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At least 1,315 records · Page 73

The multi-optics high-resolution absorption x-ray spectrometer (HiRAXS) for studies of materials under extreme conditions

We report the development of a high-resolution spectrometer for extended x-ray absorption fine structure (EXAFS) studies of materials under extreme conditions. A curved crystal and detector in the spectrometer are replaceable such that a single body is employed to perform EXAFS measurements at different x-ray energy intervals of interest. Two configurations have been implemented using toroidal crystals with Ge 311 reflection set to provide EXAFS at the Cu K-edge (energy range 8.9–9.8 keV) and Ge 400 reflection set to provide EXAFS at the Ta L3-edge (9.8–10.7 keV). Key performance characteristics of the spectrometer were found to be consistent with design parameters. The data generated at the National Ignition Facility have shown an ≃3 eV spectral resolution for the Cu K-edge configuration and ≃6 eV for the Ta L3-edge configuration.

Stoupin, S. (ORCID:0000000226225270)↗

Angle-Selective Reflective Filters for Exclusion of Background Thermal Emission

Selective filtering of spectral and angular optical transmission has recently attracted a great deal of interest. While optical passband and stop-band spectral filters are already widely used, angle-selective transmission and reflection filtering represents a less than fully explored alternative. Nonetheless, this approach can be promising for several applications, including stray radiation minimization and background emission exclusion. In this work, a concept for angle-selective reflection filtering using guided-mode resonance coupling is proposed. Although guided-mode resonance structures are already used for spectral filtering, in this work, a variation of angle-selective reflection filtering using guided-mode resonance coupling is proposed. We investigate angle-dependent properties of such structures for potential use as angle-selective reflective filters. Furthermore, we utilize interference between diffraction modes to provide tunable selectivity with a sufficient angular width. Combining these structures with thermal emitters can exclude selected emission angles for spatially selective thermal emissivity reduction toward sensitive targets, as well as directionally selective emissivity exclusion for suppression of solar heating. We show a very large selective reduction of heat exchange by 99.77% between an engineered emitter and a distant receiver using just a single-groove grating and an emitting substrate in the emitter’s side. Also, we show a selective reduction of heat exchange by approximately 77% between an emitter covered by engineered sets of angle-selective reflective filters and a nearby sensitive target. The suggested angle-selective structure may have applications in excluding background thermal radiation, in particular, thermal emission reduction for daytime radiative cooling, sensitive IR telescope detectors, and high-fidelity thermoluminescent spectroscopy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Optical atmospheric scattering and absorption limitations on offset pointing from Earth Observatory Satellite /EOS/ sensors

The Braslau-Dave atmospheric model which calculates the upward monochromatic light fluxes leaving the top of the atmosphere as a function of viewing angle, sun angle, and ground reflectance was employed to study the effect of atmospheric scattering and attenuation on universal apparent contrast for two EOS remote sensors operated at very large offset or pointing angles: the Thematic Mapper (TM) and the High Resolution Pointable Imager (HRPI). The TM offset off nadir could be plus or minus 20 degrees with an 11 degree scan angle and the HRPI pointing angle off nadir could be plus or minus 45 degrees with a 3 degree scan angle. The reduction of universal apparent contrast of EOS imagery is studied as a function of sun elevation angle, atmospheric aerosol loading, radiation wavelength and sensor look angles.

Egan, W. G.↗

A high-resolution optical survey of interstellar absorption lines toward globular clusters and extragalactic objects. II - Further data

A status report is given on an ongoing survey of narrow-line, visual absorption components, which has been expanded to include lines of sight to the 3C 273 quasar, the nucleus of M87, and the NGC 1851, NGC 2808, and 47 Tuc globular cluster cores. The number density of components of the halo is calculated to lie between one-third and one per 100 kpc, though with substantial uncertainty. This estimate is held to be consistent with the galactic halo interpretation of the origin of high column density, quasar absorption-line systems.

Songaila, A.↗

Error Reduction Methods for Integrated-path Differential-absorption Lidar Measurements

We report new modeling and error reduction methods for differential-absorption optical-depth (DAOD) measurements of atmospheric constituents using direct-detection integrated-path differential-absorption lidars. Errors from laser frequency noise are quantified in terms of the line center fluctuation and spectral line shape of the laser pulses, revealing relationships verified experimentally. A significant DAOD bias is removed by introducing a correction factor. Errors from surface height and reflectance variations can be reduced to tolerable levels by incorporating altimetry knowledge and "log after averaging", or by pointing the laser and receiver to a fixed surface spot during each wavelength cycle to shorten the time of "averaging before log".

averging before log↗

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. Furthermore, a detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-N amido complexes using a high-spin ground-state analogue as a spectral model for the 5 T 2 excited state.

14 SOLAR ENERGY↗

Long-Lived Photoinduced Charge Separation in a Trinuclear Iron-μ 3 -oxo-based Metal–Organic Framework

The presence of long-lived charge-separated excited states in metal-organic frameworks (MOFs) can enhance their photocatalytic activity by decreasing the probability that photogenerated electrons and holes recombine before accessing adsorbed reactants. Detecting these charge separated states via optical transient absorption, however, can be challenging when they lack definitive optical signatures. Here, we investigate the long-lived excited state of a MOF with such vague optical properties, MIL-100(Fe), comprised of Fe3-μ3-oxo clusters and trimesic acid linkers using Fe K-edge X-ray transient absorption (XTA) spectroscopy, to unambiguously determine its ligand-to-metal charge transfer character. Spectra measured at time delays up to 3.6 μs confirm the long lived nature of the charge separated excited state. Several trinuclear iron μ3- oxo carboxylate complexes, which model the trinuclear cores of the MOF structure, are measured for comparison using both steady state XAS and XTA to further support this assignment and corresponding decay time. The MOF is prepared as a colloidal nanoparticle suspension for these measurements so both its fabrication and particle size analysis are presented, as well.

Hanna, Lauren↗

Radiation-induced negative optical nonlinearities in fused silica, sapphire, and borosilicate glass

Here, negative nonlinear absorption is reported in neutron- and gamma-irradiated high-OH content fused silica, low-OH content fused silica, sapphire, borosilicate glass, and radiation-resistant borosilicate glass irradiated to total neutron fluences of 3.4 × 10 16 n ∙ cm –2 (42 Mrad γ), 1.7 × 10 17 n ∙ cm –2 (211 Mrad γ), and 3.6 × 10 17 n ∙ cm –2 (433 Mrad γ). Nonlinear absorption coefficients were measured via Z-scan and are on the order of – (10 –14 –10 –10 ) m∙W –1 . The Z-scan also reveals a negative nonlinear index of refraction in neutron- and gamma-irradiated radiation-resistant borosilicate glass on the order of –10 –19 m 2 ∙ W –1 . Thermal annealing at temperatures up to 800 °C is shown to restore these nonlinearities to their positive unirradiated values in all four materials. All Z-scan measurements were performed at 532 nm with a nanosecond pulsed laser. The occurrence of negative nonlinearities may be attributed to the presence of metallic impurities and the resulting saturable absorption. A limited effect of photobleaching is observed in measurements and is quantified in multiple Z-scans.

36 MATERIALS SCIENCE↗

Optical spacing effect in organic photovoltaic cells incorporating a dilute acceptor layer

The addition of spacing layers in organic photovoltaic cells (OPVs) can enhance light absorption by optimizing the spatial distribution of the incident optical field in the multilayer structure. We explore the optical spacing effect in OPVs achieved using a diluted electron acceptor layer of C{sub 60}. While optical spacing is often realized by optimizing buffer layer thickness, we find that optical spacing via dilution leads to cells with similar or enhanced photocurrent. This is observed despite a smaller quantity of absorbing molecules, suggesting a more efficient use of absorbed photons. In fact, dilution is found to concentrate optical absorption near the electron donor-acceptor interface, resulting in a marked increase in the exciton diffusion efficiency. Contrasting the use of changes in thickness to engineer optical absorption, the use of dilution does not significantly alter the overall thickness of the OPV. Optical spacing via dilution is shown to be a viable alternative to more traditional optical spacing techniques and may be especially useful in the continued optimization of next-generation, tandem OPVs where it is important to minimize competition for optical absorption between individual sub-cells.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Atmospheric Effects on Remote Sensing of the Earth's Surface

The main causes and magnitude of the atmospheric effects on remote sensing of the Earth's surface are determined. Theoretical study as well as measurements are included. The knowledge gained from this study will be used to develop atmospheric correction algorithms and to test them with satellite data. In a theoretical investigation of the relative effects of the aerosol optical thickness, absorption, and size distribution on remote sensing, it was found that aerosol absorption has a significant effect on satellite measurements of surface reflectivity. The absorption effect is stronger for high than for low surface reflectances. The aerosol optical thickness is dominant for small surface reflectances. The accuracy of clustering algorithms depends on both parameters. The vegetation index, however, is affected by the optical thickness but only weakly affected by the absorption. A laboratory simulation of the atmospheric effect on the radiance of sunlight scattered from the Earth's surface-atmosphere system was performed. This experiment verified the existence of the adjacency effect (the effect of a bright field on the radiance detected above a dark field) and was used to test 3-D radiative transfer models. In a theoretical study it was found that atmospheric scattering resulting from the adjacency effect reduces the separability between surface classes.

Fraser, R. E.↗

Stoner versus Heisenberg: Ultrafast exchange reduction and magnon generation during laser-induced demagnetization

Understanding how the electronic band structure of a ferromagnetic material is modified during laser-induced demagnetization on femtosecond timescales has been a long-standing question in condensed matter physics. Here, we use ultrafast high harmonics to measure time-, energy-, and angle-resolved M-edge magnetic asymmetry spectra for Co lms after optical pumping to induce ultrafast demagnetization. This provides a complete data set that we can compare with advanced ab initio magneto-optical calculations. Here, tur analysis identifies that the dominant mechanisms contributing to ultrafast demagnetization on timescales up to several picoseconds are a transient reduction in the exchange splitting and the excitation of ultrafast magnons. Surprisingly, we nd that the magnon contribution to ultrafast demagnetization is already strong on sub-picosecond timescales, while the reduction in exchange splitting persists to several picoseconds.

36 MATERIALS SCIENCE↗

Multicolor observations of stars in the vicinity of the Orion Nebula.

Photometry in nine colors from 0.3 to 3.4 microns of all stars brighter than V = 12 mag within half a degree square centered on theta super 1 Orionis is presented. Additionally about one-half of this area is searched for stars which, although visually fainter than twelfth magnitude, have 2.2-micron magnitudes brighter than about 8 mag. Several stars with infrared excesses and a few highly reddened stars are found. These two types of stars can be separated in an infrared two-color diagram. No star earlier than B9 has a significant infrared excess at 2 microns. There is a good correlation of 2-micron excess with optical variability. For those stars with spectral types, the visual absorption can be deduced. This varies greatly from star to star and does not correlate with position or luminosity and only weakly with 2-micron excess. There is, however, a probable correlation of visual absorption with optical variability. For nearly all stars more energy is absorbed in the visual region than is reemitted in the infrared at wavelengths up to 3.4 microns.

Penston, M. V.↗

Method of evaluating pH using an inorganic-oxide nanoparticle based optical pH sensor

A method for evaluating the pH of an aqueous solution by utilizing the optical properties of a pH sensing material includes optically active nanoparticles fixed to a substrate. The optically active nanoparticles have a localized refractive index modulation over a pH range from 2.0 to 12.0 of at least 1% and, where the plurality of optically active nanoparticles have an average nanoparticle diameter of less than about 500 nanometers. The method includes contacting the pH sensing material with the aqueous solution, illuminating the pH sensing material, and monitoring an optical signal generated through comparison of incident light and exiting light to determine the optical transmission, absorption, reflection, and/or scattering of the pH sensitive material. The optical signal of the pH sensitive material varies in response to the pH of the aqueous solution, providing a means by which the pH and any changes in the pH may be analyzed.

02 PETROLEUM↗

Method of evaluating pH using a metallic nanoparticle incorporated nanocomposite-based optical pH sensor

A method for evaluating the pH of an aqueous solution by utilizing the optical properties of a pH sensing material comprised of plurality of optically active nanoparticles dispersed in matrix material. The optically active nanoparticles have an electronic conductivity greater than about 10−1 S/cm and generally have an average nanoparticle diameter of less that about 500 nanometers, and the matrix material is a material which experiences a change in surface charge density over a pH range from 2.0 to 12.0 of at least 1%. The method comprises contacting the pH sensing material and the aqueous solution, illuminating the pH sensing material, and monitoring an optical signal generated through comparison of incident light and exiting light to determine the optical transmission, absorption, reflection, and/or scattering of the pH sensitive material. The optical signal of the pH sensitive material varies in response to the pH of the aqueous solution.

Ohodnicki, Jr., Paul R.↗

Microfluidic Liquid-Liquid Extraction Chip with Integrated Raman Sensors (Phase I and Phase II Final Report)

As demand for electricity continues to increase worldwide, the world’s nuclear power generating capacity will continue to grow. Nuclear power is the most environmentally benign way of producing electricity on a large scale. The long-term successful use of nuclear power, however, is critically dependent upon adequate and safe processing and disposal of spent nuclear fuels. A very important feature of nuclear energy is that spent fuels can be reprocessed to recover fissile and fertile materials that can then be used as fresh fuel for nuclear power plants. The DOE-NE Fuel Cycle Research and Development (FCR&D) is currently developing nuclear material reprocessing technologies. In a typical nuclear fuel reprocessing system, centrifugal contactors are used as liquid-liquid extraction devices where two immiscible liquids are mixed at high speeds using a rotor, which creates a fine dispersion of droplets of organic phase in an aqueous phase that contains the analyte. Understanding the extraction efficiency at these contactors through modeling and simulation is important in the development of reprocessing technologies and the optimization of current technologies such as the PUREX process. The outcome of this program will be a liquid-liquid microfluidic flow cell chip with embedded spectroscopic sensors for the analysis of extracted analytes. This device will be useful in the optimization of new fuel reprocessing schemes as well as existing reprocessing processes by providing a microfluidic modeling platform to optimize extraction parameters. The Phase I and Phase II work developed a microfluidic chip design that allows integration of Raman and absorption fiber optic probes and successfully demonstrated the feasibility of using Raman and absorption probes to detect key analytes that partition into the aqueous and organic phases.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗