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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 73 records · Page 4
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NASA NTRS1990

The mechanics of the South Iceland Seismic Zone

The mechanics of the South Iceland Seismic Zone is examined by means of boundary element modeling. The differences between the observed geometry of the major tectonically active features and that of a geometrically orthogonal ridge-transform system (which assumes that the upper part of the earth's crust is an elastic plate containing vertical cuts) are examined. It is suggested that north-south faults can accommodate transform deformation only if the faults are longer or more numerous than those observed so far. This is considered reasonable because earthquake surface rupture lengths are commonly less than the inferred fault length at depth. The South Iceland Seismic Zone is subject to sequences of large earthquake every 45-112 years. In comparing the seismic moment release derived from earthquake magnitudes with that predicted by the models, it is confirmed that the system of north-south faults can act as a transform fault.

Hackman, M. Christine↗
NASA NTRS2011

Cross Calibration of SeaWiFS and MODIS Using On-Orbit Observations of the Moon

Observations of the Moon provide a primary technique for the on-orbit cross calibration of Earth remote sensing instruments. Monthly lunar observations are major components of the on-orbit calibration strategies of SeaWiFS and MODIS. SeaWiFS has collected more than 132 low phase angle and 59 high phase angle lunar observations over 12 years, Terra MODIS has collected more than 82 scheduled and 297 unscheduled lunar observations over 9 years, and Aqua MODIS has collected more than 61 scheduled and 171 unscheduled lunar observations over 7 years. The NASA Ocean Biology Processing Group s Calibration and Validation Team and the NASA MODIS Characterization Support Team use the USGS RObotic Lunar Observatory (ROLO) photometric model of the Moon to compare these time series of lunar observations over time and varying observing geometries. The cross calibration results show that Terra MODIS and Aqua MODIS agree, band-to-band, at the 1-3% level, while SeaWiFS and either MODIS instrument agree at the 3-8% level. The combined uncertainties of these comparisons are 1.3% for Terra and Aqua MODIS, 1.4% for SeaWiFS and Terra MODIS, and 1.3% for SeaWiFS and Aqua MODIS. Any residual phase dependence in the ROLO model, based on these observations, is less than 1.7% over the phase angle range of -80deg to -6deg and +5deg to +82deg . The lunar cross calibration of SeaWiFS, Terra MODIS, and Aqua MODIS is consistent with the vicarious calibration of ocean color products for these instruments, with the vicarious gains mitigating the calibration biases for the ocean color bands.

Eplee, Robert E., Jr.↗
NASA NTRS2014

Cloud Thermodynamic Phase Detection with Polarimetrically Sensitive Passive Sky Radiometers

The primary goal of this project has been to investigate if ground-based visible and near-infrared passive radiometers that have polarization sensitivity can determine the thermodynamic phase of overlying clouds, i.e. if they are comprised of liquid droplets or ice particles. While this knowledge is important by itself for our understanding of the global climate, it can also help improve cloud property retrieval algorithms that use total (unpolarized) radiance to determine Cloud Optical Depth (COD). This is a potentially unexploited capability of some instruments in the NASA Aerosol Robotic Network (AERONET), which, if practical, could expand the products of that global instrument network at minimal additional cost. We performed simulations that found, for zenith observations, cloud thermodynamic phase is often expressed in the sign of the Q component of the Stokes polarization vector. We chose our reference frame as the plane containing solar and observation vectors, so the sign of Q indicates the polarization direction, parallel (negative) or perpendicular (positive) to that plane. Since the quantity of polarization is inversely proportional to COD, optically thin clouds are most likely to create a signal greater than instrument noise. Besides COD and instrument accuracy, other important factors for the determination of cloud thermodynamic phase are the solar and observation geometry (scattering angles between 40 and 60 degrees are best), and the properties of ice particles (pristine particles may have halos or other features that make them difficult to distinguish from water droplets at specific scattering angles, while extreme ice crystal aspect ratios polarize more than compact particles). We tested the conclusions of our simulations using data from polarimetrically sensitive versions of the Cimel 318 sun photometerradiometer that comprise AERONET. Most algorithms that exploit Cimel polarized observations use the Degree of Linear Polarization (DoLP), not the individual Stokes vector elements (such as Q). For this reason, we had no information about the accuracy of Cimel observed Q and the potential for cloud phase determination. Indeed, comparisons to ceilometer observations with a single polarized spectral channel version of the Cimel at a site in the Netherlands showed little correlation. Comparisons to Lidar observations with a more recently developed, multi-wavelength polarized Cimel in Maryland, USA, show more promise. This divergence between simulations and observations has prompted us to begin the development of a small test instrument called the Sky Polarization Radiometric Instrument for Test and Evaluation (SPRITE). This instrument is specifically devoted to the accurate observation of Q, and the testing of calibration and uncertainty assessment techniques, with the ultimate goal of understanding the practical feasibility of these measurements.

Knobelspiesse, Kirk D.↗
NASA NTRS2020

Fluorescence Correction Vegetation Index (FCVI): A physically based reflectance index to separate physiological and non-physiological information in far-red sun-induced chlorophyll fluorescence

Sun-induced chlorophyll fluorescence (SIF) has been used to track vegetation photosynthetic activity for improving estimation of gross primary productivity (GPP) and detecting plant stress. There are both physical and physiological controls of SIF measured at the surface and retrieved from remote sensing including satellite observations. In order to accurately use SIF for monitoring of plant physiology, the effects of physically-based radiation processes related to leaf and canopy structure, notably photosynthetically active radiation (PAR) absorption and SIF scattering and re-absorption, must be characterized. In this study, we investigate both PAR absorption and SIF scattering processes and find that although it is difficult to quantify their effects individually by using just reflectance, the combined effects of the two processes can be well approximated by a reflectance index. This index, referred to as FCVI (Fluorescence Correction Vegetation Index), is defined as the difference between near-infrared (NIR) and broad-band visible (VIS, 400–700 nm) reflectance acquired under identical sun-canopy-observer geometry of the SIF measurements. The development of the index was based on the physical connection between reflectance and far-red SIF, which was revealed by using the spectral invariant theory. The utility of FCVI to correct far-red SIF for PAR absorption and scattering effects, thus improving the link to photosynthesis, was tested with data from: (i) a field experiment for a growing season; and (ii) a numerical experiment which included a number of scenarios generated by a radiative transfer model. For both the observations and simulations, the FCVI provided a promising estimate of the impact of the physically-based radiation processes on far-red SIF of moderately dense canopies (i.e., FCVI ≥ 0.18). Normalizing the TOC far-red SIF by both the incident PAR (iPAR) and the FCVI provided a good estimate of the far-red fluorescence emission efficiency of the canopies examined. This approach enhances our ability to generalize retrievals for vegetation processes as they change through natural growth phases and seasons. Taken together, far-red SIF and FCVI may enable the assessment of the light partitioning of vegetation canopies, an essential step to facilitate the use of far-red SIF for tracking physiological processes.

Peiqi Yang↗
DOE OSTI2012

UNRAVELING THE GEOMETRY OF THE CRAB NEBULA's 'INNER RING'

Chandra images of the Crab Nebula resolve the detailed structure of its 'inner ring', possibly a termination shock where pulsar-accelerated relativistic particles begin to emit X radiation. Analysis of these images finds that the center of the ellipse-presumably a circular ring in projection-lies about 0.''9 (10 light days at 2 kpc) from the pulsar's image, at a position angle of about 300 Degree-Sign (east of north). This analysis also measures properties of the ellipse: the position angle of the semi-major axis is about 210 Degree-Sign (east of north); the aspect ratio is 0.49. In a simple-albeit, not unique-de-projection of the observed geometry, a circular ring is centered on the axis of symmetry of the pulsar wind nebula. This ring is not equatorial but rather lies near +4.{sup 0}5 latitude in pulsar-centered coordinates. Alternative geometries are briefly discussed.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2011

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↗
NASA NTRS1977

On the origin of the magnetic field in type-1 comet tails - A reply to Ershkovich

Ershkovich (1976) employed the observed geometry of the type 1 tail of comet Arend-Roland 1957 III to show that any magnetic field present there cannot be of 'internal' origin but must have been 'captured' from the magnetized solar wind. Such an 'external' origin for the magnetic field in type 1 comet tails is not disputed, but several other points raised by Ershkovich are discussed. These concern the generation of substantial magnetic fields within the coma during periods when the comet's heliocentric distance is typically not greater than 1 AU, Ershkovich's use of the pressure balance across the tail 'tangential discontinuity' to estimate that the 'captured' magnetic field is of the order of the solar wind-field, his interpretation of certain observations of motions in the tail of comet Arend-Roland, and his assertion that the distant comet tail will be transformed into a turbulent wake due to the Kelvin-Helmholtz instability. It is argued that the 'captured' magnetic field should be substantially amplified relative to the solar-wind field, that the pressure-balance equation is of limited use, and that the real configuration of a type 1 tail must be treated in detail before any definite conclusions can be reached about the Kelvin-Helmholtz instability.

Mendis, D. A.↗
DOE OSTI2014

Observation and modeling of geocoronal charge exchange X-ray emission during solar wind gusts

Solar wind charge exchange (SWCX) X-rays are emitted when highly charged solar wind ions such as O{sup 7{sup +}} collide with neutral gas, including the Earth's tenuous outer atmosphere (exosphere or geocorona) and hydrogen and helium from the local interstellar medium drifting through the heliosphere. This geocoronal and heliospheric emission comprises a significant and varying fraction of the soft X-ray background (SXRB) and is seen in every X-ray observation, with the intensity dependent on solar wind conditions and observation geometry. Under the right conditions, geocoronal emission can increase the apparent SXRB by roughly an order of magnitude for an hour or more. In this work, we study a dozen occasions when the near-Earth solar wind flux was exceptionally high. These gusts of wind lead to abrupt changes in SWCX X-ray emission around Earth, which may or may not be seen by X-ray observatories depending on their line of sight. Using detailed three-dimensional magnetohydrodynamical simulations of the solar wind's interaction with the Earth's magnetosphere, and element abundances and ionization states measured by ACE, we model the time-dependent brightness of major geocoronal SWCX emission lines during those gusts and compare with changes in the X-ray background measured by the Chandra X-ray Observatory. We find reasonably good agreement between model and observation, with measured geocoronal line brightnesses averaged over 1 hr of up to 136 photons s{sup –1} cm{sup –2} sr{sup –1} in the O VII Kα triplet around 564 eV.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRSDate not supplied

Analysis of Darkened Fragments Resulting from Laboratory Hypervelocity Experiments

NASA’s Orbital Debris Program Office (ODPO) relies on measurements from optical, radar, and in situ measurements to facilitate the development of data-driven orbital debris environmental engineering models such as the NASA Orbital Debris Engineering Model (ORDEM). For optical measurements, the ODPO relies on ground-based optical telescopes to statistically assess objects in geosynchronous orbit and, in the future, low Earth orbit (LEO). The data collected include the detected object’s orbital parameters, time of observation, and optical magnitude. The latter parameter can be converted to a size using NASA’s optical Size Estimation Model (oSEM). It is well known that the observed magnitude of orbital debris can vary based on an object's material constituents, observational geometry, and the effects of space weathering. To assess these magnitude variations, the ODPO uses the Optical Measurement Center (OMC) at NASA Johnson Space Center to characterize a variety of materials and fragments from laboratory impact tests representative of fragments that constitute the orbital debris population. One experiment was DebriSat: a 56 kg spacecraft was built to incorporate structural elements of a modern LEO spacecraft and was subjected to a hypervelocity impact test at the U.S. Air Force’s Arnold Engineering Development Complex using test parameters that may be encountered in LEO. The DebriSat project has provided an abundance of information for assessing fragmentation debris in terms of material, color, shape, size, density, mass, and other derived parameters. Prior to the impact test, the ODPO collected spectral measurements on a subset of the materials used to construct DebriSat for a “ground-truth” of their optical properties. After the successful hypervelocity impact test, the DebriSat team observed a fine, dark dust coating all the fragments. Prior research has suggested that this came from ablated material deposited on the fragments during the impact test, causing a change in the reflective properties [1]. Given that this lower reflectivity on the DebriSat fragments will influence the laboratory-acquired magnitudes used to calculate size and inform potential updates to the oSEM, it is critical to assess if this darkening effect on the DebriSat fragments is a laboratory bias or something that could occur in on-orbit breakup events. This paper will provide a brief overview of the OMC and DebriSat experiment, focused on the optical characterization of a subset of materials using broadband photometric measurements and spectroscopic measurements. In addition, elemental analysis of various DebriSat fragments and the soft-catch foam used in the hypervelocity experiment compared with pristine foam will be examined to further evaluate the source of the dark material coating all fragments. Finally, the authors will present a twofold plan 1) for assessing potential biases in laboratory impact experiments that could affect laboratory optical characterization and 2) for mitigating biases when compared with ground-based optical telescopic measurements of the orbital debris environment.

Heather Cowardin↗
NASA NTRSDate not supplied

Analysis of Darkened Fragments Resulting from Laboratory Hypervelocity Experiments

NASA’s Orbital Debris Program Office (ODPO) relies on measurements from optical, radar, and in situ measurements to facilitate the development of data-driven orbital debris environmental engineering models such as the NASA Orbital Debris Engineering Model (ORDEM). For optical measurements, the ODPO relies on ground-based optical telescopes to statistically assess objects in geosynchronous orbit and, in the future, low Earth orbit (LEO). The data collected include the detected object’s orbital parameters, time of observation, and optical magnitude. The latter parameter can be converted to a size using NASA’s optical Size Estimation Model (oSEM). It is well known that the observed magnitude of orbital debris can vary based on an object's material constituents, observational geometry, and the effects of space weathering. To assess these magnitude variations, the ODPO uses the Optical Measurement Center (OMC) at NASA Johnson Space Center to characterize a variety of materials and fragments from laboratory impact tests representative of fragments that constitute the orbital debris population. One experiment was DebriSat: a 56 kg spacecraft was built to incorporate structural elements of a modern LEO spacecraft and was subjected to a hypervelocity impact test at the U.S. Air Force’s Arnold Engineering Development Complex using test parameters that may be encountered in LEO. The DebriSat project has provided an abundance of information for assessing fragmentation debris in terms of material, color, shape, size, density, mass, and other derived parameters. Prior to the impact test, the ODPO collected spectral measurements on a subset of the materials used to construct DebriSat for a “ground-truth” of their optical properties. After the successful hypervelocity impact test, the DebriSat team observed a fine, dark dust coating all the fragments. Prior research has suggested that this came from ablated material deposited on the fragments during the impact test, causing a change in the reflective properties [1]. Given that this lower reflectivity on the DebriSat fragments will influence the laboratory-acquired magnitudes used to calculate size and inform potential updates to the oSEM, it is critical to assess if this darkening effect on the DebriSat fragments is a laboratory bias or something that could occur in on-orbit breakup events. This presentation will provide a brief overview of the OMC and DebriSat experiment, focused on the optical characterization of a subset of materials using broadband photometric measurements and spectroscopic measurements. In addition, elemental analysis of various DebriSat fragments and the soft-catch foam used in the hypervelocity experiment compared with pristine foam will be examined to further evaluate the source of the dark material coating all fragments. Finally, the authors will present a twofold plan 1) for assessing potential biases in laboratory impact experiments that could affect laboratory optical characterization and 2) for mitigating biases when compared with ground-based optical telescopic measurements of the orbital debris environment.

Heather Cowardin↗
NASA NTRS1999

Edge-Flames in Von Karman Swirling Flows

Classical understanding of diffusion flames dictates that they, unlike the premixed flames, do not possess a characteristic propagation velocity and are constrained by stoichiometric requirements at the flame surface. However, it has been commonly observed that when local extinction occurs within a diffusion flame sheet, the edges that are formed propagate with distinct speeds. In general, the propagation speed of these edges depend on their geometrical shape (concave, convex, or straight) among other factors. Recently, Buckmaster investigated the dynamics of straight diffusion flame edges separating burning and quenched regions using simplified one-dimensional models. He showed that these flame edges can have positive, negative, or zero velocity depending on the Damkoehler number of the equilibrium diffusion flame that support them. It was also shown that this unsteady flame-edge behavior is intrinsically linked to S-curve behavior of the diffusion flame with varying Damkoehler number. When the system Damkoehler number lies between the extinction and ignition limits, flame edges can propagate as an "ignition wave" or as a "failure wave," and for a critical Damkoehler number remain as a stationary flame-edge. We have extend Buckmaster's 1-d model to more general edge-flame configurations where the edges appear as "flame holes" or as "flame disks". These two configurations along with the straight-edge case cover the entire range of possible edge-flame geometry observable in planar diffusion-flame sheets. A generalized map of edge-flame propagation velocities as a function of the system Damkoehler number and the edge-flame radius is presented. Experimentally we show that edge flames can be created using diffusion flames embedded in von Karman boundary layers. In a von Karman boundary layer, the flow is generated by spinning a solid (fuel) disk in a quiescent ambient gas. Under normal gravity we were able to produce "flame disks" over a range of fuel-disk rotational velocities varying from 0 to 20 revolutions per second, by orienting the burning surface of the fuel disk facing downward.

Nayagam, Vedha↗
NASA NTRS2021

A Method for Landsat and Sentinel 2 (HLS) BRDF Normalization

The Harmonized Landsat/Sentinel-2 (HLS) project aims to generate a seamless surface reflectance product by combining observations from USGS/NASA Landsat-8 and ESA Sentinel-2 remote sensing satellites. These satellites’ sampling characteristics provide nearly constant observation geometry and low illumination variation through the scene. However, the illumination variation throughout the year impacts the surface reflectance by producing higher values for low solar zenith angles and lower reflectance for large zenith angles. In this work, we present a model to derive the bidirectional reflectance distribution function (BRDF) normalization and apply it to the HLS product at 30m spatial resolution. It is based on the BRDF parameters estimated from the MODerate Resolution Imaging Spectroradiometer (MODIS) surface reflectance product (M{O,Y}D09) at 1 km spatial resolution using the VJB method (Vermote et al., 2009). Unsupervised classification (segmentation) of HLS images is used to disaggregate the BRDF parameters to the HLS spatial resolution and to build a BRDF parameters database at HLS scale. We first test the proposed BRDF normalization for different solar zenith angles over two homogeneous sites, in particular one desert and one Peruvian Amazon forest. The proposed method reduces both the correlation with the solar zenith angle and the coefficient of variation (CV) of the reflectance time series in the red and near infrared bands to 4% in forest and keeps a low CV of 3% to 4% for the deserts. Additionally, we assess the impact of the view zenith angle (VZA) in an area of the Brazilian Amazon forest close to the equator, where impact of the angular variation is stronger because it occurs in the principal plane. The directional reflectance shows a strong dependency with the VZA. The current HLS BRDF correction reduces this dependency but still shows an under-correction, especially in the near infrared, while the proposed method shows no dependency with the view angles. We also evaluate the BRDF parameters using field surface albedo measurements as a reference over seven different sites of the US surface radiation budget observing network (SURFRAD) and five sites of the Australian OzFlux network.

Belen Franch↗
DOE OSTI2014

Complex-plane generalization of scalar Levin transforms: A robust, rapidly convergent method to compute potentials and fields in multi-layered media

We propose the complex-plane generalization of a powerful algebraic sequence acceleration algorithm, the method of weighted averages (MWA), to guarantee exponential-cum-algebraic convergence of Fourier and Fourier–Hankel (F–H) integral transforms. This “complex-plane” MWA, effected via a linear-path detour in the complex plane, results in rapid, absolute convergence of field and potential solutions in multi-layered environments regardless of the source-observer geometry and anisotropy/loss of the media present. In this work, we first introduce a new integration path used to evaluate the field contribution arising from the radiation spectra. Subsequently, we (1) exhibit the foundational relations behind the complex-plane extension to a general Levin-type sequence convergence accelerator, (2) specialize this analysis to one member of the Levin transform family (the MWA), (3) address and circumvent restrictions, arising for two-dimensional integrals associated with wave dynamics problems, through minimal complex-plane detour restrictions and a novel partition of the integration domain, (4) develop and compare two formulations based on standard/real-axis MWA variants, and (5) present validation results and convergence characteristics for one of these two formulations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]

The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Growth of faceted SiC nanostructures using vapor phase condensation: Microstructural analysis

Highlights: • Synthesis of nanocrystalline SiC using thermal plasma route. • XRD data indicates presence of both α- and β-SiC polytypes with β-SiC as the major content. • HRTEM and SAED analysis reveals polytypic arrangement with stacking faults SiC nanoparticles. • TEM micrograph reveals presence of faceted structures such as hexagonal, triangular, triangular pyramidal structure. - Abstract: The paper emphasizes the morphological and microstructural analysis of SiC nanostructures grown by thermal plasma assisted gas phase condensation process. High Resolution Transmission Electron Microscopic and Selected Area Electron Diffraction studies are used to analyze the growth directions and the polytypic arrangement with stacking faults in the as synthesized SiC nanoparticles. The results help in understanding the hierarchical poly-types related to the observed geometries and showed the presence of both α- and β-SiC polytypes. The microstructural study is supported by X-Ray diffraction and UV–Visible absorption spectroscopic studies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Chiral Spectroscopy of Nanostructures

Chirality is ubiquitous in the universe and in living creatures over detectable length scales from the subatomic to the galactic, as exemplified in the two extremes by subatomic particles (neutrinos) and spiral galaxies. Between them are living creatures that display multiple levels of chirality emerging from hierarchically assembled asymmetric building blocks. Not too far from the bottom of this pyramid are the foundational building blocks with chiral atomic centers on sp 3 carbon atoms exemplified by L-amino acids and D-sugars that are self-assembled into higher-order structures with increasing dimensions forming highly complex, amazingly functional, and energy-efficient living systems. The organization and materials employed in their construction inspired scientists to replicate complex living systems via the self-assembly of chiral components. Multiple studies pointed to unexpected and unique electromagnetic properties of chiral structures with nanoscale and microscale dimensions, including giant circular dichroism and collective circularly polarized scattering that their constituent units did not possess. To address the wide variety of chiral geometries observed in continuous materials, singular particles, and their complex systems, multiple analytic techniques are needed. Simultaneously, their spectroscopic properties create a pathway to multiple applications. For example, mirror-asymmetric vibrations at chiral centers formed by sp 3 carbon atoms lead to optical activity for the infrared (IR) wavelength regions. At the same time, understanding the optical activity in, for example, the IR region enables biomedical applications because multiple modalities of biomedical imaging and vibrational optical activity (VOA) of biomolecules are known for IR range. In turn, VOA can be realized in both absorption and emission modalities due to large magnetic transition moments, as vibrational circular dichroism (VCD) or Raman optical activity (ROA) spectroscopy. In addition to the VOA, in the range of longer wavelengths, lattice vibrational mode or phononic behavior occurs in chiral crystals and nanoassemblies, which can be readily detected by terahertz circular dichroism (TCD) spectroscopy. Meanwhile, chiral self-assembly can induce circularly polarized light emission (CPLE) regardless of the existence of chirality in coassembled fluorophores. The CPLE from self-assembled chiral materials is particularly interesting because the CPLE can originate from both circularly polarized luminescence and circularly polarized scattering (CPS). Furthermore, because self-assembled nanostructures often exhibit stronger optical activity than their building blocks owing to dimension and resonance effects, the optical activity of single assembled nanostructures can be investigated by using microscopic technology combined with chiral optics. Here, we describe the state of the art for spectroscopic methods for the comprehensive analysis of chiral nanomaterials at various photon wavelengths, addressed with special attention given to new tools emerging both for materials with self-organized hierarchical chirality and single-particle spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Molecular Cobalt Catalysts for H 2 Generation with Redox Activity and Proton Relays in the Second Coordination Sphere

Two new Co(II) complexes have been synthesized and investigated as catalysts for H 2 generation. These catalysts were designed to incorporate redox-active bipyridine components and nitrogen groups, which can participate in electron and proton transfer steps in the catalytic cycle. The two catalysts differ by only one amino group, yielding a completely closed macrocycle and an open “macrocycle” complex. Removing just one nitrogen linker between the Co(II)-binding bipyridine groups has a profound impact on the molecular geometry observed by single crystal analysis. Photocatalysis experiments show that both catalysts are highly active for aqueous proton reduction at moderate pH levels, with the closed macrocycle reaching almost 2 × 10 4 turnovers of H 2 when photodriven by [Ru(2,2'-bipyridine) 3 ] 2+ using ascorbate as an electron relay and a phosphine compound as the terminal electron donor. Measurements of the electrocatalytic activity were used to investigate key steps in the mechanism of proton reduction by the molecular catalysts. The formation of a new reversible peak on addition of moderately strong acids in organic solvents suggests that protonation of the macrocycle plays an important role in H 2 generation. Onset of the catalytic current occurs near the reduction potential of the bipyridine components, suggesting that catalysis is mediated by electron transfer from the macrocycle to the cobalt center. From these observations, we propose a mechanism for catalytic proton reduction to H 2 , which involves both intramolecular proton and electron transfer steps from the macrocycle ligand to the cobalt center. In conclusion, the vital role of the second coordination sphere in the catalytic cycle places these relatively simple complexes on the pathway toward molecular catalysts that mimic the valuable features of enzymatic catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗