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Ultraviolet Spectroscopy of Asteroid(4) Vesta

We report a comprehensive review of the UV-visible spectrum and rotational lightcurve of Vesta combining new observations by Hubble Space Telescope and Swift with archival International Ultraviolet Explorer observations. The geometric albedos of Vesta from 220 nm to 953 nm arc derived by carefully comparing these observations from various instruments at different times and observing geometries. Vesta has a rotationally averaged geometric albedo of 0.09 at 250 nm, 0.14 at 300 nm, 0.26 at 373 nm, 0.38 at 673 nm, and 0.30 at 950 nm. The linear spectral slope in the ultraviolet displays a sharp minimum ncar sub-Earth longitude of 20deg, and maximum in the eastern hemisphere. This is completely consistent with the distribution of the spectral slope in the visible wavelength. The uncertainty of the measurement in the ultraviolet is approx.20%, and in the visible wavelengths better than 10%. The amplitude of Vesta's rotational lightcurves is approx.10% throughout the range of wavelengths we observed, but is smaller at 950 nm (approx.6%) ncar the 1-micron mafic band center. Contrary to earlier reports, we found no evidence for any difference between the phasing of the ultraviolet and visible/ncar-infrared lightcurves with respect to sub-Earth longitude. Vesta's average spectrum between 220 and 950 nm can well be described by measured reflectance spectra of fine particle howardite-like materials of basaltic achondrite meteorites. Combining this with the in-phase behavior of the ultraviolet, visible. and ncar-infrared lightcurves, and the spectral slopes with respect to the rotational phase, we conclude that there is no global ultraviolet/visible reversal on Vesta. Consequently, this implies lack of global space weathering on Vesta. Keyword,: Asteroid Vesta; Spectrophotometry; Spectroscopy; Ultraviolet observations; Hubble Space Telescope observations

Li, Jian-Yang↗

High-Redox-Potential Chromophores for Visible-Light-Driven Water Oxidation at Low pH

Photochemical water oxidation at low pH requires chromophores with adequate photophysical properties and high redox potentials capable of oxidizing the catalysts. We report here a series of homoleptic Ru(II) polypyridyl complexes and their performances in photochemical water oxidation at pH 1 using persulfate as the sacrificial electron acceptor. These chromophores incorporate CF 3 or PO 3 H 2 groups to increase the RuIII/II standard potentials to 1.3–1.6 V versus NHE, while their homoleptic nature retains photophysical properties (absorption spectra, lifetimes, emission energies, emission quantum yields) comparable to [Ru(bpy) 3 ] 2+ . With [(bda)Ru(isq) 2 ] as the catalyst, the chromophores promote visible-light-driven water oxidation with high activity at low pH. The chromophores with phosphonate groups as substituents showed higher activity than expected based on driving force arguments. In addition, kinetic isotope effects as high as ~3 were measured, suggesting the involvement of concerted proton-coupled transfer pathways between the catalyst and the chromophores with the phosphonate group acting as the proton acceptor. These chromophores therefore carry out the light absorption, charge migration, and proton transfer roles of P 680 , Tyr161, and His190 in Photosystem II on a single molecule and are good candidates for photoelectrochemical water oxidation at low pH in dye-sensitized photoelectrochemical cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The band structure and photocatalytic mechanism of MoS2-modified C3N4 photocatalysts with improved visible photocatalytic activity

Highlights: • A series of MoS{sub 2}/g-C{sub 3}N{sub 4} photocatalyst were prepared by water exfoliation method. • The heterojunction enhanced the visible response and separated charge carriers. • The MoS{sub 2}/g-C{sub 3}N{sub 4} exhibits enhanced visible photocatalytic activity. - Abstract: A series of MoS{sub 2}/g-C{sub 3}N{sub 4} photocatalysts were prepared by modifying g-C{sub 3}N{sub 4} with different concentration of MoS{sub 2} via a water exfoliation method. The crystal structure, morphology, band structure of heterojunction, behaviors of charge carries and the redox ability were characterized by XRD, HR-TEM, absorption spectra, XPS, PL, cyclic voltammetry curves and transient photocurrent spectra. It is revealed that the introduction of MoS{sub 2} on the surface of g-C{sub 3}N{sub 4} nanosheets to form micro-heterojunction could enhance the visible response and separate photogenerated charge carriers effectively. Moreover, the ability of the photocatalyst for generating reactive oxygen species (ROS, such as O{sub 2}{sup −} and OH) was also investigated. Therefore, MoS{sub 2}/g-C{sub 3}N{sub 4} samples exhibit better photocatalytic performance for the photodegradation of HCHO than g-C{sub 3}N{sub 4} and MoS{sub 2} under visible irradiation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electronic States of 2,3-Diamino-1,4-naphthoquinone and Its N-Alkylated Derivatives

Diaminoquinones with a captodatively stabilized biradicaloid structure are options for singlet fission, but few such compounds are known. We report the solution spectroscopy and photophysics of 1,2,2,3-tetramethyl-2,3-dihydro-1H-naphtho[2,3-d]imidazole-4,9-dione (1): its steady-state and transient UV-visible absorption, linear dichroism in stretched poly(vinyl alcohol), and magnetic circular dichroism. We also describe the absorption spectra of the stable radical ions 1+ and 1- and of two parent structures, 2,3-diamino-1,4-naphthoquinone (2) and 2,3-bis(methylamino)-1,4-naphthoquinone (3). The spectra are interpreted and electronic transitions are assigned by comparison with the results of density functional theory and MS-CASPT2 calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A series of Ln-p-chlorobenzoic acid–terpyridine complexes: lanthanide contraction effects, supramolecular interactions and luminescent behavior

Fifteen new lanthanide p-chlorobenzoic acid complexes, [PrL3(terpy)(H2O)]2 (1), [LnL3(terpy)(H2O)]2 (Ln = Nd (2), Sm (3), and Eu (4)), and [LnL3(terpy)(H2O)] (Ln = Sm (3'), Eu (4'), Gd (5), Tb (6), Dy (7), Ho (8), Er (9), Tm (10), Yb (11), Lu (12), and Y (13); HL: p-chlorobenzoic acid; terpy: 2,2':6',2''-terpyridine), have been synthesized hydrothermally at varying temperatures and structurally characterized by single crystal and powder X-ray diffraction. The series is comprised of binuclear molecular units (Pr–Eu) that give way to mononuclear molecular complexes (Sm–Y) as the lanthanide contraction takes effect. All fifteen complexes feature a tridentate terpyridine ligand, p-chlorobenzoic acid ligands exhibiting multiple binding modes, bidentate, bridging bidentate, and monodentate, and a bound water molecule. Binuclear complexes 1–4 are stitched together via intermolecular interactions: aromatic–aromatic interactions for 1, halogen•••halogen interactions for 2–4, to form 1D chains. Mononuclear complexes 3', 4', and 5–13 utilize supramolecular hydrogen and halogen bonding to form 2D sheets. Visible and near-IR solid state luminescence studies were performed on complexes 2, 3, 3', 4, 4', 6, 7 and 11 and the characteristic visible luminescence of Sm(III), Eu(III), Tb(III), and Dy(III) was exhibited. The near-IR spectra of the Nd(III) and Yb(III) complexes exhibit weak characteristic luminescence, showing that terpy can act as a sensitizing chromophore in these systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid silicon–carbon nanostructures for broadband optical absorption

Proper design of nanomaterials for broadband light absorption is a key factor for improving the conversion efficiency of solar cells. Here we present a hybrid design of silicon–carbon nanostructures with silicon clusters coated by carbon cages, i.e. , Si m @C 2n for potential solar cell application. The optical properties of these hybrid nanostructures were calculated based on time dependent density function theory (TDDFT). The results show that the optical spectra of Si m @C 2n are very different from those of pure Si m and C 2n clusters. While the absorption spectra of pure carbon cages and Si m clusters exhibit peaks in the UV region, those of the Si m @C 2n nanostructures exhibit a significant red shift. Superposition of the optical spectra of various Si m @C 2n nanostructures forms a broad-band absorption, which extends to the visible light and infrared regions. As a result, the broadband adsorption of the assembled Si m @C 2n nanoclusters may provide a new approach for the design of high efficiency solar cell nanomaterials.

36 MATERIALS SCIENCE↗

Solvent dependent branching between C-I and C-Br bond cleavage following 266 nm excitation of CH{sub 2}BrI

It is well known that ultraviolet photoexcitation of halomethanes results in halogen-carbon bond cleavage. Each halogen-carbon bond has a dominant ultraviolet (UV) absorption that promotes an electron from a nonbonding halogen orbital (n{sub X}) to a carbon-halogen antibonding orbital (σ*{sub C-X}). UV absorption into specific transitions in the gas phase results primarily in selective cleavage of the corresponding carbon-halogen bond. In the present work, broadband ultrafast UV-visible transient absorption studies of CH{sub 2}BrI reveal a more complex photochemistry in solution. Transient absorption spectra are reported spanning the range from 275 nm to 750 nm and 300 fs to 3 ns following excitation of CH{sub 2}BrI at 266 nm in acetonitrile, 2-butanol, and cyclohexane. Channels involving formation of CH{sub 2}Br + I radical pairs, iso-CH{sub 2}Br-I, and iso-CH{sub 2}I-Br are identified. The solvent environment has a significant influence on the branching ratios, and on the formation and stability of iso-CH{sub 2}Br-I. Both iso-CH{sub 2}Br-I and iso-CH{sub 2}I-Br are observed in cyclohexane with a ratio of ∼2.8:1. In acetonitrile this ratio is 7:1 or larger. The observation of formation of iso-CH{sub 2}I-Br photoproduct as well as iso-CH{sub 2}Br-I following 266 nm excitation is a novel result that suggests complexity in the dissociation mechanism. We also report a solvent and concentration dependent lifetime of iso-CH{sub 2}Br-I. At low concentrations the lifetime is >4 ns in acetonitrile, 1.9 ns in 2-butanol and ∼1.4 ns in cyclohexane. These lifetimes decrease with higher initial concentrations of CH{sub 2}BrI. The concentration dependence highlights the role that intermolecular interactions can play in the quenching of unstable isomers of dihalomethanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bright x-ray stainless steel K-shell source development at the National Ignition Facility

High x-ray conversion efficiency (XRCE) K-shell sources are being developed for high energy density experiments for use as backlighters and for the testing of materials exposed to high x-ray fluxes and fluences. Recently, sources with high XRCE in the K-shell x-ray energy range of iron and nickel were investigated at the National Ignition Facility (NIF). The x-ray conversion efficiency in the 5–9 keV spectral range was determined to be 6.8% ± 0.3%. These targets were 4.1 mm diameter, 4 mm tall hollow epoxy tubes having a 50 μm thick wall supporting a tube of 3 to 3.5 μm thick stainless steel. The NIF laser deposited ∼460 kJ of 3ω light into the target in a 140 TW, 3.3 ns square pulse. The absolute x-ray emission of the source was measured by two calibrated Dante x-ray spectrometers. Time resolved images filtered for the Fe K-shell were recorded to follow the heating of the target. Time integrated high-resolution spectra were recorded in the K-shell range.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

VUV action spectroscopy of protonated leucine-enkephalin peptide in the 6-14 eV range

We have studied the Vacuum Ultraviolet (VUV) photodissociation of gas-phase protonated leucine-enkephalin peptide ion in the 5.7 to 14 eV photon energy range by coupling a linear quadrupole ion trap with a synchrotron radiation source. We report VUV activation tandem mass spectra at 6.7, 8.4, and 12.8 eV photon energies and photodissociation yields for a number of selected fragments. The obtained results provide insight into both near VUV radiation damage and electronic properties of a model peptide. We could distinguish several absorption bands and assign them to particular electronic transitions, according to previous theoretical studies. The photodissociation yields appear to be very different for the various observed fragmentation channels, depending on both the types of fragments and their position along the peptide backbone. The present results are discussed in light of recent gas-phase spectroscopic data on peptides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Efficient radical cation stabilization of PANI-ZnO and PANI-ZnO-GO composites and its optical activity

Polyaniline (PANI) and its composites PANI-ZnO (Zinc oxide) and PANI-ZnO-GO (Graphene oxide) were successfully constructed. These materials were characterized by electron spin resonance (ESR) technique and ultraviolet visible spectrometry. The parameters such as line width, g-factor and spin concentration were deduced from ESR spectra, from the results the radical cation stabilization of PANI, PANI-ZnO and PANI-ZnO-GO composites were compared by the polaron and bipolaron formation. The absorption features obtained in the UV absorption spectra reveal the band gap of these modified PANI composites and also predicted the information of increasing and decreasing features of signal intensity and spin concentration.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Statistical inference of collision frequencies from x-ray Thomson scattering spectra

Thomson scattering spectra measure the response of plasma particles to incident radiation. In warm dense matter, which is opaque to visible light, x-ray Thomson scattering (XRTS) enables a detailed probe of the electron distribution and has been used as a diagnostic for electron temperature, density, and plasma ionization. In this work, we examine the sensitivities of inelastic XRTS signatures to modeling details, including the dynamic collision frequency and the electronic density of states. Applying verified Monte Carlo inversion methods to dynamic structure factors obtained from time-dependent density functional theory, we assess the utility of XRTS signals as a way to inform the dynamic collision frequency, especially its direct-current limit, which is directly related to the electrical conductivity.

Collision frequency↗

EXAMINING THE BROADBAND EMISSION SPECTRUM OF WASP-19b: A NEW z-BAND ECLIPSE DETECTION

WASP-19b is one of the most irradiated hot-Jupiters known. Its secondary eclipse is the deepest of all transiting planets and has been measured in multiple optical and infrared bands. We obtained a z-band eclipse observation with a measured depth of 0.080% {+-} 0.029%, using the 2 m Faulkes Telescope South, which is consistent with the results of previous observations. We combined our measurement of the z-band eclipse with previous observations to explore atmosphere models of WASP-19b that are consistent with its broadband spectrum. We use the VSTAR radiative transfer code to examine the effect of varying pressure-temperature profiles and C/O abundance ratios on the emission spectrum of the planet. We find that models with super-solar carbon enrichment best match the observations, which is consistent with previous model retrieval studies. We also include upper atmosphere haze as another dimension in the interpretation of exoplanet emission spectra and find that particles <0.5 {mu}m in size are unlikely to be present in WASP-19b.

79 ASTRONOMY AND ASTROPHYSICS↗

KIC 9406652: AN UNUSUAL CATACLYSMIC VARIABLE IN THE KEPLER FIELD OF VIEW

KIC 9406652 is a remarkable variable star in the Kepler field of view that shows both very rapid oscillations and long term outbursts in its light curve. We present an analysis of the light curve over quarters 1-15 and new spectroscopy that indicates that the object is a cataclysmic variable with an orbital period of 6.108 hr. However, an even stronger signal appears in the light curve periodogram for a shorter period of 5.753 hr, and we argue that this corresponds to the modulation of flux from the hot spot region in a tilted, precessing disk surrounding the white dwarf star. We present a preliminary orbital solution from radial velocity measurements of features from the accretion disk and the photosphere of the companion. We use a Doppler tomography algorithm to reconstruct the disk and companion spectra, and we also consider how these components contribute to the object's spectral energy distribution from ultraviolet to infrared wavelengths. This target offers us a remarkable opportunity to investigate disk processes during the high mass transfer stage of evolution in cataclysmic variables.

79 ASTRONOMY AND ASTROPHYSICS↗

A monitoring campaign for Luhman 16AB. I. Detection of resolved near-infrared spectroscopic variability

We report resolved near-infrared spectroscopic monitoring of the nearby L dwarf/T dwarf binary WISE J104915.57–531906.1AB (Luhman 16AB), as part of a broader campaign to characterize the spectral energy distribution and temporal variability of this system. A continuous 45 minute sequence of low-resolution IRTF/SpeX data spanning 0.8-2.4 μm were obtained, concurrent with combined-light optical photometry with ESO/TRAPPIST. Our spectral observations confirm the flux reversal of this binary, and we detect a wavelength-dependent decline in the relative spectral fluxes of the two components coincident with a decline in the combined-light optical brightness of the system over the course of the observation. These data are successfully modeled as a combination of achromatic (brightness) and chromatic (color) variability in the T0.5 Luhman 16B, consistent with variations in overall cloud opacity; and no significant variability was found in L7.5 Luhman 16A, consistent with recent resolved photometric monitoring. We estimate a peak-to-peak amplitude of 13.5% at 1.25 μm over the full light curve. Using a simple two-spot brightness temperature model for Luhman 16B, we infer an average cold covering fraction of ≈30%-55%, varying by 15%-30% over a rotation period assuming a ≈200-400 K difference between hot and cold regions. We interpret these variations as changes in the covering fraction of a high cloud deck and corresponding 'holes' which expose deeper, hotter cloud layers, although other physical interpretations are possible. A Rhines scale interpretation for the size of the variable features explains an apparent correlation between period and amplitude for Luhman 16B and the variable T dwarfs SIMP 0136+0933 and 2MASS J2139+0220, and predicts relatively fast winds (1-3 km s{sup –1}) for Luhman 16B consistent with light curve evolution on an advective time scale (1-3 rotation periods). The strong variability observed in this flux reversal brown dwarf pair supports the model of a patchy disruption of the mineral cloud layer as a universal feature of the L dwarf/T dwarf transition.

79 ASTRONOMY AND ASTROPHYSICS↗

The corona of HD 189733 and its X-ray activity

Testing whether close-in massive exoplanets (hot Jupiters) can enhance the stellar activity in their host primary is crucial for the models of stellar and planetary evolution. Among systems with hot Jupiters, HD 189733 is one of the best studied because of its proximity, strong activity, and the presence of a transiting planet, which allows transmission spectroscopy and a measure of the planetary radius and its density. Here we report on the X-ray activity of the primary star, HD 189733 A, using a new XMM-Newton observation and a comparison with the previous X-ray observations. The spectrum in the quiescent intervals is described by two temperatures at 0.2 keV and 0.7 keV, while during the flares a third component at 0.9 keV is detected. With the analysis of the summed Reflection Grating Spectrometer spectra, we obtain estimates of the electron density in the range n{sub e} = (1.6-13) × 10{sup 10} cm{sup –3}, and thus the corona of HD 189733 A appears denser than the solar one. For the third time, we observe a large flare that occurred just after the eclipse of the planet. Together with the flares observed in 2009 and 2011, the events are restricted to a small planetary phase range of φ = 0.55-0.65. Although we do not find conclusive evidence of a significant excess of flares after the secondary transits, we suggest that the planet might trigger such flares when it passes close to the locally high magnetic field of the underlying star at particular combinations of stellar rotational phases and orbital planetary phases. For the most recent flares, a wavelet analysis of the light curve suggests a loop of length of four stellar radii at the location of the bright flare, and a local magnetic field of the order of 40-100 G, in agreement with the global field measured in other studies. The loop size suggests an interaction of magnetic nature between planet and star, separated by only ∼8R {sub *}. The X-ray variability of HD 189733 A is larger than the variability of field stars and young Pleiades of similar spectral type and X-ray luminosity. We also detect the stellar companion (HD 189733 B, ∼12'' from the primary star) in this XMM-Newton observation. Its very low X-ray luminosity (L{sub X} = 3.4 × 10{sup 26} erg s{sup –1}) confirms the old age of this star and of the binary system. The high activity of the primary star is best explained by a transfer of angular momentum from the planet to the star.

79 ASTRONOMY AND ASTROPHYSICS↗

Clues to the nature of SN 2009ip from photometric and spectroscopic evolution to late times

We present time series photometric and spectroscopic data for the transient SN 2009ip from the start of its outburst in 2012 September until 2013 November. These data were collected primarily with the new robotic capabilities of the Las Cumbres Observatory Global Telescope Network, a specialized facility for time domain astrophysics, and includes supporting high-resolution spectroscopy from the Southern Astrophysical Research Telescope, Kitt Peak National Observatory, and Gemini Observatory. Based on our nightly photometric monitoring, we interpret the strength and timing of fluctuations in the light curve as interactions between fast-moving ejecta and an inhomogeneous circumstellar material (CSM) produced by past eruptions of this massive luminous blue variable (LBV) star. Our time series of spectroscopy in 2012 reveals that, as the continuum and narrow Hα flux from CSM interactions declines, the broad component of Hα persists with supernova (SN)-like velocities that are not typically seen in LBVs or SN impostor events. At late times, we find that SN 2009ip continues to decline slowly, at ≲ 0.01 mag day{sup –1}, with small fluctuations in slope similar to Type IIn supernovae (SNe IIn) or SN impostors but no further LBV-like activity. The late-time spectrum features broad calcium lines similar to both late-time SNe and SN impostors. In general, we find that the photometric and spectroscopic evolution of SN 2009ip is more similar to SNe IIn than either continued eruptions of an LBV star or SN impostors but we cannot rule out a nonterminal explosion. In this context, we discuss the implications for episodic mass loss during the late stages of massive star evolution.

79 ASTRONOMY AND ASTROPHYSICS↗

How gravitational lensing helps γ-ray photons avoid γ – γ absorption

We investigate potential γ – γ absorption of γ-ray emission from blazars arising from inhomogeneities along the line of sight, beyond the diffuse Extragalactic Background Light (EBL). As plausible sources of excess γ – γ opacity, we consider (1) foreground galaxies, including cases in which this configuration leads to strong gravitational lensing, (2) individual stars within these foreground galaxies, and (3) individual stars within our own galaxy, which may act as lenses for microlensing events. We found that intervening galaxies close to the line of sight are unlikely to lead to significant excess γ – γ absorption. This opens up the prospect of detecting lensed gamma-ray blazars at energies above 10 GeV with their gamma-ray spectra effectively only affected by the EBL. The most luminous stars located either in intervening galaxies or in our galaxy provide an environment in which these gamma-rays could, in principle, be significantly absorbed. However, despite a large microlensing probability due to stars located in intervening galaxies, γ-rays avoid absorption by being deflected by the gravitational potentials of such intervening stars to projected distances ({sup i}mpact parameters{sup )} where the resulting γ – γ opacities are negligible. Thus, neither of the intervening excess photon fields considered here, provide a substantial source of excess γ – γ opacity beyond the EBL, even in the case of very close alignments between the background blazar and a foreground star or galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗

Optical and ultraviolet observations of a low-velocity type II plateau supernova 2013am in M65

Optical and ultraviolet observations for the nearby type II plateau supernova (SN IIP) 2013am in the nearby spiral galaxy M65 are presented in this paper. The early spectra are characterized by relatively narrow P-Cygni features, with ejecta velocities much lower than observed in normal SNe IIP (i.e., ∼2000 km s{sup –1} versus ∼5000 km {sup –1} in the middle of the plateau phase). Moreover, prominent Ca II absorptions are also detected in SN 2013am at relatively early phases. These spectral features are reminiscent of those seen in the low-velocity and low-luminosity SN IIP 2005cs. However, SN 2013am exhibits different photometric properties, having shorter plateau phases and brighter light curve tails if compared to SN 2005cs. Adopting R{sub V} = 3.1 and a mean value of total reddening derived from the photometric and spectroscopic methods (i.e., E(B – V) = 0.55 ± 0.19 mag), we find that SN 2013am may have reached an absolute V-band peak magnitude of –15.83 ± 0.71 mag and produced an {sup 56}Ni mass of 0.016{sub −0.006}{sup +0.010} M {sub ☉} in the explosion. These parameters are close to those derived for SN 2008in and SN 2009N, which have been regarded as 'gap-filler' objects linking the faint SNe IIP to the normal ones. This indicates that some low-velocity SNe IIP may not necessarily result from the low-energetic explosions. The low expansion velocities could be due to a lower metallicity of the progenitor stars, a larger envelope mass ejected in the explosion, or the effect of viewing angle where these SNe were observed at an angle away from the polar direction.

79 ASTRONOMY AND ASTROPHYSICS↗