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At least 1,225 records · Page 68

Structural and Spectroscopic Analysis of Ln(II) 18-crown-6 and Benzo-18-crown-6 Complexes (Ln = Sm, Eu, Yb)

Three Ln 2+ 18-crown-6 complexes of the formula Ln(18-crown-6)I 2 (Ln = Sm, Eu, Yb) were isolated from the explicit synthesis of the corresponding LnI 2 salts with 18-crown-6 and tetrabutylammonium tetraphenylborate in organic media under air-free conditions. Each metal complex forms a distorted hexagonal bipyramidal geometry and crystallizes in the monoclinic space group P2 1 /n. Comparatively, crystallization of Ln(benzo-18-crown-6)I 2 (Ln = Sm, Eu, Yb) from the reaction of LnI2 with tetrabutylammonium tetraphenylborate and benzo-18-crown-6 in THF/ethanol under similarly air-free conditions yields two polymorphs. The first form, α, crystallizes in the monoclinic space group P2 1 /c (or the nonstandard setting P2 1 /n for α-Yb); whereas the second polymorph, β, crystallizes in P$\bar{1}$. While the geometries of the molecules only vary slightly, the molecular packing and intramolecular contacts are quite different. In the structure of β, π–π interactions between the benzo- moieties of adjacent molecules are observed, whereas these interactions are absent in α. Despite the similarities in these classically 4f n+1 lanthanide systems, the complexes display distinct spectroscopic features in their respective absorption and photoluminescence spectra. Broadband 5d → 4f photoluminescence was observed for the Sm and Eu compounds in the NIR region and UV–visible region, respectively. None of the three Yb compounds exhibit photoluminescence UV–visible-NIR region; however, a unique photooxidation event was observed resulting in characteristic Yb(III) 4f → 4f transitions in the NIR region of the absorption spectra of these compounds. Finally, these findings are discussed along with structural comparisons of the 18-crown-6 and benzo-18-crown-6 compounds as well as other reported Ln(II) crown complexes in the literature.

crystals↗

Thermal emission measurements (5-25 microns) of palagonite/Fe-substituted montmorillonite intimate mixtures: Applications to Mars

The emissivity of a Mauna Kea palagonitic soil mixed with an Fe-substituted montmorillonite (FeM) was measured. The emission spectra of all samples were measured at the TES spectroscopy laboratory at Arizona State University. The data were converted to emissivity using blackbody measurements combined with measurements of each sample at different temperatures. This preliminary study has demonstrated that both naturally-occurring palagonites, thought to be good visible to near-IR spectral analogs for Mars, and FeM exhibit complex emissivity spectra at thermal wavelengths. FeM exhibits greater emissivity variations than palagonite, and emissivity peaks observed in the FeM spectrum allows its identification for abundances greater than or equal to 15 percent when mixed with palagonite. Smaller abundances of FeM are potentially identifiable when mixed with palagonite, but this remains to be determined.

Roush, Ted L.↗

Stacking spectra in protoplanetary disks: detecting intensity profiles from hidden molecular lines in HD 163296

We introduce a new stacking method in Keplerian disks that (1) enhances signal-to-noise ratios (S/Ns) of detected molecular lines and (2) makes visible otherwise-undetectable weak lines. Our technique takes advantage of the Keplerian rotational velocity pattern. It aligns spectra according to their different centroid velocities at their different positions in a disk and stacks them. After aligning, the signals are accumulated in a narrower velocity range as compared to the original line width without alignment. Moreover, originally correlated noise becomes decorrelated. Stacked and aligned spectra thus have a higher S/N. We apply our method to Atacama Large Millimeter/Submillimeter Array (ALMA) archival data of DCN (3–2), DCO{sup +} (3–2), N{sub 2}D{sup +} (3–2), and H{sub 2}CO (3{sub 0,3}–2{sub 0,2}), (3{sub 2,2}–2{sub 2,1}), and (3{sub 2,1}–2{sub 2,0}) in the protoplanetary disk around HD 163296. As a result, (1) the S/Ns of the originally detected DCN (3–2), DCO{sup +} (3–2), H{sub 2}CO (3{sub 0,3}–2{sub 0,2}), and N{sub 2}D{sup +} (3–2) lines are boosted by a factor of ≳4–5 at their spectral peaks, implying one order of magnitude shorter integration times to reach the original S/N; and (2) the previously undetectable spectra of the H{sub 2}CO (3{sub 2,2}–2{sub 2,1}) and (3{sub 2,1}–2{sub 2,0}) lines are materialized at more than 3σ. These dramatically enhanced S/Ns allow us to measure intensity distributions in all lines with high significance. The principle of our method can be applied not only to Keplerian disks but also to any systems with ordered kinematic patterns.

79 ASTRONOMY AND ASTROPHYSICS↗

Radio evidence for nonthermal particle acceleration on stars of late spectral type

Radio evidence for nonthermal particle acceleration on stars of late spectral type (G, K, and M) is reviewed, including the pre-main-sequence T Tauri stars, the dwarf M flare stars, and the RS CVn binary stars. Both the long-lasting radio emission and the transient radio flares can be attributed to nonthermal electrons accelerated in magnetically confined coronae, radiating by either incoherent gyrosynchrotron radiation or by coherent processes. Related observations of the Sun provide the framework for interpreting the radio emission of late-type stars. We review recent Very Long Base Interferometry (VLBI) observations of single and binary stars, observations of rapid acceleration and dynamic spectra of dwarf M flare stars, and models for long-lasting radio emission from dwarf M flare stars and RS CVn stars. The VLBI data provide evidence for nonthermal particle acceleration in large-scale magnetospheres several times larger than the stellar radius for T Tauri and RS CVn stars. In contrast, rapid radio flares on dwarf M stars require sources much smaller than the visible star in size, and this is consistent with the VLBI data. Dynamic spectra suggest particle acceleration by relativistic electron beams on dwarf M stars. The long-lived radio radiation of dwarf M stars and RS CVn stars requires more-or-less continuous particle acceleration over periods of hours, perhaps by persistent low-amplitude flaring.

Lang, Kenneth R.↗

A Search for Laser Emission with Megawatt Thresholds from 5600 FGKM Stars

We searched high-resolution spectra of 5600 nearby stars for emission lines that are both inconsistent with a natural origin and unresolved spatially, as would be expected from extraterrestrial optical lasers. The spectra were obtained with the Keck 10 m telescope, including light coming from within 0.5 arcsec of the star, corresponding typically to within a few to tens of astronomical units of the star, and covering nearly the entire visible wavelength range from 3640 to 7890 Å. We establish detection thresholds by injecting synthetic laser emission lines into our spectra and blindly analyzing them for detections. We compute flux density detection thresholds for all wavelengths and spectral types sampled. Our detection thresholds for the power of the lasers themselves range from 3 kW to 13 MW, independent of distance to the star but dependent on the competing “glare” of the spectral energy distribution of the star and on the wavelength of the laser light, launched from a benchmark, diffraction-limited 10 m class telescope. We found no such laser emission coming from the planetary region around any of the 5600 stars. Because they contain roughly 2000 lukewarm, Earth-size planets, we rule out models of the Milky Way in which over 0.1% of warm, Earth-size planets harbor technological civilizations that, intentionally or not, are beaming optical lasers toward us. A next-generation spectroscopic laser search will be done by the Breakthrough Listen initiative, targeting more stars, especially stellar types overlooked here including spectral types O, B, A, early F, late M, and brown dwarfs, and astrophysical exotica.

79 ASTRONOMY AND ASTROPHYSICS↗

Facile construction of vertically aligned EuS-ZnO hybrid core shell nanorod arrays for visible light driven photocatalytic properties

We demonstrated the development of coupled semiconductor in the form of hybrid heterostructures for significant advancement in catalytic functional materials. In this article, we report the preparation of vertically aligned core shell ZnO-EuS nanorod photocatalyst arrays by a simple chemical solution process followed by sulfudation process. The XRD pattern confirmed formation of the hexagonal wurtzite structure of ZnO and cubic nature of the EuS. Cross sectional FESEM images show vertical rod array structure, and the size of the nanorods ranges from 80 to 120 nm. UV-Vis DRS spectra showed that the optical absorption of ZnO was significantly enhanced to the visible region by modification with EuS surfaces. TEM study confirmed that the surface of ZnO was drastically improved by the modification with EuS nanoparticle. The catalytic activity of EuS−ZnO core shell nanorod arrays were evaluated by the photodegradation of Methylene Blue (MB) dye under visible irradiation. The results revealed that the photocatalytic activity of EuS−ZnO was much higher than that of ZnO under natural sunlight. EuS−ZnO was found to be stable and reusable without appreciable loss of catalytic activity up to four consecutive cycles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Analysis of the Intrinsic Mid-infrared L band to Visible–Near-infrared Flux Ratios in Spectral Synthesis Models of Composite Stellar Populations

We analyze the intrinsic flux ratios of various visible–near-infrared filters with respect to 3.5 μm for simple and composite stellar populations (CSPs), and their dependence on age, metallicity, and star formation history (SFH). UV/optical light from stars is reddened and attenuated by dust, where different sightlines across a galaxy suffer varying amounts of extinction. Tamura et al. (2009) developed an approximate method to correct for dust extinction on a pixel-by-pixel basis, dubbed the “β{sub V}” method, by comparing the observed flux ratio to an empirical estimate of the intrinsic ratio of visible and ∼3.5 μm data. Through extensive modeling, we aim to validate the “β{sub V}” method for various filters spanning the visible through near-infrared wavelength range, for a wide variety of simple and CSPs. Combining Starburst99 and BC03 models, we built spectral energy distributions (SEDs) of simple (SSP) and composite (CSP) stellar populations for various realistic SFHs, while taking metallicity evolution into account. We convolve various 0.44–1.65 μm filter throughput curves with each model SED to obtain intrinsic flux ratios β{sub λ,0}. When unconstrained in redshift, the total allowed range of β{sub V,0} is 0.6–4.7, or almost a factor of eight. At known redshifts, and in particular at low redshifts (z ≲ 0.01), β{sub V,0} is predicted to span a narrow range of 0.6–1.9, especially for early-type galaxies (0.6–0.7), and is consistent with observed β{sub V} values. The β{sub λ} method can therefore serve as a first-order dust-correction method for large galaxy surveys that combine JWST (rest-frame 3.5 μm) and HST (rest-frame visible–near-IR) data.

79 ASTRONOMY AND ASTROPHYSICS↗

Photocatalytic activity of BiFeO{sub 3} nanoparticles synthesized through hydrothermal method

Multiferroic BiFeO{sub 3} (BFO) nanoparticles (Nps) were synthesized using hydrothermal method. From the X-Ray diffraction analysis (XRD), the synthesized Nps were found to having rhombohedral structure with R3c space group confirmed by Rietveld analysis. Fourier transform infrared spectroscopy (FTIR) analysis was carried out to identify the chemical bonds present in the BFO Nps. Photocatalytic properties of synthesized Nps were studied for the degradation of Methylene Blue (MB) dye under visible light of 150W.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Encoding Multilayer Complexity in Anti‐Counterfeiting Heterometallic MOF‐Based Optical Tags

Abstract Optical tags provide a way to quickly and unambiguously identify valuable assets. Current tag fluorophore options lack the tunability to allow combined methods of encoding in a single material. Herein we report a design strategy to encode multilayer complexity in a family of heterometallic rare‐earth metal–organic frameworks based on highly connected nonanuclear clusters. To impart both intricacy and security, a synergistic approach was implemented resulting in both overt (visible) and covert (near‐infrared, NIR) properties, with concomitant multi‐emissive spectra and tunable luminescence lifetimes. Tag authentication is validated with a variety of orthogonal detection methodologies. Importantly, the effect induced by subtle compositional changes on intermetallic energy transfer, and thus on the resulting photophysical properties, is demonstrated. This strategy can be widely implemented to create a large library of highly complex, difficult‐to‐counterfeit optical tags.

Deneff, Jacob I.↗

Interlayer Interactions in Twisted WSe 2 /WS 2 Bilayer Heterojunctions: Synthesis, Characterization, and Modeling

Twisting adjacent layers in van der Waals solids can significantly alter their interlayer interactions for tunable optical and electronic properties. Here, we report theoretical calculations, fabrication, and detailed characterizations of WSe 2 /WS 2 bilayer heterojunctions with various twist angles that were synthesized by artificially stacking monolayers of CVD-grown WS 2 and WSe 2 . Density functional calculations predicted the formation of type-II heterojunctions for the stamped bilayers, with band structures that strongly depend on the interlayer twist angle. Raman spectroscopy reveals strong interlayer coupling with the appearance of a layer-number sensitive mode of WS 2 at 311 cm -1 in WSe 2 /WS 2 bilayers. This strong interlayer coupling resulted in a 1~2 order of magnitude quenching of the photoluminescence. The broadening and shifts were observed in micro-absorption spectroscopy of WSe 2 /WS 2 bilayers, which resulted in a net ~10% enhancement in integrated absorption strength across the visible spectrum with respect to the sum of the individual monolayer spectra. The observed 24 4 meV broadening of the WSe 2 A-exciton absorption band in the bilayers provided an estimate on the rate of charge transfer between the layers that ranged from 23 to 33 fs, and was supported by direct femtosecond pump-probe measurements. These results indicate that interlayer exciton formation and non-radiative decay channels dominate optical properties in these bilayers, which may be important for tunable future photovoltaics and detector applications.

36 MATERIALS SCIENCE↗

Origins of the odd optical observables in plutonium and americium tungstates

A series of trivalent f-block tungstates, MW 2 O 7 (OH)(H 2 O) (M = La, Ce, Pr, Nd, and Pu) and AmWO 4 (OH), have been prepared in crystalline form using hydrothermal methods. Both structure types take the form of 3D networks where MW 2 O 7 (OH)(H 2 O) is assembled from infinite chains of distorted tungstate octahedra linked by isolated MO 8 bicapped trigonal prisms; whereas AmWO 4 (OH) is constructed from edge-sharing AmO 8 square antiprisms connected by distorted tungstate trigonal bipyramids. PuW 2 O 7 (OH)(H 2 O) crystallizes as red plates; an atypical color for a Pu( III ) compound. Optical absorption spectra acquired from single crystals show strong, broadband absorption in the visible region. A similar feature is observed for CeW 2 O 7 (OH)(H 2 O), but not for AmWO 4 (OH). Here we demonstrate that these significantly different optical properties do not stem directly from the 5f electrons, as in both systems the valence band has mostly O-2p character and the conduction band has mostly W-5d character. Furthermore, the quasi-particle gap is essentially unaffected by the 5f degrees of freedom. Despite this, our analysis demonstrates that the f-electron covalency effects are quite important and substantially different energetically in PuW 2 O 7 (OH)(H 2 O) and AmWO 4 (OH), indicating that the optical gap alone cannot be used to infer conclusions concerning the f electron contribution to the chemical bond in these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inhomogeneous models of the atmosphere of Saturn

Ultraviolet spectra and absorption band measurements of H2, CH4 and NH3 at visible and near-infrared wavelengths are referred to in developing an inhomogeneous atmospheric model for Saturn. The atmospheric model includes a clear gas layer which lies above an absorbing particle layer surmounting an ammonia haze layer. The distribution of particles in the atmosphere, the radiative transfer calculations, and atmospheric mixing are considered. Comparisons are made with an atmospheric model of Saturn based on infrared observations.

Macy, W.↗

A Fourier transform spectrometer for visible and near ultra-violet measurements of atmospheric absorption

The development of a prototype, ground-based, Sun-pointed Michelson interferometric spectrometer is described. Its intended use is to measure the atmospheric amount of various gases which absorb in the near-infrared, visible, and near-ultraviolet portions of the electromagnetic spectrum. Preliminary spectra which contain the alpha, 0.8 micrometer, and rho sigma tau water vapor absorption bands in the near-infrared are presented to indicate the present capability of the system. Ultimately, the spectrometer can be used to explore the feasible applications of Fourier transform spectroscopy in the ultraviolet where grating spectrometers were used exclusively.

Parsons, C. L.↗

C III spectra in WC Wolf-Rayet stars - Does collisional excitation dominate?

A direct comparison of the spectra emitted by an improved collisionally excited C III atomic model, with observations of C III spectra in Wolf-Rayet WC stars, shows agreement for UV, visible, and near-infrared lines including lines usually considered to be recombination lines. The agreement implies high-density and temperature source conditions corresponding to log (Ne Te) is greater than 16 as a lower limit, whereas most current modeling assumes log (Ne Te) is less than 15.5. This raises questions concerning the photoionization/recombination assumptions on which most WR modeling is based. Recent models are discussed from this point of view.

Kastner, S. O.↗

Tropospheric Formaldehyde Measurements from the ESA GOME Instrument

The Global Ozone Monitoring Experiment (GOME) was launched on the European Space Agency's ERS-2 satellite on April 20, 1995. GOME measures the Earth's atmosphere in the nadir geometry, using a set of spectrometers that cover the UV and visible (240-790 nm) at moderate resolution (0.2 nm in the UV, 0.4 nm in the visible), employing silicon diode array detectors. GOME takes some 30,000 spectra per day, obtaining full global coverage in three days. We directly fit GOME radiance spectra using nonlinear least-squares analysis to obtain column amounts of several trace species with significant tropospheric concentrations, including ozone (O3), nitrogen dioxide (NO2), sulfur dioxide (SO2), and formaldehyde (HCHO). Measurements of HCHO due to biogenic activity in the troposphere are presented here.

Chance, K.↗

Spectral Comparison and Stability of Red Regions on Jupiter

A study of absolute color on Jupiter from Hubble Space Telescope imaging data shows that the Great Red Spot (GRS) is not the reddest region of the planet. Rather, a transient red cyclone visible in 1995 and the North Equatorial Belt both show redder spectra than the GRS (i.e., more absorption at blue and green wavelengths). This cyclone is unique among vortices in that it is intensely colored yet low altitude, unlike the GRS. Temporal analysis shows that the darkest regions of the NEB are relative constant in color from 1995 to 2008, while the slope of the GRS core may vary slightly. Principal component analysis shows several spectral components are needed, in agreement with past work, and further highlights the differences between regions. These color differences may be indicative of the same chromophore(s) under different conditions, such as mixing with white clouds, longer UV irradiation at higher altitude, and thermal processing, or may indicate abundance variations in colored compounds. A single compound does not fit the spectrum of any region well and mixes of multiple compounds including NH4SH, photolyzed NH3, hydrocarbons, and possibly P4, are likely needed to fully match each spectrum.

cyclonic↗

Interstellar PAHs: From Ground to Space, Expanding Spectroscopic Frontiers

Recent progress in astrochemistry and in our understanding of the Molecular Universe has been driven by new detector technologies and advances in ground-, airborne- and space astronomy coupled to new, innovative approaches in molecular spectroscopy. The search for the complex carbon-based molecules (PAHs, Fullerenes, nanoparticles) thought to be responsible for the ubiquitous infrared emission bands (UIBs) and optical absorption bands (DIBs) that are observed in various regions of the interstellar medium of local- and extragalactic environments illustrates the progress in spectroscopy techniques that has been driven by astronomy. Recent progresses reached in this domain will be discussed together with the laboratory techniques that have been developed to measure the spectra of laboratory analogs of cosmic molecules in the UV Visible-NIR range under experimental conditions that attempt to reproduce the interstellar conditions.

Laboratory astrophysics and astrochemistry↗

Orbital Elements and Stellar Parameters of the Active Binary UX Arietis

Stellar activity observed as large surface spots, radio flares, or emission lines is often found in binary systems. UX Arietis exhibits these signs of activity, originating on the K0 subgiant primary component. Our aim is to resolve the binary, measure the orbital motion, and provide accurate stellar parameters such as masses and luminosities to aid in the interpretation of the observed phenomena. Using the CHARA six-telescope optical long-baseline array on Mount Wilson, California, we obtained amplitudes and phases of the interferometric visibility on baselines up to 330 m in length, resolving the two components of the binary. We reanalyzed archival Center for Astrophysics spectra to disentangle the binary component spectra and the spectrum of the third component, which was resolved by speckle interferometry. We also obtained new spectra with the Nordic Optical Telescope, and we present new photometric data that we use to model stellar surface spot locations. Both interferometric visibilities and spectroscopic radial velocities are modeled with a spotted primary stellar surface using the Wilson–Devinney code. We fit the orbital elements to the apparent orbit and radial velocity data to derive the distance (52.1 ± 0.8 pc) and stellar masses (M{sub P}=1.30±0.06 M{sub ⊙}, M{sub S}=1.14±0.06 M{sub ⊙}). The radius of the primary can be determined to be R{sub P}=5.6±0.1 R{sub ⊙} and that of the secondary to be R{sub S}=1.6±0.2 R{sub ⊙}. The equivalent spot coverage of the primary component was found to be 62% with an effective temperature 20% below that of the unspotted surface.

79 ASTRONOMY AND ASTROPHYSICS↗