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At least 325 records · Page 18

Photochemical Explanation for Sprites

Lightning-induced discharges occurring well above clouds showing vigorous lightning activity have recently been observed from high flying aircraft and the space shuttle. The nature of, and mechanisms that produce, these "sprites" are unknown. A numerical model has been constructed to investigate the possibility that ultraviolet light emitted by the hot discharge columns at the cloud top penetrate to sufficiently high altitudes that atomic and molecular species present at those altitudes are excited and then produce the visible light by fluorescence. calculations show that at altitudes above the clouds, strong absorption by oxygen and ozone removes most of radiation at photoreactive wavelengths with the exception of a narrow band at 200 nm. Further calculations are being performed to identify the species responsible for the radiation.

Borucki, W. J.↗

Mars Odyssey THEMIS-VIS: Surface-Atmosphere Separation and Derivation of Aerosol Properties

Scattering by atmospheric aerosols can contribute a substantial fraction of the visible-light radiance observed in any remote sensing of Mars. Our objective is to develop techniques to separate this aerosol component from the surface-reflectance component in Mars Odyssey's THEMIS Visible Imaging Subsystem (THEMIS-VIS) dataset. The primary purpose of this study is the production of accurate surface reflectance data in order to allow for reliable color and mineralogical unit mapping. The second principal goal is to study the feasibility of using VIS measurements to derive quantitative information about ice and dust aerosol properties such as particle size and optical depth.

T H McConnochie↗

Light-Driven Expansion of Spiropyran Hydrogels

The incorporation of molecular switches in organic structures is of great interest in the chemical design of stimuli-responsive materials that mimic the complex functions of living systems. Merocyanine dyes that convert to spiropyran moieties upon exposure to visible light have been extensively studied as they can be incorporated in hydrated covalent networks that will expel water when this conversion occurs and induce a volumetric shrinkage. We report here on a sulfonatebased water soluble photoswitch that in contrast to the well-known system triggers a volumetric expansion in hydrogels upon exposure to photons. Contraction is in turn observed under dark conditions in a highly reversible manner. The novel behavior of the photoswitch incorporated in the covalent network was also predicted by coarse grain simulations of the system’s chemical structure. Using pH control and polymeric structures that differ in lower critical solution temperature we were able to develop hydrogels with highly tunable volumetric expansion. Furthermore, the novel molecular function of the systems developed here led to materials with the negative phototaxis observed in plants, and can expand the potential use of hydrogels as sensors, soft robots, and actuators.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Triplet Photosensitized para -Hydrogen Induced Polarization

Despite its enormous utility in structural characterization, nuclear magnetic resonance (NMR) spectroscopy is inherently limited by low spin polarization. One method to address the low polarization is para-hydrogen (p-H 2 ) induced polarization (PHIP) which uses the singlet spin isomer of H 2 to generate disparate nuclear spin populations to amplify the associated NMR signals. PHIP often relies on thermal catalysis or, more infrequently, UV-activated catalytic hydrogenation. Light-activated hydrogenation enables direct and timed control over the hyperpolarization of target substrates, critical for identifying short-lived intermediates. Here, we use an established Ir(III) triplet photosensitizer (PS) to visible light sensitize the triplet ligand-field states in the d6-transition metal dihydride Ru(CO)(PPh 3 ) 3 (H) 2 (1). Excitation inside a 9.4 T NMR spectrometer with the PS and a 420 nm blue LED, under 3 atm of p-H 2 , successfully photosensitized hyperpolarization in 1 and in a range of unsaturated substrates at and below room temperature, up to 1630-fold. In otherwise identical experimental conditions without light activation, no polarization was realized in 1 or the substrates evaluated. We believe triplet-sensitized PHIP (Trip- PHIP) represents a facile experimental means for probing triplet sensitized light activation in transition metal catalysts possessing low-lying triplet ligand-field states, providing mechanistic insight of potentially tremendous value in chemical catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

What we Hope to Learn about Global Mineral Dust Aerosols from EOS Multi-Angle Imaging SpectroRadiometer (MISR)

On global scales, just a few broad atmospheric aerosol compositional groups are commonly observed. Of these, "mineral dust" is the only group which both contains non-spherical particles, and typically has size distributions with enough large particles for particle shape to affect its visible-light-scattering properties. The MISR instrument is scheduled for launch into a 10:30 AM sun-synchronous, polar orbit aboard the EOS Terra satellite in 1999. MISR will measure the upwelling visible radiance from Earth in 4 spectral bands centered at 446, 558, 672, and 866 nm, at each of 9 emission angles spread out in the forward and aft directions along the flight path at +/-70.5 deg, +/-60.0 deg, +/-45.6 deg, +/-26.1deg, and nadir. Over a period of 7 minutes, as the spacecraft flies along, a 360 km wide swath of Earth will successively be viewed by each of the cameras, allowing MISR to sample a very large range of scattering angles; in mid latitudes, the instrument will observe scattering angles between about 60 deg and 160 deg. Global coverage will be acquired about once in 9 days at the equator; the nominal mission lifetime is 6 years. The distinction in single scattering phase function between natural distributions of spherical and randomly oriented, non-spherical particles, with a broad range of aspect ratios, shows up strongly for scattering angles ranging from about 90 deg to near 180 deg. For non-spherical particle distributions, single scattering phase functions tend to be much flatter in this region than for spherical particles. Since MISR samples the relevant range of scattering angles very well, we expect to be able to make critical distinctions between natural distributions of spherical and randomly oriented, non-spherical particles with MISR data. We anticipate that the new multiangle, multispectral data from MISR will also contain other information about particle properties, a major step beyond current spacecraft remote sensing retrievals, which obtain aerosol optical depth based on entirely assumed particle microphysical properties. According to simulations over cloud-free, calm ocean, for pure particles with natural ranges of optical depth, particle size, and indices of refraction, MISR should retrieve column optical depth for all but the darkest particles, to an uncertainty of at most 0.05 or 20%, whichever is larger, even if the particle properties are poorly known. For one common particle type, soot, constraints on the optical depth over dark ocean are very poor. The simulated measurements also should allow us to separate two to four compositional groups based on indices of refraction, and to identify three to four distinct size groups between 0.1 and 2.0 microns characteristic radius at most latitudes. The technique is most sensitive to particle microphysical properties in the "accumulation mode" sizes. where particle scattering undergoes the transition from Rayleigh to large-particle regimes for the MISR wavelengths. Based on these results, we expect to distinguish air masses containing different aerosol types, routinely and globally, with multiangle remote sensing data. Such data complements in situ and field data, which can provide details about aerosol size and composition locally that are needed to assess the radiative effects of aerosols quantitatively. Both field data and correlations in space and time with likely source and sink regions will also be helpful in developing a global picture of mineral dust aerosol budgets. Further work on the expected sensitivity of MISR to natural mixtures of pure particles, including climatologically likely mineral dust components, is currently underway.

Kahn, Ralph↗

Optically enhanced patternable photosensitivity via oxygen excitation

The present disclosure relates to a method for performing a three dimensional (3D) printing process. A primary light beam having a wavelength sufficient to initiate polymerization of a photoresin is generated and patterned into a patterned primary beam. The patterned primary beam is directed toward an ultraviolet (UV) or visible light sensitive photoresin to initiate polymerization of select areas of the photoresin. The photoresin is also illuminated with a secondary light beam having a wavelength of at least one of about 765 nm, 1064 nm, or 1273 nm. The secondary light beam stimulates triplet oxygen into singlet oxygen, which controls oxygen inhibition in additional areas bordering the select areas, to enable controlled polymerization inhibition in the additional areas bordering the select areas.

Hensleigh, Ryan↗

Evolution of an impact-generated dust cloud and its effects on the atmosphere

A simulation is carried out of the evolution of an optically thick dust cloud in the earth's atmosphere, and calculations are made of the effects that such a dust cloud would have on the amount of visible light reaching the surface and the temperature at the earth's surface. It is found that large quantities of dust remain in the atmosphere for periods of only three to six months. This duration is fixed by the physical processes of coagulation; these cause the rapid formation of micron-sized particles and sedimentation that quickly removes the particles from the atmosphere. The duration of the event is found to be nearly independent of the initial altitude, initial particle size, initial mass, atmospheric vertical diffusive mixing rate, and rainout rate. It depends to a slight extent on the particle density and the probability that colliding particles stick together to form a larger particle. In addition, the duration is limited by the rate at which the debris spreads from the initial impact site. A doubling code is used to calculate the visible radiative transfer in the dust clouds. It is found that light levels are too low for vision for one to six months and too low for photosynthesis for two months to one year.

Toon, O. B.↗

The HR 4796A Debris System: Discovery of Extensive Exo-Ring Dust Material

The optically and IR-bright and starlight-scattering HR 4796A ringlike debris disk is one of the most- (and best-) studied exoplanetary debris systems. The presence of a yet-undetected planet has been inferred (or suggested) from the narrow width and inner/outer truncation radii of its r = 1farcs05 (77 au) debris ring. We present new, highly sensitive Hubble Space Telescope (HST) visible-light images of the HR 4796A circumstellar debris system and its environment over a very wide range of stellocentric angles from 0farcs32 (23 au) to ≈15'' (1100 au). These very high-contrast images were obtained with the Space Telescope Imaging Spectrograph (STIS) using six-roll PSF template–subtracted coronagraphy suppressing the primary light of HR 4796A, with three image-plane occulters, and simultaneously subtracting the background light from its close angular proximity M2.5V companion. The resulting images unambiguously reveal the debris ring embedded within a much larger, morphologically complex, and biaxially asymmetric exo-ring scattering structure. These images at visible wavelengths are sensitive to and map the spatial distribution, brightness, and radial surface density of micron-size particles over 5 dex in surface brightness. These particles in the exo-ring environment may be unbound from the system and interacting with the local ISM. Herein, we present a new morphological and photometric view of the larger-than-prior-seen HR 4796A exoplanetary debris system with sensitivity to small particles at stellocentric distances an order of magnitude greater than has previously been observed.

starlight-scattering HR 4796A↗

A computer controlled television detector for light, X-rays and particles

A versatile, high resolution, software configurable, two-dimensional intensified vidicon quantum detector system has been developed for multiple research applications. A thin phosphor convertor allows the detection of X-rays below 20 keV and non-relativistic particles in addition to visible light, and a thicker scintillator can be used to detect X-rays up to 100 keV and relativistic particles. Faceplates may be changed to allow any active area from 1 to 40 mm square, and active areas up to 200 mm square are possible. The image is integrated in a digital memory on any software specified array size up to 4000 x 4000. The array size is selected to match the spatial resolution, which ranges from 10 to 100 microns depending on the operating mode, the active area, and the photon or particle energy. All scan and data acquisition parameters are under software control to allow optimal data collection for each application.

Kalata, K.↗

Technology Plan for the Terrestrial Planet Finder Interferometer

The technology plan for the Terrestrial Planet Finder Interferometer (TPF-I) describes the breadth of technology development currently envisaged to enable TPF-I to search for habitable worlds around nearby stars. TPF-I is currently in Pre-Phase A (the Advanced Study Phase) of its development. For planning purposes, it is expected to enter into Phase A in 2010 and be launched sometime before 2020. TPF-I is being developed concurrently with the Terrestrial Planet Finder Coronagraph (TPF-C), whose launch is anticipated in 201 6. The missions are being designed with the capability to detect Earth-like planets should they exist in the habitable zones of Sun-like (F,G, and K) stars out to a distance of about 60 light-years. Each mission will have the starlight-suppression and spectroscopic capability to enable the characterization of extrasolar planetary atmospheres, identifying biomarkers and signs of life. TPF-C is designed as a visible-light coronagraph; TPF-I is designed as a mid-infrared formation-flying interferometer. The two missions, working together, promise to yield unambiguous detections and characterizations of Earth-like planets. The challenges of planet detections with mid-infrared formation-flying interferometry are described within this technology plan. The approach to developing the technology is described through roadmaps that lead from our current state of the art through the different phases of mission development to launch. Technology metrics and milestones are given to measure progress. The emphasis of the plan is development and acquisition of technology during pre-Phase A to establish feasibility of the mission to enter Phase A sometime around 2010. Plans beyond 2010 are outlined. The plan contains descriptions of the development of new component technology as well as testbeds that demonstrate the viability of new techniques and technology required for the mission. Starlight-suppression (nulling) and formation-flying technology are highlighted. Although the techniques are described herein, the descriptions are only at a high-level, and tutorial material is not included. The reader is expected to have some familiarity with the principles of long-baseline mid-infrared interferometry. Selected references to existing literature are given where relevant.

Lawson, Peter R.↗

Metrology and Alignment of Light Weight Grazing Incidence X-Ray Mirrors

Metrology and alignment of light weight X-ray optics have been a challenge for two reasons: (1) that the intrinsic mirror quality and distortions caused by handling can not be easily separated, and (2) the diffraction limits of the visible light become a severe problem at the order of one arc-minute. Traditional methods of using a normal incident pencil or small parallel beam which monitors a tiny fraction of the mirror in question at a given time can not adequately monitor those distortions. We are developing a normal incidence setup that monitors a large fraction, if not the whole, of the mirror at any given time. It will allow us to align thin X-ray mirrors to-an accuracy of a few arc seconds or to a limit dominated by the mirror intrinsic quality.

Zhang, William↗

Solar light systems, and related components and methods

A solar light system may include two stages of optical concentration with intermediate removal of infrared radiation between the optical concentration stages. A second stage of optical concentration may prepare multiple concentrating beams of processed solar radiation with visible light with each such concentrating beam directed to a different corresponding light conduit for transmission to an interior space for interior lighting. System modularization may provide flexibility to accommodate a variety of interior lighting applications.

14 SOLAR ENERGY↗

Hot Views on Cold Crystals: The Application of Thermal Imaging in Cryocrystallography

We have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. Cryocooling is a common technique used for structural data collection to reduce radiation damage in intense X-ray beams and decrease the thermal motion of the atoms. From the thermal images it was clear that during cryocooling a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. As an extension to this work, we used thermal imaging to study small crystals, held in a cryo-loop, in the presence of vitrified mother liquor. The different infrared transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop for automated structural genomics studies. Data from initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryocooled and imaged in large loops, both with visible light and with infrared radiation. The crystals were clearly distinguished from the vitrified solution in the infrared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

Snell, Eddie↗

Hot Views on Cold Crystals: The Application of Thermal Imaging in Cryocrystallography

In the past we have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. From these images it was clear that a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. During these studies we used large volume crystals, which were clearly distinguished from the loop holding them. These large crystals, originally grown for neutron diffraction studies, were chosen deliberately to enhance the imaging. As an extension to this work, we used thermal imaging to study small crystals, held in a cryo- loop, in the presence of vitrified mother liquor. The different infrared transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop. Data from initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryo-cooled and imaged in large loops, both with visible light and with infrared radiation. The crystals were clearly distinguished from the vitrified solution in the infrared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied .

Snell, Eddie H.↗

Hot Views on Cold Crystals: The Application of Thermal Imaging in Cryo-crystallography

In the past we have used thermal imaging techniques to visualize the cryocooling processes of macromolecular crystals. From these images it was clear that a cold wave progresses through a crystal starting at the face closest to the origin of the cold stream and ending at the point furthest away. During these studies we used large volume crystals, which were clearly distinguished from the loop holding them. These large crystals, originally grown for neutron diffraction studies, were chosen deliberately to enhance the imaging. As an extension to this work, we present used thermal imaging to study small crystals, held in a cryo-loop, in the presence of vitrified mother liquor. The different infrared transmission and reflectance properties of the crystal in comparison to the mother liquor surrounding it are thought to be the parameter that produces the contrast that makes the crystal visible. An application of this technology may be the determination of the exact location of small crystals in a cryo-loop. Data from initial tests in support of application development was recorded for lysozyme crystals and for bFGF/dna complex crystals, which were cryo-cooled and imaged in large loops, both with visible light and with infrared radiation. The crystals were clearly distinguished from the vitrified solution in the infrared spectrum, while in the case of the bFGF/dna complex the illumination had to be carefully manipulated to make the crystal visible in the visible spectrum. These results suggest that the thermal imaging may be more sensitive than visual imaging for automated location of small crystals. However, further work on small crystals robotically mounted at SSRL did not clearly visualize those crystals. The depth of field of the camera proved to be limiting and a different cooling geometry was used, compared to the previous, successful experiments. Analysis to exploit multiple images to improve depth of field and experimental work to understand cooling geometry effects is ongoing. These results will be presented along with advantages and disadvantages of the technique and a discussion of how it might be applied.

Snell, E. H.↗

Uncooled IR Detector

Detector combines liquid crystal film with light-sensitive solid-state array. Liquid-crystal film acts as IR detector when maintained just below temperature of transition from opacity to transparancey. When IR radiation is absorbed by film, resultant heating changes visiblelight transmission, modulating uniform visible light beam as it passes through film.

Shlichta, P. J.↗

Theory of the photomolecular effect

It is well-known that water in liquid and vapor phases exhibits weak visible-light absorption. Recent experiments, however, show that at the liquid-air interface, absorption drastically increases, accelerating evaporation beyond thermal limits by 2–5 times. Strikingly, evaporation peaks at green wavelengths, despite no corresponding absorptance peak. The underlying mechanism of this observation, termed the photomolecular effect, remains puzzling, particularly as water molecules do not exhibit resonance peaks in the visible spectrum. Here, we present a theoretical model explaining the effect. We show that surface-bound water clusters undergo non-resonant photon-driven evaporation, with green light being particularly effective. Crucially, we do not expect green light to couple more strongly than other wavelengths to the molecules at the surface, rather the energy of green light is more effectively used to vaporize water. Our model accounts for why the evaporation peak does not align with absorptance and provides a quantum mechanical explanation of how a single photon can vaporize an entire molecular cluster. This model challenges conventional views on water-light interactions, revealing a fundamentally non-thermal evaporation mechanism. Furthermore, our findings have implications for water purification, energy-efficient drying, and climate modeling, opening new pathways for optimizing evaporation-based technologies.

Interfacial evaporation↗

Two-Dimensional Electronic Spectroscopy of the Far-Red-Light Photosystem II Reaction Center

Understanding the role of specific pigments in primary energy conversion in the photosystem II (PSII) reaction center has been impeded by the spectral overlap of its constituent pigments. When grown in far-red light, some cyanobacteria incorporate chlorophyll-f and chlorophyll-d into PSII, relieving the spectral congestion. Here we employ two-dimensional electronic spectroscopy to study PSII at 77 K from Synechococcus sp. PCC 7335 cells that were grown in far-red light (FRL-PSII). We observe the formation of a radical pair within ~3 ps that we assign to Chl D1 •– P D1 •+ . While Pheo D1 is thought to act as the primary electron acceptor in PSII from cells grown in visible light, we see no evidence of its involvement, which we attribute to its reduction by dithionite treatment in our samples. Our work demonstrates that primary charge separation occurs between Chl D1 and P D1 in FRL-PSII, suggesting that P D1 /P D2 may play an underappreciated role in PSII’s charge separation mechanism.

14 SOLAR ENERGY↗