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At least 1,315 records · Page 73

Molecular Switch Cobalt Redox Shuttle with a Tunable Hexadentate Ligand

Strong-field hexadentate ligands were synthesized and coordinated to cobalt metal centers to result in three new low-spin to low-spin Co(III/II) redox couples. The ligand backbone has been modified with dimethyl amine groups to result in redox potential tuning of the Co(III/II) redox couples from –200 to –430 mV versus Fc +/0 . The redox couples surprisingly undergo a reversible molecular switch rearrangement from five-coordinate Co(II) to six-coordinate Co(III) despite the ligands being hexadentate. The complexes exhibit modestly faster electron self-exchange rate constants of 2.2–4.2 M –1 s –1 compared to the high-spin to low-spin redox couple [Co(bpy) 3 ] 3 + /2 + at 0.27 M –1 s –1 , which is attributed to the change in spin state being somewhat offset by this coordination switching behavior. The complexes were utilized as redox shuttles in dye-sensitized solar cells with the near-IR AP25 + D35 dye system and exhibited improved photocurrents over the [Co(bpy) 3 ] 3 + /2 + redox shuttle (19.8 vs 18.0 mA/cm 2 ). Finally, future directions point toward pairing the low-spin to low-spin Co(II/III) tunable series to dyes with significantly more negative highest occupied molecular orbital potentials that absorb into the near-IR where outer sphere redox shuttles have failed to produce efficient dye regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Innovating the next generation of commercial smart building software

Nearly 30% of commercial building energy use is wasted due to equipment faults and HVAC controls problems. The result is increased emissions, compromised comfort and productivity, and less reliable coordination of building power needs with a clean grid. The energy impact alone represents $17 billion in potential savings. Today’s smart building software provides a robust solution to address these operational deficiencies. Energy management and information systems (EMIS) are saving up to 9% on average, with two-year paybacks. They are being incorporated into energy management processes, commissioning services, and utility programs. As effective as they are, two barriers prevent even deeper benefits; limited personnel to fix problems once they are identified, and the expense and time to manually implement changes in control systems. In partnership with the research community, the EMIS industry is developing new capabilities to overcome these barriers. Moving beyond siloed products for either fault detection and diagnostics, or optimal control, these new capabilities empower users to not only automatically identify faults, but also to push corrective action, and control improvements to their buildings. In this paper, several areas for enhancements are documented: ‘one-time’ correction of faults such as setpoints, schedules, and economizer lockouts; short-term active testing for automated proportional integral derivative (PID) loop tuning and functional testing; and continuous supervisory control for demand flexibility and year-round efficiency. Results are presented from a pair of partner implementations out of a dozen providers integrating these enhancements into their products, including field tests from across the country, and insights into operator acceptance and integration into operations and maintenance practices.

Casillas, Armando↗

Open-circuit voltage improvements in low-resistivity solar cells

Mechanisms limiting the open-circuit voltage in 0.1 ohm-cm solar cells were investigated. It was found that a rather complicated multistep diffusion process could produce cells with significantly improved voltages. The voltage capabilities of various laboratory cells were compared independent of their absorption and collection efficiencies. This was accomplished by comparing the cells on the basis of their saturation currents or, equivalently, comparing their voltage outputs at a constant current-density level. The results show that for both the Lewis diffused emitter cell and the Spire ion-implanted emitter cell the base component of the saturation current is voltage controlling. The evidence for the University of Florida cells, although not very conclusive, suggests emitter control of the voltage in this device. The data suggest further that the critical voltage-limiting parameter for the Lewis cell is the electron mobility in the cell base.

Godlewski, M. P.↗

Solar-terrestrial data access distribution and archiving

It is recommended that a central data catalog and data access network (CDC/DAN) for solar-terrestrial research be established, initially as a NASA pilot program. The system is envisioned to be flexible and to evolve as funds permit, starting from a catalog to an access network for high-resolution data. The report describes the various functional requirements for the CDC/DAN, but does not specify the hardware and software architectures as these are constantly evolving. The importance of a steering committee, working with the CDC/DAN organization, to provide scientific guidelines for the data catalog and for data storage, access, and distribution is also stressed.

Source record↗

Aerodynamic properties of fractal grains: Implications for the primordial solar nebula

Under conditions in the primordial solar nebula and dense interstellar clouds, small grains have low relative velocities. This is the condition for efficient sticking and formation of fractal aggregates. A calculation of the ratio of cross section, sigma, to number of primary particles, N, for fractal clusters yielded 1n sigma/N = 0.2635 + 0.5189N sup (-0.1748). This ratio decreases slowly with N and approaches a constant for large N. Under the usual assumption of collisions producing spherical compact, uniform density aggregates, sigma/N varies as N sup -1/3 and decreases rapidly. Fractal grains are therefore much more closely coupled to the gas than are compact aggregates. This has a significant effect on the aerodynamic behavior of aggregates and consequently on their evolution and that of the nebula.

Meakin, P.↗

Global optical climatology of the free tropospheric aerosol from 1.0-micron satellite occultation measurements

Measurements of the aerosol/molecular extinction ratio at 1-micron wavelength, obtained from the SAGE I, SAGE II, and SAM II solar occultation satellite experiments between 1978 and 1986, have been used to study the global-scale behavior of the upper tropospheric aerosol. The distribution of extinction ratio values shows a pronounced mode between about 0.5 and 5 in all data subsets, regardless of latitude and season. Within a given latitude band and season with mode value is nearly constant over the altitude range from about 5 km above the earth's surface to 3 km below the tropopause. The mode shows a distinct seasonal variation, with maxima in local spring and summer, and is significantly enhanced following vlocanic injection of material into the stratosphere. South of latitude 20-deg N, mode values in the absence of volcanic contamination are normally between 0.5 and 1.0 north of 20-deg N, values up to about 5 are observed, probably associated with aerosol derived from surface dust or anthropogenic sources. A secondary mode, with extinction ratios of 30 or greater and little or no variation of extinction with wavelength, is apparent just below the tropopause. This mode is believed to be associated with thin cloud along the ray path from the sun to the satellite.

Kent, G. S.↗

Dynamics of the Venus atmosphere

The superrotation of the Venus atmosphere is a major unanswered problem in planetary science. At cloud-top levels (65-70 km altitude) the atmosphere rotates with a five-day period, corresponding to an equatorial wind speed of 90 m/s. Angular velocity is roughly constant on spherical shells, and decreases linearly with altitude to zero at the surface. The direction of rotation is the same as that of the solid planet, which is retrograde--opposite to the direction of orbital motion, but the 5-day period is short compared to the 243-day spin period of the solid planet or to the mean solar day, which is 117 Earth-days at the surface. The problem with the superrotation is that shearing stresses tend to transfer angular momentum downward, and would slow the atmosphere until it is spinning with the solid planet. Some organized circulation pattern is counteracting the tendency, but the pattern has not been identified. A simple Hadley-type circulation cannot do it because such a circulation is zonally symmetric and Hide's Theorem states that in an axisymmetric circulation an extremum in angular momentum per unit mass M can exist only at the surface. Venus violates the last condition, having a maximum of retrograde M on the equator at 70-80 km altitude. This leaves waves and eddies to maintain the superrotation but the length scales and forcing mechanisms for these motions need to be specified. Possible forcing mechanisms associated with waves, eddies and tides are discussed.

Ingersoll, A. P.↗

Constraints on Climate and Habitability for Earth-like Exoplanets Determined from a General Circulation Model

Conventional definitions of habitability require abundant liquid surface water to exist continuously over geologic timescales. Water in each of its thermodynamic phases interacts with solar and thermal radiation and is the cause for strong climatic feedbacks. Thus, assessments of the habitable zone require models to include a complete treatment of the hydrological cycle over geologic time. Here, we use the Community Atmosphere Model from the National Center for Atmospheric Research to study the evolution of climate for an Earth-like planet at constant CO2, under a wide range of stellar fluxes from F-, G-, and K-dwarf main sequence stars. Around each star we find four stable climate states defined by mutually exclusive global mean surface temperatures (Ts); snowball (Ts ≤ 235 K), waterbelt (235 K ≤ Ts ≤ 250 K), temperate (275 K ≤ Ts ≤ 315 K), and moist greenhouse (Ts ≥ 330 K). Each is separated by abrupt climatic transitions. Waterbelt, temperate, and cooler moist greenhouse climates can maintain open-ocean against both sea ice albedo and hydrogen escape processes respectively, and thus constitute habitable worlds. We consider the warmest possible habitable planet as having Ts ∼ 355 K, at which point diffusion limited water-loss could remove an Earth ocean in ∼1 Gyr. Without long timescale regulation of non-condensable greenhouse species at Earth-like temperatures and pressures, such as CO2, habitability can be maintained for an upper limit of ∼2.2, ∼2.4, and ∼4.7 Gyr around F-, G-, and K-dwarf stars respectively, due to main sequence brightening.

Eric T Wolf↗

Constraints on Climate and Habitability for Earth-like Exoplanets Determined from a General Circulation Model

Conventional definitions of habitability require abundant liquid surface water to exist continuously over geologic timescales. Water in each of its thermodynamic phases interacts with solar and thermal radiation and is the cause for strong climatic feedbacks. Thus, assessments of the habitable zone require models to include a complete treatment of the hydrological cycle over geologic time. Here, we use the Community Atmosphere Model from the National Center for Atmospheric Research to study the evolution of climate for an Earth-like planet at constant CO2, under a wide range of stellar fluxes from F-, G-, and K-dwarf main sequence stars. Around each star we find four stable climate states defined by mutually exclusive global mean surface temperatures (T(sub s)); snowball (T(sub s) ≼ 235 K), waterbelt (235 K ≼ T(sub s) ≼ 250 K), temperate (275 K ≼ T(sub s) ≼ 315 K), and moist greenhouse (T(sub s) ≽ 330 K). Each is separated by abrupt climatic transitions. Waterbelt, temperate, and cooler moist greenhouse climates can maintain open-ocean against both sea ice albedo and hydrogen escape processes respectively, and thus constitute habitable worlds. We consider the warmest possible habitable planet as having T(sub s) ∼ 355 K, at which point diffusion limited water-loss could remove an Earth ocean in ∼1 Gyr. Without long timescale regulation of non-condensable greenhouse species at Earth-like temperatures and pressures, such as CO2, habitability can be maintained for an upper limit of ∼2.2, ∼2.4, and ∼4.7 Gyr around F-, G-, and K-dwarf stars respectively, due to main sequence brightening.

Astrobiology↗

Quasi-Decadal Oscillations Generated by the QBO

Quasi-decadal oscillations (QDO) have been observed in the stratosphere and have been linked to the equatorial Quasi-Biennial Oscillation (QBO) and to the 11-year solar activity cycle. With the use of a 2D version of our Numerical Spectral Model (NSM) that incorporates Hines'Doppler Spread Parameterization (DSP) for gravity waves (GW), we demonstrate that beat periods between 9 and I I years can be generated by the QBO as it interacts through GW filtering with the Annual Oscillation (AO) and Semi-annual Oscillation (SAO). Results are discussed from computations covering up to 50 years, and our analyses leads to the following conclusions. The QDO as a stand-alone signature is largely confined to the upper mesosphere. Its largest signature appears in the form of amplitude modulations of the QBO, AO and SAO, and these extend into the lower stratosphere. The downward control that characterizes the QBO apparently comes into play, and the longer time constants for diffusion and radiative loss at lower altitudes facilitate the QDO response. Although excited by the QBO, which is confined to low latitudes, the QDO is shown to extend to high latitudes. The effect is particularly large for the QBO with period around 33.5 month (near the upper limit of observations), which interacts with the SAO to produce a hemispherically symmetric QDO. Our analysis indicates that the QDO is transferred to high latitudes by the meridional circulation, which prominently exhibits this periodicity particularly in the amplitude modulation of the AO. The propensity for beat periods around 10 years may help to increase significantly the efficiency for generating solar cycle signatures in the atmosphere, and we discuss numerical experiments related to that.

Mayr, Hans G.↗

Double Power-law Formation by Sequential Particle Acceleration

Spectral double power laws are common in solar high-energy phenomena such as flares and interplanetary energetic-electron events. However, the physical mechanism that produces the changes in power-law index within a single spectrum is unclear. We developed a fully analytical method of forming single power-law spectra from sequential acceleration of particles orbiting inside and hopping between simulated large-scale magnetic islands formed by flare reconnection. Here, we extend the analytical method to the formation of double power-law spectra by assuming sequential acceleration in two successive regions with different acceleration and particle-transport rates. The resulting spectral distribution is continuous and smooth, with a flattening at low energies, two power-law regions at mid-energies, and a steep rollover at high energies. The model provides analytical expressions for the spectral indices, all energy breaks, and normalization constants as functions of just three physical parameters of each acceleration region: (1) the energy gain in each accelerator, (2) the percentage of particles transferred between accelerators, and (3) the number of accelerators visited. One of the most salient predictions of our work is that the spectral index at high (low) energies is determined by the parameters of the first "seed" (second) acceleration region. By constructing the spectral distribution through an iterative analytical process, the evolution toward a double power law is easily characterized and explained. Our analytical model provides tools to interpret space- and ground-based observations from RHESSI, FOXSI, NuSTAR, Solar Orbiter/STIX, EOVSA, and future high-energy missions.

Solar flares↗

Determination of Coronal Magnetic Fields from Vector Magnetograms

During the course of the present contract we developed an 'evolutionary technique' for the determination of force-free coronal magnetic fields from vector magnetograph observations. The method can successfully generate nonlinear force- free fields (with non-constant-a) that match vector magnetograms. We demonstrated that it is possible to determine coronal magnetic fields from photospheric measurements, and we applied it to vector magnetograms of active regions. We have also studied theoretical models of coronal fields that lead to disruptions. Specifically, we have demonstrated that the determination of force-free fields from exact boundary data is a well-posed mathematical problem, by verifying that the computed coronal field agrees with an analytic force-free field when boundary data for the analytic field are used; demonstrated that it is possible to determine active-region coronal magnetic fields from photospheric measurements, by computing the coronal field above active region 5747 on 20 October 1989, AR6919 on 15 November 1991, and AR7260 on 18 August 1992, from data taken with the Stokes Polarimeter at Mees Solar Observatory, University of Hawaii; started to analyze active region 7201 on 19 June 1992 using measurements made with the Advanced Stokes Polarimeter at NSO/Sac Peak; investigated the effects of imperfections in the photospheric data on the computed coronal magnetic field; documented the coronal field structure of AR5747 and compared it to the morphology of footpoint emission in a flare, showing that the 'high- pressure' H-alpha footpoints are connected by coronal field lines; shown that the variation of magnetic field strength along current-carrying field lines is significantly different from the variation in a potential field, and that the resulting near-constant area of elementary flux tubes is consistent with observations; begun to develop realistic models of coronal fields which can be used to study flare trigger mechanisms; demonstrated that magnetic nonequilibrium can disrupt sheared coronal arcades, and that helmet streamers can disrupt, leading to coronal mass ejections. Our model has significantly extended the realism with which the coronal magnetic field can be inferred from actual observations. In a subsequent contract awarded by NASA, we have continued to apply and improve the evolutionary technique, to study the physical properties of active regions, and to develop theoretical models of magnetic fields.

Mikic, Zoran↗

3D Propagation of Relativistic Solar Protons through Interplanetary Space

Context. Solar Energetic Particles (SEPs) with energy in the GeV range can propagate to Earth from their acceleration region near the Sun and produce Ground Level Enhancements (GLEs). The traditional approach to interpreting and modelling GLE observations assumes particle propagation only parallel to the magnetic field lines of interplanetary space, i.e. it is spatially 1D. Recent measurements by PAMELA have characterised SEP properties at 1 AU for the ~100 MeV-1 GeV range at high spectral resolution. Aims. We model the transport of GLE-energy solar protons using a 3D approach, to assess the effect of the Heliospheric Current Sheet (HCS) and drifts associated to the gradient and curvature of the Parker spiral. We derive 1 AU observables and compare the simulation results with data from PAMELA. Methods. We use a 3D test particle model including a HCS. Monoenergetic populations are studied first to obtain a qualitative picture of propagation patterns and numbers of crossings of the 1 AU sphere. Simulations for power law injection are used to derive intensity profiles and fluence spectra at 1 AU. A simulation for a specific event, GLE 71, is used to compare with PAMELA data. Results. Spatial patterns of 1 AU crossings and the average number of crossings are strongly influenced by 3D effects, with significant differences between periods of A+ and A- polarities. The decay time constant of 1 AU intensity profiles varies depending on the position of the observer and is not a simple function of the mean free path as in 1D models. Energy dependent leakage from the injection flux tube is particularly important for GLE energy particles, resulting in a rollover in the spectrum.

Solar energetic particles↗

Experimental screening of salt hydrates for thermochemical energy storage for building heating application

The selection of a suitable salt hydrate for use in a thermochemical energy storage system is challenging. In this work, the most promising salts to store intermediate heat energy were selected and tested. The criteria set are; volumetric energy density of >500 kWh m-3 with a dehydration temperature of <100 degrees C, material cost of <3.5 USD kg-1 (<15 USD kWh-1), melting does not occur during dehydration and safety. Based on that, the salt hydrates SrCl 2 , MgSO 4 , Na 3 PO 4 , MgCl 2 and SrBr 2 were selected and tested experimentally. A constant temperature and humidity chamber was used to measure moisture sorption of different salts. The hydration is investigated under the conditions of 20 degrees C and 20, 30, 40, 60 and 80% RH, while dehydration is investigated under the conditions of 70, 100 and 140 degrees C using an oven. These dehydration temperatures of <100 degrees C are suitable for solar application whereas the dehydration temperature of 140 degrees C is suitable for waste heat. Furthermore, the salts are cycled over 30 times under the hydration conditions of 20 degrees C, 60% RH with a dehydration temperature of 100 degrees C. From these results, it is concluded that SrCl 2 and SrBr 2 are the most promising salts. This study outlines both the advantages and disadvantages of each salt and states the conditions they are most suitable for.

25 ENERGY STORAGE↗

Realistic Estimation of CO2 Emission Reductions Due to Building Retrofit

Constant CO2 emission factors of electricity are often used to study the emissions of buildings. However, in the era of increased renewable energy for power generation, emission factors of electricity are dynamically changing. This study is to investigate the impact of dynamic CO2 emission factors, which are more realistic than constant ones, on the emission reductions due to building retrofits. The results reveal that if dynamic CO2 emission factors are used for U.S. medium office buildings, improving the efficiency of lighting or electric equipment will lead to more emission reductions in locations with high wind power penetration (e.g., 12% more reductions in Rochester) and fewer reductions in locations with high solar power penetration (e.g., 8% fewer reductions in San Diego). As for improving envelope insulation, dynamic CO2 emission factors have more impact on the emission reductions in hot climates than in cold climates.

Lou, Yingli↗

Polarization of the reflected light of asteroid 433 Eros

Linear polarizations measured for asteroid 433 Eros at various wavelengths and at solar phase angles ranging from 9 to 53 deg are presented. The polarization results are entirely typical of main-belt S asteroids, and indicate a dusty surface with geometric albedo 0.20. The derived effective diameter at photometric maximum is 21 km. Eros is quite uniform polarimetrically; no dependence on aspect is detected, and the polarization is shown to be constant during a single rotation with a precision of one part in forty.

Zellner, B.↗

Accretion of rotating fluids by barytropes - Numerical results for white-dwarf models

Numerical sequences of rotating axisymmetric nonmagnetic equilibrium models are constructed which represent the evolution of a barytropic star as it accretes material from a rotating medium. Two accretion geometries are considered - one approximating accretion from a rotating cloud and the other, accretion from a Keplerian disk. It is assumed that some process, such as Ekman spin-up or nonequilibrium oscillations, maintains nearly constant angular velocity along cylinders about the rotation axis. Transport of angular momentum in the cylindrically radial direction by viscosity is included. Fluid instabilities and other physical processes leading to enhancement of this transport are discussed. Particular application is made to zero-temperature white-dwarf models, using the degenerate electron equation of state. An initially nonrotating 0.566-solar-mass white dwarf is followed during the accretion of more than one solar mass of material. Applications to degenerate stellar cores, to mass-transfer binary systems containing white dwarfs, such as novae and dwarf novae, to Type I supernovae, and to galactic X-ray sources are considered.

Durisen, R. H.↗

Empirical data on the origin of 'new' comets

The mass distribution of a group of 62 comets from the sample of Marsden et al (1978) was determined by assuming that the size of a comet is in proportion to the surface area of its vaporizing nucleus. A bimodal distribution was found, with a gap between magnitudes 8.1 and 9. The 50 brighter comets (magnitudes 1 to 8) have been tentatively identified as true 'new' comets; their size distribution cannot be fit to a constant slope on a log-log graph. These comets were apparently formed by a mechanism which differs from the fragmentation process. The 12 fainter may be fragments of comets which split or dimmed during their first passages. Results indicate that new comets could be identified with pristine planetesimals; they decay rapidly, probably by splitting when they enter the inner solar system.

Delsemme, A. H.↗