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At least 91 records · Page 5

The Maturing of High Contrast Imaging and Starlight Suppression Techniques for Future NASA Exoplanet Characterization Missions

Over 3000 exoplanets and hundreds of exoplanetary systems have been detected to date and we are now rapidly moving toward an era where the focus is shifting from detection to direct imaging and spectroscopic characterization of these new worlds and their atmospheres. NASA is currently studying several exoplanet characterization mission concepts for the 2020 Decadal Survey ranging from probe class to flagships. Detailed and comprehensive exoplanet characterization, particularly of exo-Earths, leading to assessment of habitability, or indeed detection of life, will require significant advances beyond the current state-of-the-art in high contrast imaging and starlight suppression techniques which utilize specially shaped precision optical elements to block the light from the parent star while controlling scattering and diffraction thus revealing and enabling spectroscopic study of the orbiting exoplanets in reflected light. In this paper we describe the two primary high contrast starlight suppression techniques currently being pursued by NASA: 1) coronagraphs (including several design variations) and 2) free-flying starshades. These techniques are rapidly moving from the technology development phase to the design and engineering phase and we discuss the prospects and projected performance for future exoplanet characterization missions utilizing these techniques coupled with large aperture telescopes in space.

high contrast↗

Direct Observation of Plasma-Stimulated Activation of Surface Species Using Multimodal In Situ/Operando Spectroscopy Combining Polarization-Modulation Infrared Reflection-Absorption Spectroscopy, Optical Emission Spectroscopy, and Mass Spectrometry

Nonthermal plasmas (NTPs) produce reactive chemical environments, including electrons, ions, radicals, and vibrationally excited molecules, that can drive chemistry at temperatures at which such species are thermally inaccessible. There has been growing interest in the integration of conventional catalysis with reactive NTPs to promote novel chemical transformations. Unveiling the full potential of plasma-catalytic processes requires a comprehensive understanding of plasma-catalytic synergies, including characterization of plasma-catalytic surface interactions. In this work, we report on a newly designed multimodal spectroscopic instrument combining polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS), mass spectrometry, and optical emission spectroscopy (OES) for the investigation of plasma–surface interactions such as those found in plasma catalysis. In particular, this tool has been utilized to correlate plasma-phase chemistry with both surface chemistry and gas-phase products in situ (1) during the deposition of carbonaceous surface species via NTP-promoted nonoxidative coupling of methane and (2) during subsequent activation of surface deposits with an atmospheric pressure and temperature argon plasma jet on both nickel (Ni) and silicon dioxide (SiO 2 ) surfaces. For the first time, the activation of carbonaceous surface species by a NTP on Ni and SiO 2 surfaces to form hydrogen gas and C 2 hydrocarbons was directly observed, where both PM-IRAS and OES measurements suggest that they may form through different pathways. Furthermore, this unique tool for studying plasma–surface interactions could enable more rational design of plasma-stimulated catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revisiting the Anisotropic Complex Refractive Indices of Sodium Nitrate for Interpretation of the Reflectance Spectrum of Pressed Pellets

Reflectance spectroscopy is notoriously confounding in that the measured spectral response is highly dependent upon the morphology of the sample. Fortunately, all such perturbations are neatly encoded by the complex refractive index of the sample. Herein, we seek to quantitatively model the measured infrared reflectance spectrum of a specularly flat pressed pellet sample of the birefringent compound, sodium nitrate. Single crystals of sodium nitrate were synthesized via a slow evaporation process and spectroscopically analyzed using polarization-dependent infrared single-angle reflectance spectroscopy. The anisotropic complex refractive index was measured from 7500 to 300 cm-1 (1.33 to 33.33 µm). The deduced anisotropic optical constants were found to be consistent with those previously reported. Once measured and validated, the optical constants were applied to model the pressed pellet reflectance spectrum. It was evident that an average of the anisotropic refractive indices was insufficient to account for the measured pellet reflectance. In order to account for contributions of all possible microcrystalline orientations within the pellet, the Python package PYELLI was used to calculate a basis set of orientation-dependent reflection spectra spanning the distinct ? and ? Euler rotations of the uniaxial crystal. When the population of orientations was allowed to vary freely in a spectral fit analysis, the fit-deduced orientations were tightly clustered along f = 45º, hinting at residual anisotropy in the pressed pellet sample. Conversely, an equally valid spectral fit (with marginally worse fit metric) was obtained when the population was constrained to an isotropic distribution of orientations. Subsequent non-zero cross-polarization reflectance measurements likewise suggested anisotropy in the pellet. However, both grazing incidence wide-angle x-ray scattering and scanning electron microscopy measurements revealed that the microcrystal orientations at the surface of the pressed pellet sample were isotropically distributed (and that the average crystallite size was larger than ?/10). Application of the measured complex refractive indices for modeling the reflectance spectrum of the pressed pellet, and rectification of these seemingly contradictory observations will be discussed.

Wilhelm, Michael J.↗

Spectroscopic Properties of Metamorphosed Mafic Rocks: Remote Sensing Applications on Mars

Reflectance spectroscopy in the visible and near-infrared wavelengths, between 420 mn to 2588 nm. was utilized on a suite of hydrothermally metamorphosed mafic rocks from the Smartville complex in the northern Sierra Nevada mountains in California. A detailed data base of 102 samples was compiled in order to distinguish differences in mineralogy, petrology, and degree of metamorphism for remote sensing applications. Study was limited to metaigneous and metasedimentary rocks in an attempt to spectrally characterize terrestrial rocks analogous to the possible surface of Mars, for a better understanding and possible detection of the geologic features on the remote surface. Diagnostic absorption bands of iron, water, and hydroxyl produced the majority of discernible features in this study. Mossbauer spectroscopy was performed in order to determine specific iron sites. The resulting spectral data base along with thin section mineral identification, metamorphic zone, rock type and location were recorded and available for future application and research. Continued exploration of Mars in the advancing years, will further advance our understanding of the geology of Mars. Spectroscopic techniques will undoubtedly be integral parts of these future missions. Work on terrestrial analogs to the Martian surface must continue, in order to produce extensive data bases and broaden our knowledge of spectral features.

Graff, Trevor G.↗

Quantitative infrared spectroscopy of aerosols: Mie theory modeling with experimental validation

Infrared spectroscopy is a well-established method for identifying solid, liquid, and gas-phase chemicals. Accurate infrared spectroscopic analysis requires reference libraries where library endmembers reflect all optical phenomena contributing to the observed spectra. Traditional spectral libraries most often contain molecular-based absorption spectra, but these do not account for the complex scattering effects that become significant when measuring aerosols. In this work, we combine the laboratory-derived, wavelength-dependent complex optical vectors ( n / k ) of liquid dioctyl sebacate (DOS) with Mie scattering theory and the Beer–Lambert law to generate synthetic infrared transmission spectra of aerosolized DOS. Additionally, we record experimental infrared transmission spectra using an FTIR spectrometer coupled to a simple aerosol chamber filled with a quantified number size distribution of aerosolized DOS. The modeled and measured spectra show strong agreement, with Mie scattering effects clearly altering the overall spectral shape as well as the positions and profiles of absorption features. The results demonstrate that synthetic spectra generated from n / k values can reliably capture aerosol-specific spectral behavior and thus serve as a foundation for building scalable, physics-based aerosol reference libraries to enable infrared spectroscopic detection of aerosols.

Salcido, Jessica M. O. [Pacific Northwest National↗

Reflectance spectroscopy of ferric sulfate-bearing montmorillonites as Mars soil analog materials

Spectroscopic analyses have shown that smectites enhanced in the laboratory with additional ferric species exhibit important similarities to those of the soils on Mars. Ferrihydrite in these chemically treated smectites has features in the visible to near-infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. New samples have been prepared with sulfate as well, because S was found by Viking to be a major component in the surface material on Mars. A suite of ferrihydrite-bearing and ferric sulfate-bearing montmorillonites, prepared with variable Fe3+ and S concentrations and variable pH conditions, has been analyzed using reflectance spectroscopy in the visible and infrared regions, Mossbauer spectroscopy at room temperature and 4 K, differential thermal analysis, and X-ray diffraction. These analyses support the formation of ferrihydrite of variable crystallinity in the ferrihydrite-bearing montmorillonites and a combination of schwertmannite and ferrihydrite in the ferric sulfate-bearing montmorillonites. Small quantities of poorly crystalline or nanophase forms of other ferric materials may also be present in these samples. The chemical formation conditions of the ferrihydrite-bearing and ferric sulfate-bearing montmorillonites influence the character of the low temperature Mossbauer sextets and the visible reflectance spectra. An absorption minimum is observed at 0.88-0.89 micrometers in spectra of the ferric sulfate-bearing samples, and at 0.89-0.92 micrometers in spectra of the ferrihydrate-bearing montmorillonites. Mossbauer spectra of the ferric sulfate-bearing montmorillonites indicate variable concentrations of ferrihydrite and schwertmannite in the interlaminar spaces and along grain surfaces. Dehydration under reduced atmospheric pressure conditions induces a greater effect on the adsorbed and interlayer water in ferrihydrite-bearing montmorillonite than on the water in ferric sulfate-bearing montmorillonite. Reflectance spectra of ferric sulfate-bearing montmorillonite include a strong 3-micrometers band that is more resistant to dry atmospheric conditions than the 3-micrometers band in spectra of similarly prepared ferrihydrite-bearing montmorillonites.

NASA Discipline Exobiology↗

Infrared spectroscopic observations of the outer planets, their satellites, and the asteroids

An infrared spectroscopic data base is described for such planetary studies as (1) the detection of atmospheric constituents, (2) the establishment of the column abundances of known atmospheric constituents, and (3) the determination of the thermal properties of planetary atmospheres. Jupiter, Saturn, Uranus, Neptune, Titan and Triton are discussed with reference to middle- and far-IR data, the chemical and thermal properties of their atmospheres, atmospheric constituents and absolute reflectivities, or albedos. Attention is also given to infrared spectroscopic studies of satellite and asteroid surfaces. It is noted that the most abundant surface materials are condensed volatiles and silicate minerals. Water ice has been detected on many surfaces and on the rings of Saturn; CH-4 has been found on Pluto, and CO2 has been identified as a component of the polar caps on Mars. It is concluded that some asteroid surfaces are mineralogically compatible with the relatively unevolved low-temperature remnant of nebular condensation, while others are composed of high-temperature silicates spectrally identical to the products of magmatic differentiation.

Larson, H. P.↗

Effect of Water Concentration in LiPF 6 -Based Electrolytes on the Formation, Evolution, and Properties of the Solid Electrolyte Interphase on Si Anodes

A trace amount of water in an electrolyte is one of the factors detrimental to the electrochemical performance of silicon (Si)-based lithium-ion batteries that adversely affect the formation and evolution of the solid electrolyte interphase (SEI) on Si-based anodes and change its properties. Thus far, a lack of fundamental and mechanistic understanding of SEI formation, evolution, and properties in the presence of water has inhibited efforts to stabilize the SEI for improved electrochemical performance. As such, we investigated the SEI formed in a Gen2 electrolyte (1.2 M LiPF6 in ethylene carbonate/ethyl methyl carbonate, 3:7 wt %, water content: <10 ppm) with and without additional water (50 ppm) at varying potentials (1.0, 0.5, 0.2, and 0.01 V vs Li/Li + ). The impact of additional water on the morphological, (electro)chemical, and structural properties of SEI was studied using microscopic (atomic force microscopy and scanning spreading resistance microscopy) and spectroscopic (X-ray photoelectron spectroscopy, attenuated total reflection Fourier-transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry) techniques. The SEI exhibits both potential- and water concentration-dependent trends in its morphology and chemical composition. The presence of additional water in the electrolyte causes parasitic reactions, which onset at ~1.0 V, resulting in a reduction of electrolyte components and result in the formation of an insulating, fluorophosphate-rich SEI. In addition, hydrolysis of LiPF 6 creates hydrofluoric acid, which reacts with the surface oxide layer on the Si electrode, leading to a pitted and inhomogeneous SEI structure.

36 MATERIALS SCIENCE↗

Method to derive the infrared complex refractive indices n(λ) and k(λ) for organic solids from KBr pellet absorption measurements

Obtaining the complex refractive index vectors $n($$\tilde{v})$ and $k($$\tilde{v})$ allows calculation of the (infrared) reflectance spectrum that is obtained from a solid in any of its many morphological forms. Here, we report an adaptation to the KBr pellet technique using two gravimetric dilutions to derive quantitative $n($$\tilde{v})$/$k($$\tilde{v})$ for dozens of powders with greater repeatability. The optical constants of bisphenol A and sucrose are compared to those derived by other methods, particularly for powdered materials. The variability of the $k$ values for bisphenol A was examined by 10 individual measurements, showing an average coefficient of variation for $k$ peak heights of 5.6%. Though no established standards exist, the pellet-derived $k$ peak values of bisphenol A differ by 11% and 31% from their single-angle- and ellipsometry-derived values, respectively. These values provide an initial estimate of the precision and accuracy of complex refractive indices that can be derived using this method. Limitations and advantages of the method are discussed, the salient advantage being a more rapid method to derive $n$/$k$ for those species that do not readily form crystals or specular pellets.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

A redetermination of the Uranus rotation period

The rotation velocity of Uranus has been measured by a comparison of spectroscopic profiles for the 5281.8 A Fraunhofer line reflected from Uranus and the moon. This method yields a rotation velocity which is insensitive to atmospheric seeing conditions. Our value for the equatorial velocity is 3.5 + or - 0.4 km/sec.

Trauger, J. T.↗

Voyager 2 observations of NGC 7023 - Dust scattering shortward of 1600 A

We report the first observational determination of the nebular-to-stellar flux ratio out to wavelengths as short as 1000 A for the reflection nebula NGC 7023, using a combination of spectroscopic data from Voyager 2 and from the Hopkins Ultraviolet Telescope (HUT) on the Astro 1 mission. After accounting for contributions by H2 fluorescence to the nebular flux, the wavelength variation of the ratio of the residual dust scattered flux to that observable from the embedded star is consistent with a reduction of the dust albedo by 25 percent over the wavelength interval 1300-1000 A. This is most easily interpreted, if the particles responsible for the FUV rise in the extinction curve are low-albedo, not necessarily zero-albedo, grains. The direct proportionality between the nebular surface brightness, measured at 22 arcsec offset by HUT, and the nebular flux suggests that the phase function of scattering does not vary in the 2000-1000 A range.

Witt, A. N.↗

The Orbiting Carbon Observatory: Mission Overview

OCO will acquire the space-based data needed to identify CO2 sources and sinks and quantify their variability over the seasonal cycle. Approach: a) Collect spatially resolved, high resolution spectroscopic observations of CO2 and O2 absorption in reflected sunlight; b) Use these data to resolve spatial and temporal variations in the column averaged CO2 dry air mole fraction, X cub CO2) over the sunlit hemisphere; and c) Employ independent calibration and validation approaches to produce X(sub CO2) estimates with random errors and biases no larger than 1-2 ppm (0.3-0.5%) on regional scales at monthly intervals.

CO2↗

The Orbiting Carbon Observatory Mission: Watching the Earth Breathe Mapping CO2 from Space

Approach: Collect spatially resolved, high resolution spectroscopic observations of CO2 and O2 absorption in reflected sunlight. Use these data to resolve spatial and temporal variations in the column averaged CO2 dry air mole fraction, X(sub CO2) over the sunlit hemisphere. Employ independent calibration and validation approaches to produce X(sub CO2) estimates with random errors and biases no larger than 1-2 ppm (0.3-0.5%) on regional scales at monthly intervals.

three channel grating spectrometry↗

Study of the Effect of Reflections on High-Power, 110-GHz Pulsed Gyrotron Operation

The effect of reflection is studied experimentally and theoretically on a high-power 110-GHz gyrotron operating in the TE 22,6 mode in 3 μs pulses at 96 kV, 40 A. The experimental setup allows variation of the reflected power from 0 to 33% over a range of gyrotron operating conditions. The phase of the reflection is varied by translating the reflector along the axis. Operating at a higher efficiency point, at 4.40 T with 940kW of output power, reflected power exceeding 11% causes a switch from operation in the TE 22,6 to simultaneous operation in the TE 22,6 and TE 21,6 modes with a large decrease of the total gyrotron output power. This switching effect is in good agreement with simulations using the MAGY code. Operating at a more stable point, 4.44 T with 580kW of output power, when the reflection is increased, the output power remains in the TE 22,6 mode but it decreases monotonically with increasing reflection, dropping to 200kW at 33% reflection. Furthermore, at a reflection above 22%, a power modulation at 25 to 30MHz is observed, independent of the phase of the reflected wave. Such a modulated signal may be useful in spectroscopic and other applications.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Metallized Capillaries as Probes for Raman Spectroscopy

A class of miniature probes has been proposed to supplant the fiber-optic probes used heretofore in some Raman and fluorescence spectroscopic systems. A probe according to the proposal would include a capillary tube coated with metal on its inside to make it reflective. A microlens would be hermetically sealed onto one end of the tube. A spectroscopic probe head would contain a single such probe, which would both deliver laser light to a sample and collect Raman or fluorescent light emitted by the sample.

Pelletier, Michael↗

Reflectance and Mossbauer spectroscopy of ferrihydrite-montmorillonite assemblages as Mars soil analog materials

Spectroscopic analyses show that Fe(3+)-doped smectites prepared in the laboratory exhibit important similarities to the soils on Mars. Ferrihydrite has been identified as the interlayer ferric component in Fe(3+)-doped smectites by a low quadrupole splitting and magnetic field strength of approximately 48 tesla in Mossbauer spectra measured at 4.2 K, as well as a crystal field transition at 0.92 micrometer. Ferrihydrite in these smectites explains features in the visible-near infrared region that resemble the energies and band strengths of features in reflectance spectra observed for several bright regions on Mars. Clay silicates have met resistance in the past as Mars soil analogs because terrestrial clay silicates exhibit prominent hydrous spectral features at 1.4, 1.9, and 2.2 micrometers; and these are observed weakly, if at all, in reflectance spectra of Mars. However, several mechanisms can weaken or compress these features, including desiccation under low-humidity conditions. The hydration properties of the interlayer cations also effect band strengths, such that a ferrihydrite-bearing smectite in the Martian environment would exhibit a 1.9 micrometers H2O absorption that is even weaker than the 2.2 micrometers structural OH absorption. Mixing experiments demonstrate that infrared spectral features of clays can be significantly suppressed and that the reflectance can be significantly darkened by mixing with only a few percent of a strongly absorbing opaque material. Therefore, the absolute reflectance of a soil on Mars may be disproportionately sensitive to a minor component. For this reason, the shape and position of spectral features and the chemical composition of potential analogs are of utmost importance in assessing the composition of the soil on Mars. Given the remarkable similarity between visible-infrared reflectance spectra of soils in bright regions on Mars and Fe(3+)-doped montmorillonites, coupled with recent observations of smectites in SNC meteorites and a weak 2.2 micrometers absorption in some Mars soils, ferrihydrite-bearing smectites warrant serious consideration as a Mars soil analog.

NASA Discipline Exobiology↗

High efficiency spectrographs for the EUV and soft X-rays

The use of grazing incidence optics and reflection grating designs is shown to be a method that improves the performance of spectrographs at wavelengths shorter than 1200 A. Emphasis is laid on spectroscopic designs for X ray and EUV astronomy, with sample designs for an objective reflection grating spectrograph (ORGS) and an echelle spectrograph for wavelengths longer than 100 A. Conical diffraction allows operations at grazing incidence in the echelle spectrograph. In ORGS, the extreme distance of X ray objects aids in collimating the source radiation, which encounters conical diffraction within the instrument, proceeds parallel to the optical axis, and arrives at the detector. A series of gratings is used to achieve the effect. A grazing echelle is employed for EUV observations, and offers a resolution of 20,000 over a 300 A bandpass.

Cash, W.↗

Computational Investigation of the Role of Active Site Heterogeneity for aSupported Organovanadium(III) Hydrogenation Catalyst

A crucial consideration for supported heterogeneous catalysts is the nonuniformity of the active sites, particularly for supported organometallic catalysts. Standard spectroscopic techniques, such as X-ray absorption spectroscopy, reflect the nature of the most populated sites, which are often intrinsically structurally distinct from the most active catalytic sites. Additionally, with computational models, often, only a few representative structures are used to depict catalytic active sites on a surface, even though there are numerous observable factors of surface heterogeneity that contribute to the kinetically favorable active species. A previously reported study on the mechanism of a surface organovanadium-(III) catalyst [(SiO 2 )V III (Mes)(THF)] for styrene hydrogenation yielded two possible mechanisms: heterolytic cleavage and redox cycling. These two mechanistic scenarios are challenging to differentiate experimentally since the kinetic readouts of the catalyst are identical. To showcase the importance of modeling surface heterogeneity and its effect on catalytic activity, density functional theory (DFT) computational models of a series of potential active sites of [(SiO 2 )V III (Mes)(THF)] for the reaction pathways are applied in combination with kinetic Monte Carlo (kMC) simulations. Computed results were then compared to the previously reported experimental kinetic study: (1) DFT free-energy reaction pathways indicated the likely active site and pathway for styrene hydrogenation, a heterolytic cleavage pathway requiring a bare tripodal vanadium site. (2) From the kMC simulations, a mixture of different bond lengths from the support oxygen to the metal center was required to qualitatively describe the experimentally observed kinetic aspects of a supported organovanadium(III) catalyst for olefin hydrogenation. This work underscores the importance of modeling surface heterogeneity in computational catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗