N 2 , as well as to the photodissociation of H 2 , which we find to be orders of magnitude higher than previous estimates. We give parameterisations for both the photorates and the integrated UV photon flux as a function of the CR ionisation rate, which implicitly depends on the H 2 column density, as well as the dust properties.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

X-ray absorption spectroscopy study of Mn reference compounds for Mn speciation in terrestrial surface environments

Abstract X-ray absorption spectroscopy (XAS) offers great potential to identify and quantify Mn species in surface environments by means of linear combination fit (LCF), fingerprint, and shell-fit analyses of bulk Mn XAS spectra. However, these approaches are complicated by the lack of a comprehensive and accessible spectrum library. Additionally, molecular-level information on Mn coordination in some potentially important Mn species occurring in soils and sediments is missing. Therefore, we investigated a suite of 32 natural and synthetic Mn reference compounds, including Mn oxide, oxyhydroxide, carbonate, phosphate, and silicate minerals, as well as organic and adsorbed Mn species, by Mn K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The ability of XAS to infer the average oxidation state (AOS) of Mn was assessed by comparing XANES-derived AOS with the AOS obtained from redox titrations. All reference compounds were studied for their local (<5 Å) Mn coordination environment using EXAFS shell-fit analysis. Statistical analyses were employed to clarify how well and to what extent individual Mn species (groups) can be distinguished by XAS based on spectral uniqueness. Our results show that LCF analysis of normalized XANES spectra can reliably quantify the Mn AOS within ~0.1 v.u. in the range +2 to +4. These spectra are diagnostic for most Mn species investigated, but unsuitable to identify and quantify members of the manganate and Mn(III)-oxyhydroxide groups. First-derivative XANES fingerprinting allows the unique identification of pyrolusite, ramsdellite, and potentially lithiophorite within the manganate group. However, XANES spectra of individual Mn compounds can vary significantly depending on chemical composition and/or crystallinity, which limits the accuracy of XANES-based speciation analyses. In contrast, EXAFS spectra provide a much better discriminatory power to identify and quantify Mn species. Principal component and cluster analyses of k2-weighted EXAFS spectra of Mn reference compounds implied that EXAFS LCF analysis of environmental samples can identify and quantify at least the following primary Mn species groups: (1) Phyllo- and tectomanganates with large tunnel sizes (2 × 2 and larger; hollandite sensu stricto, romanèchite, todorokite); (2) tectomanganates with small tunnel sizes (2 × 2 and smaller; cryptomelane, pyrolusite, ramsdellite); (3) Mn(III)-dominated species (nesosilicates, oxyhydroxides, organic compounds, spinels); (4) Mn(II) species (carbonate, phosphate, and phyllosilicate minerals, adsorbed and organic species); and (5) manganosite. All Mn compounds, except for members of the manganate group (excluding pyrolusite) and adsorbed Mn(II) species, exhibit unique EXAFS spectra that would allow their identification and quantification in mixtures. Therefore, our results highlight the potential of Mn K-edge EXAFS spectroscopy to assess bulk Mn speciation in soils and sediments. A complete XAS-based speciation analysis of bulk Mn in environmental samples should preferably include the determination of Mn valences following the “Combo” method of Manceau et al. (2012), EXAFS LCF analyses based on principal component and target transformation results, as well as EXAFS shell-fit analyses for the validation of LCF results. For this purpose, all 32 XAS reference spectra are provided in the Online Materials1 for further use by the scientific community.

Geochemistry & Geophysics↗
NASA NTRS1982

Comet Bowell /1980b/ - An active-looking dormant object

The absence of molecular emissions in the spectrum of Comet Bowell, a nearly constant amount of dust in its coma, a slow expansion rate of the coma and implied low particle velocities, a tail width that does not increase with increasing distance from the nucleus, the absence of tail particles less than 0.5 mm in diameter, and the development of an elongated coma, lead to the conclusion that the solid particles in the coma and tail are not recent ejecta, and that the comet has probably been dormant. It is speculated that 10 to the 13th g of observed coma and tail particles is either a leftover pristine material that has never contacted the nucleus surface, or a product of erratic activity associated with chemical instability, at temperatures below 40 K, stimulated by cosmic ray and/or UV irradiation of the surface layer during the comet's Oort cloud stay. It remains possible that the comet may temporarily become active near perihelion.

Sekanina, Z.↗
NASA NTRS1985

Ozone in the free atmosphere

The present book provides a summary of the state of scientific knowledge of stratospheric and free tropospheric ozone as it exists at the beginning of 1983. Ozone photochemistry in the stratosphere is discussed, taking into account fundamental molecular properties, the absorption spectrum of ozone, photodissociation, ozone formation and destruction in the upper atmosphere, the photochemistry of odd-hydrogen, the photochemistry of odd-nitrogen, the photochemistry of odd-chlorine, and photochemistry-temperature coupling. The observed distribution of atmospheric ozone and its variations are considered along with ozone transport, ozone in the troposphere, stratospheric ozone perturbations, and climatic and biological effects. Attention is given to the techniques of observing atmospheric ozone, horizontal-vertical ozone transport and conservative quantities, measurements of tropospheric ozone, the tropospheric ozone budget, ozone models, natural ozone variations, and anthropogenic ozone perturbations.

Whitten, R. C.↗
NASA NTRS1988

Calculation of space station infrared irradiance from atmosphere-induced emissions

The excitation mechanisms and radiance estimates over the 1 to 10 micron region for CO2(v), H2O(v), CO(v), OH(v), NO2(2B-2A) and N2(B3 pi - A3 sigma) are discussed. The infrared irradiance of the Space Station at an altitude of 460 km was estimated. The surface material was presumed to be non-carbonaceous and inert. The determined number densities of the various gases relevant to the Space Station from both ambient and outgassing sources are presented. A model for the production of and emission from the infrared active molecules was constructed that considers two classes of production processes: (1) gas phase excitation of molecules in the near Station environment by collision with ambient flux; and (2) surface processes that lead to molecular excitation. A composite spectrum of all major emitting species shows that the observed irradiance is non-uniform over the 1 to 8 micron region. The comparison of predicted irradiance with the zodiacal background indicates that the Space Station infrared background from atmosphere-induced emissions may be a problem of consequence.

Fraser, M. E.↗
NASA NTRS1995

10 micron spectroscopy of younger stars in the rho Ophiuchi cloud

Spectra in the 10 micrometer region were obtained of 14 young stars associated with the central core of the rho Oph dark cloud complex. Silicate dust emission and absorption features can be fairly well reproduced with simple models using the emissivity of the silicates in the Orion Trapezium region, believed to be typical of molecular cloud dust. A spectrum of the Trapezium star theta(sup 1) Ori D was obtained to define the emissivity more precisely. The emissivity of silicate dust around the late-type giant Mu Cep does not improve the fits to the absorption features and provides a poorer match to the emission features. None of the sources display a strong 11.2 micrometer peak like that seen in comet Halley and attributed to crystalline olivine. A broad weak feature near 11.2 micrometer, possibly related to the comet feature, may be present in the emission spectrum of the Herbig Ae star HD 150193. Absorption features toward two of the objects are narrower than would be expected from Trapezium-like silicates, suggesting differences in the composition of the silicates. The relation between the silicate extinction band depth and H2O ice band depths is determined for the deeply embedded objects. One late-type object, Elias 14, clearly shows the 11.25 micrometer aromatic hydrocarbon emission feature, possibly excited by the nearby B star, HD 147889, though the latter does not exhibit the feature.

Hanner, M. S.↗
NASA NTRS2010

Measurement of Anomalously Strong Emission from the 1s-9p Transition in the Spectrum of H-like Phosphorus Following Charge Exchange with Molecular Hydrogen

We have measured K-shell x-ray spectra of highly ionized argon and phosphorus following charge exchange with molecular hydrogen at low collision energy in an electron beam ion trap using an x-ray calorimeter array with approx.6 eV resolution. We find that the emission at the high-end of the Lyman series is greater by a factor of two for phosphorus than for argon, even though the measurement was performed concurrently and the atomic numbers are similar. This does not agree with current theoretical models and deviates from the trend observed in previous measurements.

Leutenegger, M. A.↗
DOE OSTI2025

Two-dimensional burn velocity and analysis of burn products of nitromethane at high pressure

We have studied the laser-initiated deflagration of nitromethane (CH 3 NO 2 ) under high static pressure in the diamond anvil cell. Time-resolved images of the deflagrations have been obtained using intensified CCDs (ICCD). In contrast with previous work, we rely on spontaneous emission from the reaction, rather than changes in the speckle pattern produced by artificial illumination of the sample. Furthermore, as opposed to the 1D records obtained previously with streak cameras, ICCDs permit imaging of the burn in two dimensions providing the ability to directly observe anisotropic deflagration behavior. Here, we report several examples of this behavior and discuss its possible origins. We have also investigated the products of the reaction using Raman spectroscopy. At pressures below 25 GPa, the burn product is observed to be opaque and has a Raman spectrum consistent with a carbonaceous soot. At pressures above 25 GPa, the burn product is observed to be transparent (consistent with earlier reports) and its Raman spectrum reveals the presence of molecular N 2 and a nitrogen-carbonate species. The latter species can be recovered to ambient pressure and has a Raman spectrum consistent with ammonium carbonate or ammonium bicarbonate. To aid interpretation of the Raman spectra, measurements have also been made on the isotopologues CH 3 15 NO 2 and 13 CH 3 NO 2 . This work establishes the importance of advanced time-resolved imaging to reveal the details of deflagration under high pressure and further advances our understanding of the corresponding chemistry.

Deflagration↗
NASA NTRS1978

Synthetic spectra of C2 in comets

With the key result of Krishna Swamy and O'Dell (1977), a complete fluorescence equilibrium calculation has been used to predict the detailed Swan-band spectrum in comets. A rotational Boltzmann temperature of approximately 3000 K and small changes in published molecular constants lead to a theoretical spectrum in excellent agreement with that observed. The Fox-Herzberg bands are predicted to be quite weak compared with previously observed ultraviolet features in cometary spectra. The Ballik-Ramsay bands should be observable in the near-infrared.

Ahearn, M. F.↗
NASA NTRS2005

Simultaneous Conoscopic Holography and Raman Spectroscopy

A new instrument was developed for chemical characterization of surfaces that combines the analytical power of Raman spectroscopy with the three-dimensional topographic information provided by conoscopic holography. The figure schematically depicts the proposed hybrid instrument. The output of the conoscopic holographic portion of the instrument is a topographical map of the surface; the output of the Raman portion of the instrument is hyperspectral Raman data, from which the chemical and/or biological composition of the surface would be deduced. By virtue of the basic principles of design and operation of the instrument, the hyperspectral image data would be inherently spatially registered with the topographical data. In conoscopic holography, the object and reference beams of classical holography are replaced by the ordinary and extraordinary components generated by a single beam traveling through a birefringent, uniaxial crystal. In the basic conoscopic configuration, a laser light is projected onto a specimen and the resulting illuminated spot becomes a point source of diffuse light that propagates in every direction. The laser beam is rasterscanned in two dimensions (x and y) perpendicular to the beam axis (z), and at each x,y location, the pattern of interference between the ordinary and extraordinary rays is recorded. The recorded interferogram constitutes the conoscopic hologram. Of particular significance for the proposed instrument is that the conoscopic hologram contains information on the z coordinate (height) of the illuminated surface spot. Hence, a topographical map of the specimen is constructed point-by-point by rastering the laser beam in the x and y directions and correlating the x and y coordinates with the z information obtained from the interferograms. Conoscopic imaging is an established method, and conoscopic laboratory instruments for surface metrology are commercially available. In Raman spectroscopy of a surface, one measures the spectrum of laser light scattered inelastically from a laser-illuminated spot on the surface. The wavelengths of the inelastically scattered light differ from that of the incident laser beam by amounts that correspond to the energies of molecular vibrations. The resulting vibrational spectrum can be used to identify the molecules. Raman spectroscopy is a standard laboratory technique for identifying mineralogical, biological, and other specific chemical compositions.

Schramm, Harry F.↗
NASA NTRS1979

Near-infrared observations of a new molecular feature in IRC + 10216

This letter presents a spectrum of IRC + 10216 in the 3000-4400-kayser region at 9-kayser resolution. A molecular feature at 3400-3600 kaysers has been detected which is attributed to an unspecified N-H bonded molecule; the feature appears to be variable in phase with the infrared light curve. Evidence is given for temperature variations of the emitting dust shell in phase with the infrared light curve. The results suggest that the variability of the molecular feature is due to reversible dissociation of the responsible molecule, which could occur at the higher temperatures accompanying the maxima of the light curve.

Krassner, J.↗
DOE OSTI2021

Failure of molecular dynamics to provide appropriate structures for quantum mechanical description of the aqueous chloride ion charge-transfer-to-solvent ultraviolet spectrum

The lowest band in the charge-transfer-to-solvent ultraviolet absorption spectrum of aqueous chloride ion is studied by experiment and computation. Interestingly, the experiments indicate that at concentrations up to at least 0.25 M, where calculations indicate ion pairing to be significant, there is no notable effect of ionic strength on the spectrum. The experimental spectra are fitted to aid comparison with computations. Classical molecular dynamic simulations are carried out on dilute aqueous Cl - , Na + , and NaCl, producing radial distribution functions in reasonable agreement with experiment and, for NaCl, clear evidence of ion pairing. Clusters are extracted from the simulations for quantum mechanical excited state calculations. Accurate ab initio coupled-cluster benchmark calculations on a small number of representative clusters are carried out and used to identify and validate an efficient protocol based on time-dependent density functional theory. The latter is used to carry out quantum mechanical calculations on thousands of clusters. The resulting computed spectrum is in excellent agreement with experiment for the peak position, with little influence from ion pairing, but is in qualitative disagreement on the width, being only about half as wide. It is concluded that simulation by classical molecular dynamics fails to provide an adequate variety of structures to explain the experimental CTTS spectrum of aqueous Cl - .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

The 825-1110 angstroms EUV spectrum of Venus

On 15 August 1994 we launched the EUVS sounding rocket payload to observe the 825-1110 angstrom region of Venus's far ultraviolet airglow spectrum. The EUVS telescope/spectrograph obtained good data at five times higher spectral resolution than was previously available in the far ultraviolet. We present these data and compare our results to those obtained by the Galileo UVS and Venera 11/12 UV spectrophotometers. We identify several new spectral emission features, including both singly ionized nitrogen and molecular nitrogen in Venus's spectrum. We also see evidence for electron-impact-induced emission from CO. Finally, the EUVS data indicate that the "Ar" emissions detected in Venus's far ultraviolet spectrum by Venera 11/12 spectrophotometers are in fact not due to argon, thus eliminating the discrepancy between in situ and remote sensing measurements.

Flight Experiment↗