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At least 163 records · Page 9

Nanocrystalline Chalcopyrite Materials (CuInS2 and CuInSe2) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors

Nanometer sized particles of the chalcopyrite compounds CuInS2 and CuInSe2 were synthesized by thermal decomposition of molecular single-source precursors (PPh3)2CuIn(SEt)4 and (PPh3)2CuIn(SePh)4, respectively, in the non-coordinating solvent dioctyl phthalate at temperatures between 200 and 300 C. The nanoparticles range in size from 3 - 30 nm and are aggregated to form roughly spherical clusters of about 500 nm in diameter. X-ray diffraction of the nanoparticle powders shows greatly broadened lines indicative of very small particle sizes, which is confirmed by TEM. Peaks present in the XRD can be indexed to reference patterns for the respective chalcopyrite compounds. Optical spectroscopy and elemental analysis by energy dispersive spectroscopy support the identification of the nanoparticles as chalcopyrites.

Castro, Stephanie L.↗

Revealing electronic state-switching at conical intersections in alkyl iodides by ultrafast XUV transient absorption spectroscopy

Conical intersections between electronic states often dictate the chemistry of photoexcited molecules. Recently developed sources of ultrashort extreme ultraviolet (XUV) pulses tuned to element-specific transitions in molecules allow for the unambiguous detection of electronic state-switching at a conical intersection. Here, the fragmentation of photoexcited iso-propyl iodide and tert-butyl iodide molecules (i-C 3 H 7 I and t-C 4 H 9 I) through a conical intersection between 3 Q 0 / 1 Q 1 spin-orbit states is revealed by ultrafast XUV transient absorption measuring iodine 4d core-to-valence transitions. The electronic state-sensitivity of the technique allows for a complete mapping of molecular dissociation from photoexcitation to photoproducts. In both molecules, the sub-100 fs transfer of a photoexcited wave packet from the 3 Q 0 state into the 1 Q 1 state at the conical intersection is captured. The results show how differences in the electronic state-switching of the wave packet in i-C 3 H 7 I and t-C 4 H 9 I directly lead to differences in the photoproduct branching ratio of the two systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Infrared Spectroscopy of Black Hole Candidates

ISO LWS and SWS observations of the approx. solar mass black hole candidates 1E1740.7-2942 and GRS1758-258 are presented. For 1E1740.7-2942, it has been suggested that the luminosity is provided in whole or part by Bondi-Hoyle accretion from a surrounding black hole (Bally & Leventhal 1991, Nat, 353,234). Maloney et al. (1997, ApJ482, L41) have predicted that detectable far-infrared line emission from [0I] (63 microns), [CII] (158 microns), [SiII] (35 microns) and other lines will arise from black holes which are embedded in molecular clouds. No strong line emission associated with either 1E1740.7-2942 or GRS1758-258 was detected, implying either that 1) these sources are not embedded in dense molecular clouds, or 2) that their average X-ray luminosity over the past 100 years is significantly lower than its current value. The measured upper limits to the line fluxes are compared with the models of Maloney et al.to constrain the properties of the ISM in the vicinity of these X-ray sources.

Colgan, Sean W.↗

Generation of Optical Combs in a WGM Resonator from a Bichromatic Pump

Optical combs generated by a monolithic resonator with Kerrmedium can be used in a number of applications, including orbital clocks and frequency standards of extremely high accuracy, such as astronomy, molecular spectroscopy, and the like. The main difficulty of this approach is the relatively high pump power that has to be used in such devices, causing undesired thermorefractive effects, as well as stimulated Raman scattering, and limiting the optical comb quality and utility. In order to overcome this problem, this innovation uses a different approach to excitation of the nonlinear oscillations in a Kerr-nonlinear whispering gallery mode (WGM) resonator and generation of the optical comb. By coupling to the resonator two optical pump frequencies instead of just one, the efficiency of the comb source can be increased considerably. It therefore can operate in a lowerpower regime where the undesirable effects are not present. This process does not have a power threshold; therefore, the new optical component can easily be made strong enough to generate further components, making the optical comb spread in a cascade fashion. Additionally, the comb spacing can be made in an arbitrary number of the resonator free spectral ranges (FSR). The experimental setup for this innovation used a fluorite resonator with OMEGA= 13.56 GHz. This material has very low dispersion at the wavelength of 1.5 microns, so the resonator spectrum around this wavelength is highly equidistant. Light was coupled in and out of the resonator using two optical fibers polished at the optimal coupling angle. The gap between the resonator and the fibers, affecting the light coupling and the resonator loading, was controlled by piezo positioners. The light from the input fiber that did not go into the resonator reflected off of its rim, and was collected by a photodetector. This enabled observation and measurement of the (absorption) spectrum of the resonator. The input fiber combined light from two lasers centered at around 1,560 nanometers. Both laser frequencies were simultaneously scanned around the selected WGMs of the same family. However, they were separated by one, two, three, or ten FSRs. This was achieved by fine-tuning each laser frequency offset until the selected resonances overlap on the oscilloscope screen. The resonator quality factor Q = 7 x 10(exp 7) was relatively low to increase the linewidth and, therefore, the duty cycle of both lasers simultaneously coupled into their WGMs. The optical spectrum analyzer (OSA) connected to the output fiber was continuously acquiring data, asynchronously with the laser scan. The instrument was set to retain the peak power values; therefore, a trace recorded for a sufficiently long period of time reflected the situation with both lasers maximally coupled to the WGMs.

Strekalov, Dmitry V.↗

10 micron spectroscopy of younger stars in the rho Ophiuchi cloud

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

Hanner, M. S.↗

Far UV Spectroscopy of eta Carinae

We present the first high spectral resolution observations of the Luminous Blue Variable eta Carinae between the Lyman limit and 1180 Angstroms. High resolution spectra (R approximately 20,000) were obtained with the Far Ultraviolet Spectroscopic Explorer (FUSE) satellite on Feb. 1 and Mar. 20, 2000. The observations were made with a 30x30 arcsec aperture and includes the entire Homunculus region. However, the spatial extent of the far UV flux is consistent with a point source. With the limited spatial resolution of the FUSE instrument, we can only constrain the far UV emission to be within +/-5 arcsec of the star. The far UV spectrum of eta Car is dominated by strong absorption features of molecular hydrogen. The observed flux level at 1150 Angstroms is approximately 4\times 10(exp 12) erg/sq cm/s/Angstrom and decreases approximately linearly to approximately 920 Angstroms where converging HI and HII features completely blanket the spectrum. These observations were obtained as part of the FUSE Early Release Observation program.

Iping, R. C.↗

Surface stability of SrNbO 3+δ grown by hybrid molecular beam epitaxy

4d transition metal oxides have emerged as promising materials for numerous applications including high mobility electronics. SrNbO 3 is one such candidate material, serving as a good donor material in interfacial oxide systems and exhibiting high electron mobility in ultrathin films. However, its synthesis is challenging due to the metastable nature of the d 1 Nb 4+ cation and the limitations in the delivery of refractory Nb. To date, films have been grown primarily by pulsed laser deposition (PLD), but development of a means to grow and stabilize the material via molecular beam epitaxy (MBE) would enable studies of interfacial phenomena and multilayer structures that may be challenging by PLD. To that end, SrNbO 3 thin films were grown using hybrid MBE for the first time using a tris(diethylamido)(tert-butylimido) niobium precursor for Nb and an elemental Sr source on GdScO 3 substrates. Varying thicknesses of insulating SrHfO 3 capping layers were deposited using a hafnium tert-butoxide precursor for Hf on top of SrNbO 3 films to preserve the metastable surface. Grown films were transferred in vacuo for x-ray photoelectron spectroscopy to quantify elemental composition, density of states at the Fermi energy, and Nb oxidation state. Ex situ studies by x-ray absorption near edge spectroscopy and scanning transmission electron microscopy illustrate that the SrHfO 3 capping plays an important role in preserving the crystalline quality of the material and the Nb 4d 1 metastable charge state under atmospheric conditions.

36 MATERIALS SCIENCE↗

Atomic fluctuations in electronic materials revealed by dephasing

The microscopic origin and timescale of the fluctuations of the energies of electronic states has a significant impact on the properties of interest of electronic materials, with implication in fields ranging from photovoltaic devices to quantum information processing. Spectroscopic investigations of coherent dynamics provide a direct measurement of electronic fluctuations. Modern multidimensional spectroscopy techniques allow the mapping of coherent processes along multiple time or frequency axes and thus allow unprecedented discrimination between different sources of electronic dephasing. Exploiting modern abilities in coherence mapping in both amplitude and phase, we unravel dissipative processes of electronic coherences in the model system of CdSe quantum dots (QDs). The method allows the assignment of the nature of the observed coherence as vibrational or electronic. The expected coherence maps are obtained for the coherent longitudinal optical (LO) phonon, which serves as an internal standard and confirms the sensitivity of the technique. Fast dephasing is observed between the first two exciton states, despite their shared electron state and common environment. This result is contrary to predictions of the standard effective mass model for these materials, in which the exciton levels are strongly correlated through a common size dependence. In contrast, the experiment is in agreement with ab initio molecular dynamics of a single QD. Electronic dephasing in these materials is thus dominated by the realistic electronic structure arising from fluctuations at the atomic level rather than static size distribution. The analysis of electronic dephasing thereby uniquely enables the study of electronic fluctuations in complex materials.

36 MATERIALS SCIENCE↗

Moderate-resolution K-band Spectroscopy of Substellar Companion κ Andromedae b

We present moderate-resolution (R ∼ 4000) K-band spectra of the “super-Jupiter,” κ Andromedae b. The data were taken with the OSIRIS integral field spectrograph at Keck Observatory. The spectra reveal resolved molecular lines from H{sub 2}O and CO, and are compared to a custom PHOENIX atmosphere model grid appropriate for young planetary-mass objects. We fit the data using a Markov chain Monte Carlo forward-modeling method. Using a combination of our moderate-resolution spectrum and low-resolution, broadband data from the literature, we derive an effective temperature of T {sub eff} = 1950–2150 K, a surface gravity of logg=3.5--4.5, and a metallicity of [M/H] = −0.2–0.0. These values are consistent with previous estimates from atmospheric modeling and the currently favored young age of the system (<50 Myr). We derive a C/O ratio of 0.70{sub −0.24}{sup +0.09} for the source, broadly consistent with the solar C/O ratio. This, coupled with the slightly subsolar metallicity, implies a composition consistent with that of the host star, and is suggestive of formation by a rapid process. The subsolar metallicity of κ Andromedae b is also consistent with predictions of formation via gravitational instability. Further constraints on formation of the companion will require measurement of the C/O ratio of κ Andromedae A. We also measure the radial velocity of κ Andromedae b for the first time, with a value of −1.4 ± 0.9 km s{sup −1} relative to the host star. We find that the derived radial velocity is consistent with the estimated high eccentricity of κ Andromedae b.

79 ASTRONOMY AND ASTROPHYSICS↗

Infrared spectroscopic measurements of halogenated source gases in the stratosphere with the ATMOS instrument

The volume mixing ratios of the six most important halogenated source species (CH3Cl, CF2Cl2, CFCl3, CHF2Cl, CCl4, and CF4) have been retrieved over the 10- to 30-km altitude range from the analysis of 0.01/cm resolution infrared solar occultation spectra recorded near 30 deg N and 47 deg S latitudes with the ATMOS (Atmospheric Trace Molecule Spectroscopy) instrument, operating from on board Spacelab 3 (April-May 1985). The results reported here, although in satisfactory agreement with recent in situ values obtained from air sampling techniques, are limited in accuracy by the limited absorption representative of most of the species and by uncertainties in the spectroscopic parameters currently available for these gases. They demonstrate, however, the power of the IR remote sensing approach for evaluating on a global scale the total chlorine budget of the atmosphere, and they provide an independent set of simultaneous data acquired for the important source and reservoir halogenated molecular species in the upper atmosphere.

Zander, R.↗

Far UV Spectroscopy of eta Carinae

We present the first high spectral resolution observations of the Luminous Blue Variable eta Carinae between the Lyman limit and 1180 A. High resolution spectra (R approx. 20,000) were obtained with the Far Ultraviolet Spectroscopic Explorer (FUSE) satellite on Feb. 1 and Mar. 20, 2000. The observations were made with a 30 x 30 arcsec aperture and includes the entire Homunculus region. However, the spatial extent of the far UV flux is consistent with a point source. With the limited spatial resolution of the FUSE instrument, we can only constrain the far UV emission to be within +/- 5 arcsec of the star. The far UV spectrum of eta Car is dominated by strong absorption features of molecular hydrogen. The observed flux level at 1150A is approx. 4 times 10(exp 12) erg /cm(exp -2) /sec(exp -1) / A(exp -1) and decreases approximately linearly to approx. 920 A where converging H1 and H2 features completely blanket the spectrum. These observations were obtained as part of the FUSE Early Release Observation program.

Iping, R. C.↗

Crystallization and preliminary X-ray analysis of Der f 2, a potent allergen derived from the house dust mite (Dermatophagoides farinae)

Although a number of allergens have been identified and isolated, the underlying molecular basis for the potent immune response is poorly understood. House dust mites (Dermatophagoides sp.) are ubiquitous contributors to atopy in developed countries. The rhinitis, dermatitis and asthma associated with allergic reactions to these arthropods are frequently caused by relatively small (125-129 amino acids) mite proteins of unknown biological function. Der f 2, a major allergen from the mite D. farinae, has been recombinantly expressed, characterized and crystallized. The crystals belong to the tetragonal space group I4(1)22, with unit-cell parameters a = b = 95.2, c = 103.3 A. An essentially complete (97.2%) data set has been collected to 2.4 A at a synchrotron source. Attempts to solve the crystal structure of Der f 2 by molecular replacement using the NMR coordinates for either Der f 2 or Der p 2 (the homologous protein from D. pteronyssinus) failed, but preliminary searches using the crystalline Der p 2 atomic coordinates appear to be promising.

Pyroglyphidae/chemistry/immunology↗

Prospects for Habitable World Detections Using James Webb Space Telescope (JWST)

Doppler and transit surveys are finding extrasolar planets of ever smaller mass and radius, and are now sampling the domain of superEarths. Recent results from the Doppler surveys suggest that discovery of a transiting superEarth in the habitable zone of a lower main sequence star may be possible. We evaluate the prospects for an all-sky transit survey targeted to the brightest stars I that would find the most favorable cases for photometric and spectroscopic characterization using the James Webb Space Telescope. We use the proposed Transiting Exoplanet Survey Satellite (TESS) as representative of an all-sky survey. We couple the simulated TESS yield to a sensitivity model for the MIRI and NIRSpec instruments on JWST. Our sensitivity model includes all currently known and anticipated sources of random and systematic error for these instruments. We focus on the TESS planets with radii between Earth and Neptune. Our simulations consider secondary eclipse filter photometry using JWST/MIRI, comparing the 11- and 15- micron bands to measure carbon dioxide absorption in superEarths, as well as JWST!NIRSpec spectroscopy of water absorption from 1.7-3.0 microns, and carbon dioxide absorption at 4.3 microns. We find that JWST will be capable of characterizing dozens of TESS superEarths with temperatures above the habitable range, using both MIRI and NIRspec. We project that TESS will discover about eight nearby habitable transiting superEarths, all orbiting lower main sequence stars. The principal sources of uncertainty in the prospects for JWST characterization of habitable superEarths are superEarth frequency and the nature of superEarth atmospheres. Based on our estimates of these uncertainties, we project that JWST will be able to measure the temperature, and identify molecular absorptions (water, carbon dioxide) in one to four nearby habitable TESS superEarths orbiting lower main sequence stars.

Deming, Drake↗

Balloon-borne diode-laser absorption spectrometer for measurements of stratospheric trace species

An instrument has been designed for the measurement of stratospheric trace species which utilizes tunable infrared diode lasers as sources for sensitive in situ absorption spectroscopy in selected wavelength regions. This instrument, the Balloon-Borne Laser In Situ Sensor (BLISS), is a high-resolution absorption spectrometer designed to provide measurements of the concentrations of stratospheric species and their diurnal variations. The instrument employs second-harmonic detection of the absorption of tunable diode laser (TDL) radiation (3-30 microns) in a 1 km path length defined by a retroreflector lowered 0.5 km below the BLISS gondola. Retroreflector tracking under microprocessor control is obtained using a He-Ne laser and coaligned TV camera with CID imaging. Simultaneous measurements of molecular species in the 20-40 km altitude range will be performed using four TDLs, with the predicted minimum-detectable mixing ratio at 30 km being typically less than or equal to 0.1 ppbv.

Menzies, R. T.↗

The UCB/MPE Cassegrain Submillimeter Heterodyne Spectrometer

The UCB/MPE Submillimeter Heterodyne Spectrometer is a system for astronomical spectroscopy in the high-frequency atmospheric windows from 500 to 1000 GHz. It contains a molecular laser local oscillator, a cooled Schottky open structure mixer, a quasi-optical coupling system, and an acoustooptical spectrometer. The compact receiver mounts at the Cassegrain focus of large infrared astronomical telescopes. The receiver noise temperature on the telescope is approximately 3500 K (DSB) during observations of the CO J = 7-6 line at 806.652 GHz. The spectrometer's frequency resolution and instantaneous bandwidth (less than 2 MHz resolution across 1.1 GHz) are well suited for observations of molecular emission lines from a variety of astronomical sources.

Harris, A. I.↗

Defect Generation and Evolution in Irradiated Epitaxial Films and Heterostructures of Fe 3 O 4 and Cr 2 O 3

Abstract The functionality of nuclear structural materials, sensors, and microelectronics in harsh environments such as radiation relies on understanding defect generation and evolution processes in oxide layers. The initial radiation response of epitaxial thin films of Fe 3 O 4 (111), Cr 2 O 3 (0001), and Fe 3 O 4 (111)/Cr 2 O 3 (0001) heterostructures deposited on Al 2 O 3 (0001) by oxygen‐assisted molecular beam epitaxy and irradiated with 200 keV He + is characterized. X‐ray diffraction and X‐ray absorption near edge spectroscopy showed that the Cr 2 O 3 layers underwent significant lattice expansion and disordering under irradiation, whereas the Fe 3 O 4 layers do not exhibit noticeable changes. In contrast, positron annihilation spectroscopy revealed an evolution of cation vacancy point defects in the Fe 3 O 4 layers into larger vacancy clusters with increasing irradiation, while the cation vacancies in Cr 2 O 3 remained primarily as single vacancies and small clusters. The results suggest that the Fe 3 O 4 lattice can utilize the free volume of the larger vacancy clusters to relax but the small vacancies in the Cr 2 O 3 lattice do not facilitate relaxation. Comparing defect concentrations in the single layer films versus the heterostructure suggests that point defects may cross the interface from Fe 3 O 4 into Cr 2 O 3 . Together, these results enhance the understanding of the initial defect evolution mechanisms in oxide layers in harsh irradiation environments.

36 MATERIALS SCIENCE↗

Velocity-Map Imaging and Magnetic-Bottle Photoelectron Spectroscopy of [SeCCH] – : Electronic Properties and Spin–Orbit Splitting

In this work, the recently synthesized acetylide compound KSeCCH containing the main group element selenium within the novel and in crystalline form unprecedented [SeCCH] – anion was successfully investigated in the gas phase by high-resolution velocity-map imaging (VMI) and magnetic-bottle (MB) photoelectron spectroscopy coupled with an electrospray ionization source. Both VMI and MB spectra exhibited identical electron affinities (EA, 2.517 ± 0.002 eV), spin–orbit coupling (SOC) splittings (1492 ± 20 cm –1 ), and Se–C stretching frequencies (573 ± 20 cm –1 ) of the corresponding neutral tetra-atomic radical [SeCCH] • with the VMI spectrum possessing six times higher spectral resolution compared with the MB spectrum. These experimental values were well reproduced by calculations at the CCSD(T) level, in which both the isolated [SeCCH] – anion and the [SeCCH] • radical adopted linear geometries. The simulated spectra based on the calculated Franck–Condon factors, the SOC splitting, and the experimental line width matched well with the measured spectra. Furthermore, comparisons of the EA and SOC splitting values with the previously reported isolobal species [SeCN] • are also made and discussed. The decrease in the EA and SOC splitting of [SeCCH] • is ascribed to the differences in the electronegativities between C and N atoms as well as the electron density on the Se atom in its singly occupied molecular orbital (SOMO).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Clock transitions guard against spin decoherence in singlet fission

Short coherence times present a primary obstacle in quantum computing and sensing applications. In atomic systems, clock transitions (CTs), formed from avoided crossings in an applied Zeeman field, can substantially increase coherence times. We show how CTs can dampen intrinsic and extrinsic sources of quantum noise in molecules. Conical intersections between two periodic potentials form CTs in electron paramagnetic resonance experiments of the spin-polarized singlet fission photoproduct. We report on a pair of CTs for a two-chromophore molecule in terms of the Zeeman field strength, molecular orientation relative to the field, and molecular geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗