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NASA NTRS2019

A Preliminary Look at Space Weathering on 101955 Bennu: A Radiative Tranfer Modeling Perspective

The surfaces of airless bodies, such as 101955 Bennu, are vulnerable to micrometeoroids, high-energy particles, and solar wind particles. As a result, material on the surface of these bodies experience physical and chemical changes that are collectively known as space weathering. Space weathering processes result in the production of sub-micronsized particles called submicroscopic particles. There are two types of submicroscopic particles, nanophase (<33 nm in size) and microphase particles (>33 nm in size). Studies of lunar samples show that nanophase particles occur within the glassy rims that surround grains and agglutinates. In contrast, microphase iron particles occur only within agglutinates. Another important difference between these two particles is that nanophase and microphase particles affect visible to near-infrared reflectance spectra differently. From lunar samples, the presence of nanophase particles in a regolith causes the regolith’s reflectance spectrum to darken and redden, whereas the presence of microphase particles in a regolith causes it to only darken. In addition, the reflectance spectra of submicroscopic particle-bearing regolith exhibit weakened absorptions and spectral features. Lantz et al. (2018) found that these particles also affect spectral curvature [8]. By taking advantage of these spectral characteristics, with global spectral data, it is possible to model the nanophase and microphase particle abundances across a planetary surface resulting in the production of global space weathering maps.

Trang, D.↗

NASA NTRSDate not supplied

Surface Temperature and the Compositional Effects of Electron Bombardment on Dione

Saturn’s icy moons are composed of mostly water ice with minor “contaminants,” such as CO2 ice, and a dark component thought to be organics, hematite and/or metallic Fe [1]. The space weathering process of electron bombardment is expected to be particularly important on the surfaces of Saturn’s inner moons (Mimas, Tethys, Dione, and Rhea), as they orbit within the extended plasma sheet of Saturn’s magnetosphere. Terrains exhibiting thermal anomalies (i.e., colder temperatures in the day and warmer temperatures at night than surrounding areas) correspond to regions of high energy electron bombardment [2; 3]. Energetic electrons impact the surfaces, fracturing ice particles into sub-micron sized grains, and this process becomes more effective for increasing particle energies [4]. In addition to alteration of ices, the dark material may also be modified or generated within icy surfaces by interaction with solar UV radiation, cosmic rays, or by particles trapped in Saturn’s magnetic field [5]. CO2 could be sourced from irradiation of dark organic material [7]. Many of these alterations should be observable in Visible and Infrared Mapping Spectrometer (VIMS) spectra [8]. We used surface temperatures derived from Cassini’s Composite Infrared Spectrometer (CIRS) to help isolate areas where space weathering due to electron bombardment is more predominant and investigated the subtle changes in VIMS spectra using machine learning techniques. We present our results here for Dione. On ocean worlds, space weathering products would be present along with any potential indications of life. We will need to understand the manifestation of space weathering in the data to separate the two processes.

Cindy Lee Young↗

NASA NTRSDate not supplied

Electron Bombardment on Dione: Surface Compositional Effects and Temperature Anomalies

Saturn’s icy moons are composed primarily of water ice with minor other “contaminants,” such as CO2 ice, and a dark component thought to be organics, hematite and/or metallic Fe [1]. The space weathering process of electron bombardment is expected to be particularly important on the surfaces of Saturn’s inner moons (Mimas, Tethys, Dione, and Rhea), as they orbit within Saturn’s inner magnetosphere. Terrains exhibiting thermal anomalies (i.e., colder temperatures in the day and warmer temperatures at night than surrounding areas) correspond to regions of high energy electron bombardment [2; 3; 4; 5]. Energetic electrons impact the surfaces, sintering ice grains together, and this process becomes more effective for increasing particle energies [6]. Solar UV radiation, cosmic rays, dust in-fall, and cold plasma particles trapped in Saturn’s magnetic field also play an important role in altering the nature and the structure of the native surface ices by the implantation of contaminants, ionization, sputtering, and dissociation of water ice molecules [7]. Additionally, CO2 could be sourced from irradiation of dark organic material [8]. Many of these surface alterations are observable in Cassini’s Visible and Infrared Mapping Spectrometer (VIMS) spectra [9]. We used similar methodologies as have been employed in previous works [e.g., 10] to derive surface temperatures from Cassini’s Composite Infrared Spectrometer (CIRS), which helped to isolate areas where space weathering due to electron bombardment is more predominant. The subtle changes in VIMS spectra were investigated using machine learning techniques. We present here our results for Dione.

Cindy Lee Young↗

NASA NTRSDate not supplied

Electron Bombardment on Dione: Surface Compositional Effects and Temperature Anomalies

Saturn’s icy moons are composed primarily of water ice with minor other “contaminants,” such as CO2 ice, and a dark component thought to be organics, hematite and/or metallic Fe. The space weathering process of electron bombardment is expected to be particularly important on the surfaces of Saturn’s inner moons (Mimas, Tethys, Dione, and Rhea), as they orbit within Saturn’s inner magnetosphere. Terrains exhibiting thermal anomalies (i.e., colder temperatures in the day and warmer temperatures at night than surrounding areas) correspond to regions of high energy electron bombardment. Energetic electrons impact the surfaces, sintering ice grains together, and this process becomes more effective for increasing particle energies. Solar UV radiation, cosmic rays, dust in-fall, and cold plasma particles trapped in Saturn’s magnetic field also play an important role in altering the nature and the structure of the native surface ices by the implantation of contaminants, ionization, sputtering, and dissociation of water ice molecules. Additionally, CO2 could be sourced from irradiation of dark organic material. Many of these surface alterations are observable in Cassini’s Visible and Infrared Mapping Spectrometer (VIMS) spectra. We used similar methodologies as have been employed in previous works to derive surface temperatures from Cassini’s Composite Infrared Spectrometer (CIRS), which helped to isolate areas where space weathering due to electron bombardment is more predominant. The subtle changes in VIMS spectra were investigated using machine learning techniques. We present here our results for Dione.

C L Young↗

NASA NTRSDate not supplied

Electron Bombardment on Dione: Surface Compositional Effects and Temperature Abnormalities

C L Young↗

DOE OSTI2015

Energy transfer and optical gain properties of P{sub 2}O{sub 5}-ZnO-LiF: (Yb{sup 3+}, Er{sup 3+}) glasses

The present paper reports on the results pertaining to the emission properties of 0.5 mol% Er{sup 3+} and together (0.5 Yb{sup 3+} /0.5 Er{sup 3+}) doped PZL (P{sub 2}O{sub 5}-ZnO-LiF) glasses prepared by a melt quenching method. From the optical absorption data, absorption and stimulated emission cross-sections have been evaluated using McCumber’s theory and further cross-sectional gain has also been computed for Yb{sup 3+}/Er{sup 3+} doped glass. On exciting the single (Er{sup 3+}) and dual rare earth ions (Yb{sup 3+}/Er{sup 3+}) doped glass sample at λ{sub exci} = 379 nm, three emission bands in the visible region {sup 2}H{sub 11/2}→{sup 4}I{sub 15/2} (526 nm), {sup 4}S{sub 3/2}→{sup 4}I{sub 15/2} (549 nm) and {sup 4}F{sub 9/2}→{sup 4}I{sub 15/2} (664 nm) are observed and while at λ{sub exci} = 980 nm (Laser Diode) excitation a broad emission at 1530 nm attributed to {sup 4}H{sub 13/2}→{sup 4}I{sub 15/2} is observed in the NIR region. The enhancement in visible and NIR emission intensities with the addition of Yb{sup 3+} to Er{sup 3+} due to an energy transfer process from Yb{sup 3+} to Er{sup 3+} has been explained in terms of an energy level diagram.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2015

Solar photocatalytic activities of porous Nb-doped TiO{sub 2} microspheres by coupling with tungsten oxide

Highlights: • Nb-TiO{sub 2}/WO{sub 3} was prepared by USP method combined impregnation method. • Nb-doping extend the spectral absorption of TiO{sub 2} into visible spectrum. • Nb-TiO{sub 2}/WO{sub 3} has a similar optical band gap as Nb-TiO{sub 2}. • PL spectra indicate WO{sub 3} can accept the photoexcited electrons from Nb-TiO{sub 2}. • Nb-TiO{sub 2}/WO{sub 3} shows higher activity than TiO{sub 2} and Nb-TiO{sub 2} under solar light. - Abstract: Nb doped TiO{sub 2} microspheres modified with WO{sub 3} (Nb-TiO{sub 2}/WO{sub 3}) was prepared by ultrasonic spray pyrolysis method combined with impregnation method. The microspheres were characterized with SEM, TEM, XRD, BET, photoluminescence and UV–vis absorption spectra. The Nb-doping was observed to extend the spectral absorption of TiO{sub 2} into visible spectrum, and the absorption onset was red-shifted for about 88 nm compared to pristine TiO{sub 2} microspheres. Nb-TiO{sub 2}/WO{sub 3} microspheres do not display a red-shifted absorption edge compared with Nb doped TiO{sub 2} microspheres. Under solar irradiation, Nb-TiO{sub 2}/WO{sub 3} microspheres showed higher photocatalytic activity for methylene blue degradation compared with that of pure TiO{sub 2} microspheres and Nb doped TiO{sub 2} microspheres, which could be ascribed to the extended light absorption range and the suppression of electron-hole pair recombination.

36 MATERIALS SCIENCE↗

NASA NTRS1976

Laboratory reflection spectra for the determination of chemical composition of ice bodies

The visible (0.3 to 1.03 microns) spectral reflectances of N2O, NH3, H2S, and NH4HS frosts and mixtures of these frosts as well as their UV-irradiated products have been measured. These spectra are compared with the spectra of the Galilean satellites of Jupiter, Saturn's rings, and Saturn's satellites to place limits on their surface compositions.

Lebofsky, L. A.↗

DOE OSTI2018

Carbon nitrides modified with suitable electron withdrawing groups enhancing the visible-light-driven photocatalytic activity for degradation of the Rhodamine B

Highlights: • Different acid anhydrides all improve the photocatalytic activity of modified g-C{sub 3}N{sub 4}. • PMDA is the more satisfactory acid anhydride. • The photocatalytic and photosensitized paths both exist in the degradation of Rh B. • The PMDA introduction can improve the generated capability of • O{sub 2}{sup −} on the PCN. - Abstract: Carbon nitrides (CN) were modified with acid anhydrides to improve the separation efficiency of the electron-hole and pyromellitic dianhydride (PMDA), was screened as the most suitable groups introduced into the CN. The factors including preparation condition factors, the degree of the CN polymerization and degradation condition factors were researched. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and the infrared spectra (IR) show the structural changes and confirm the successful introduction of PMDA to the bulk CN. The optical properties of modified photocatalyst are investigated by UV–vis diffused reflection spectra (UV–vis DRS) and photoluminescence (PL) spectra and the adsorption performance is detected by the Brunauer-Emmett-Teller (BET). Moreover, the concentration of the main active species O{sub 2}{sup −} increased evidently after the modification during the degradation process. Compared with CN, the photocatalytic degradation efficiency of PCN-290 is about 2 times of that under visible irradiation (λ > 400 nm).

36 MATERIALS SCIENCE↗

DOE OSTI2015

UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

In this paper, transition metal complexes (NH 3 ) 5 CoX2 + (X = CH 3 , Cl) and L(H 2 O)MX 2+ , where M = Rh or Co, X = CH 3 , NO, or Cl, and L is a macrocyclic N 4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH 3 ) 5 CoCH 3 2+ and L(H 2 O)M III X 2+ (X = CH 3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO 2 , visible light photolysis leads to dissociation of X – and/or cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO 2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH 3 ) 5 CoCH 3 2+ and L 1 (H 2 O)CoCH 3 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Reflectance Spectra of Ureilites: Nature of the Mafic Silicate Absorption Features

Ureilites are unique carbon-bearing achondrites. They are composed primarily of olivine and pyroxene with minor amounts of finely dispersed matrix material consisting mostly of carbon, metal, sulfides and fine-grained silicates. As is the case with many classes of meteorites, no clear chain of evidence exists which can relate them to specific asteroidal parent bodies. In order to provide insights into parent body connections, visible and near-IR (VNIR) reflectance spectra of a number of ureilites have been measured and analyzed in light of their mineralogy.

Cloutis, E. A.↗

DOE OSTI2021

Modeling dark- and light-induced crystal structures and single-crystal optical absorption spectra of ruthenium-based complexes that undergo SO 2 -linkage photoisomerization

A family of coordination complexes of the type [Ru(SO 2 )(NH 3 ) 4 X] m+ Y n – (m, n = 1 or 2) exhibit optical switching capabilities in their single-crystal states. This striking effect is caused by the light-induced formation of SO 2 -linkage photoisomers, which are metastable if kept at suitably cool temperatures. We modeled the dark- and light-induced states of these large crystalline complexes via plane-wave (PW)- and molecular-orbital (MO)-based density functional theory (DFT) and time-dependent DFT in order to calculate their structural and optical properties; the calculated results are compared with experimental data. We show that the PW-DFT-based periodic models replicate the structural properties of these complexes more effectively than the MO-DFT-based molecular-fragment models, observing only small deviations in key bond lengths relative to the experimentally derived crystal structures. The periodic models were also found to more effectively simulate trends seen in experimental optical absorption spectra, with optical absorbance and coverage of the visible region increasing with the formation of the photoinduced geometries. The contribution of the metastable photoisomeric species more heavily focuses on the lower-energy end of the spectra. Spectra generated from the molecular-fragment models are limited by the geometry of the fragment used and the number of excited-state roots considered in those calculations. In general, periodic models outperform the molecular-fragment models owing to their ability to better appreciate the periodic phenomena that are present in these crystalline materials as opposed to MO approaches, which are finite methods. We thus demonstrate that PW-DFT-based periodic models should be considered as a more than viable method for simulating the optical and electronic properties of these single-crystal optical switches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

A quick look method of detecting water of hydration in small solar system bodies

The action of aqueous alteration of the near-subsurface material on asteroids and probably some satellites in the Solar System constitutes part of the formation history of the Solar System. The C-class asteroids (and subclasses B, G, and F) were initially believed to have undergone aqueous alteration based on their low albedos and neutral broadband visible and near-infrared colors. These spectra exhibit a sharp drop at wavelengths shorter than 0.55 microns due to a strong ferric oxide intervalence change transfer transition. This IVCT comprises multiple absorptions that are not uniquely indicative of phyllosilicates, but rather are present in the spectrum of any object containing Fe(2+) and Fe(3+) in its surface material. A definitive indication of aqueous alteration came when the broad IR absorption feature having a minimum near 3.0 microns indicative of structural hydroxyl (OH) and interlayer and and absorbed water in phyllosilicates was identified in the IR photometry of many C-class asteroids. Additional mineralogical compositional evidence of aqueously-altered asteroids has come as the result of high SNR narrowband spectrophotometry in the visible and near-infrared spectral regions taken using a CCD/spectrograph combination. An absorption feature centered at 0.7 microns indicative of an Fe(2+) - Fe(3+) charge transfer transition in oxidized iron in phyllosilicates in spectra of some low-albedo asteroids, especially C and G class, and CM2 carbonaceous chondrite meteorites was identified in the CCD spectra. The correlation and covariance of the 0.7-micron and 3.0-micron features were examined by comparing observations of asteroids common to both the CCD reflectance spectra and the 3.0-micron multicolor photometry data sets. Thirty-one pairs of observations were included in this training group. The results of the statistical study indicate that with a 95% confidence level, 84% of the objects observed either having or not having the 0.7-micron feature will correspondingly have the 3.0-micron water of hydration feature.

Vilas, F.↗

NASA NTRS1978

Simultaneous visible and ultraviolet spectroscopy of stellar wind variability in Zeta Puppis

Spectra of He II 4686 A and H-alpha in Zeta Pup were obtained simultaneously with Copernicus ultraviolet scans of several P Cygni profiles in this O4 If supergiant with strong mass loss. The visible-wavelength data show significant variations in the profiles of both lines, consisting of doubling of the emission over times of less than a day. Recent theoretical calculations show that the observed profile variations in 4686 A can be produced by significant fluctuations in the wind density. The Copernicus data show less variability, although in one scan of the 1400-A Si IV doublet there appears to be a significant enhancement of the emission which may be correlated with one of the doublings observed in 4686 A and H-alpha, as though a density enhancement formed at low levels and then moved outward in the wind.

Wegner, G. A.↗

DOE OSTI2016

Room temperature photoluminescence properties of ZnO nanorods grown by hydrothermal reaction

Zinc oxide (ZnO) nanorods were fabricated by a hydrothermal reaction on silicon (Si) substrate at 95 °C for 6 hours. The ZnO seed layer was fabricated by depositing ZnO thin films on Si substrates by ultrasonic spray pyrolisis (USP). The annealing effects on crystal structure and optical properties of ZnO nanorods were investigated. The post-annealing treatment was performed at 800 °C with different environments. The annealed of ZnO nanorods were characterized by X-ray diffraction (XRD) and photoluminescence (PL) in order to analyze crystal structure and optical properties, respectively. The results show the orientations of [002], [101], [102], and [103] diffraction peaks were observed and hexagonal wurtzite structure of ZnO nanorods were vertically grown on Si substrates. The room temperature PL spectra show ultra-violet (UV) and visible emissions. The annealed of ZnO nanorods in vacuum condition (3.8 × 10{sup −3} Torr) has dominant UV emission. Meanwhile, non-annealed of ZnO nanorods has dominant visible emission. It was expected that the annealed of ZnO in vacuum condition suppresses the existence of native defects in ZnO nanorods.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2014

Synthesis of single phase chalcopyrite CuIn{sub 1−x}Ga{sub x}Se{sub 2} (0 ≤ x ≤ 1) nanoparticles by one-pot method

Graphical abstract: - Highlights: • A facile and rapid one-pot synthesis method is presented. • The effects of various Ga contents are investigated. • Single phase chalcopyrite CuIn{sub 1−x}Ga{sub x}Se{sub 2} nanoparticles can be easily synthesized. • The phase formation sequence is from CuSe to CuGaSe{sub 2}, then to CuIn{sub 1−x}Ga{sub x}Se{sub 2}. • The possible reaction mechanism of CuIn{sub 1−x}Ga{sub x}Se{sub 2} nanoparticles is proposed. - Abstract: Single phase chalcopyrite and near stoichiometric CuIn{sub 1−x}Ga{sub x}Se{sub 2} (0 ≤ x ≤ 1) nanoparticles were successfully synthesized by using a facile and rapid one-pot method. The effects of various Ga contents on crystal phase, morphology, element composition and absorption spectrum of the as-synthesized CuIn{sub 1−x}Ga{sub x}Se{sub 2} nanoparticles were investigated in detail. The XRD and Raman patterns indicated that the as-synthesized nanoparticles had a single phase chalcopyrite structure, and the diffraction peaks shifted toward larger diffraction angles or higher frequencies with increasing Ga content. The FE-SEM images showed that the as-synthesized nanoparticles were polydispersed in both size and shape, and the nanoparticles with higher Ga content were more prone to aggregate. The Vis–IR absorption spectra showed strong absorption in the entire visible light region. The estimated band gap increased from 1.00 eV to 1.68 eV as Ga content increasing.

36 MATERIALS SCIENCE↗

NASA NTRS1981

The spectral reflectance of water-mineral mixtures at low temperatures

Laboratory reflectance spectra in the 0.325-2.5 micron region of bound water, water-mineral mixtures, mineral grains on frost, and frost on minerals are presented. The materials used in this study are montmorillonite, kaolinite, beryl, Mauna Kea red cinder, and black charcoal. It is found that the wavelengths of bound water and bound OH absorptions do not shift appreciably with temperature and can be detected when large amounts of free water ice are present. The decrease in the visible reflectance seen in many planetary reflectance spectra containing strong water ice absorptions can be explained by water-mineral mixtures, mineral grains on frost, or frost on mineral grains. Mineral grains on frost are detectable in very small quantities (fractional areal coverage less than approximately 0.005) depending on the mineral reflectance features, while it takes a thick layer of frost (greater than approximately 1 mm) to mask a mineral below 1.4 microns, again depending on the mineral reflectance. Frost on a very dark surface (albedo about 6%) is easily seen; however, a dark mineral mixed with water could completely mask the water absorptions (shortward of 2.5 microns).

Clark, R. N.↗

DOE OSTI2024

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab) 3 ](PF 6 ) 2 , where dab is 4,4′-dicarbaldehyde-2,2′-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH 3 CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M –1 cm –1 ) and an infrared (IR) band at 1712 cm –1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕ PL = 0.048, and an excited state lifetime, τ ο = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, k r = 9.1 × 10 4 s –1 and knr = 1.8 × 10 6 s –1 . Pulsed visible light excitation yielded transient UV–vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH 3 CN solution with 0.1 M TBAPF 6 electrolyte revealed a quasi-reversible oxidation, E°(Ru III/II ) = +1.25 V vs. Fc +/0 , and three sequential one-electron reductions at −1.10, −1.25, and −1.54 V vs. Fc +/0 . Here, an excited state reduction potential of E°(Ru *2+/+ ) = +0.89 V vs. Fc +/0 was estimated with the Rehm–Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD 3 CN solution of [Ru(dab) 3 ](PF 6 ) 2 resulted in significant shifts in the aldehyde H atom and 3,3′-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which K eq = 460 M –1 was extracted, increasing to 5800 M –1 when the solvent was changed to acetone-d 6 . Iodide titrations resulted in a significant quenching of the [Ru(dab) 3 ] *2+ lifetime and quantum yield in both CH 3 CN and acetone solvents. In CH 3 CN, the quenching was mainly dynamic and well described by the Stern–Volmer model, from which a quenching rate constant, k q , of 4.5 × 10 10 M –1 s –1 and an equilibrium constant, K eq , of 8.3 × 10 3 M –1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a K eq of 1.2 × 10 4 M –1 and a higher k q of 9.2 × 10 10 M –1 s –1 .

Aldehydes↗