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At least 397 records · Page 22

Effective Storage of Electrons in Water by the Formation of Highly Reduced Polyoxometalate Clusters

Aqueous solutions of polyoxometalates (POMs) have been shown to have potential as high-capacity energy storage materials due to their potential for multi-electron redox processes, yet the mechanism of reduction and practical limits are currently unknown. Herein, we explore the mechanism of multi-electron redox processes that allow the highly reduced POM clusters of the form {MO 3 } y to absorb y electrons in aqueous solution, focusing mechanistically on the Wells-Dawson structure X 6 [P 2 W 18 O 62 ], which comprises 18 metal centers and can uptake up to 18 electrons reversibly (y = 18) per cluster in aqueous solution when the countercations are lithium. This unconventional redox activity is rationalized by density functional theory, molecular dynamics simulations, UV-vis, electron paramagnetic resonance spectroscopy, and small-angle X-ray scattering spectra. These data point to a new phenomenon showing that cluster protonation and aggregation allow the formation of highly electron-rich meta-stable systems in aqueous solution, which produce H 2 when the solution is diluted. Finally, we show that this understanding is transferrable to other salts of [P 5 W 30 O 110 ] 15- and [P 8 W 48 O 184 ] 40- anions, which can be charged to 23 and 27 electrons per cluster, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kicking the can down the road: understanding the effects of delaying the deployment of stratospheric aerosol injection

Abstract Climate change is a prevalent threat, and it is unlikely that current mitigation efforts will be enough to avoid unwanted impacts. One potential option to reduce climate change impacts is the use of stratospheric aerosol injection (SAI). Even if SAI is ultimately deployed, it might be initiated only after some temperature target is exceeded. The consequences of such a delay are assessed herein. This study compares two cases, with the same target global mean temperature of ∼1.5° C above preindustrial, but start dates of 2035 or a ‘delayed’ start in 2045. We make use of simulations in the Community Earth System Model version 2 with the Whole Atmosphere Coupled Chemistry Model version 6 (CESM2-WACCM6), using SAI under the SSP2-4.5 emissions pathway. We find that delaying the start of deployment (relative to the target temperature) necessitates lower net radiative forcing (−30%) and thus larger sulfur dioxide injection rates (+20%), even after surface temperatures converge, to compensate for the extra energy absorbed by the Earth system. Southern hemisphere ozone is higher from 2035 to 2050 in the delayed start scenario, but converges to the same value later in the century. However, many of the surface climate differences between the 2035 and 2045 start simulations appear to be small during the 10–25 years following the delayed SAI start, although longer simulations would be needed to assess any longer-term impacts in this model. In addition, irreversibilities and tipping points that might be triggered during the period of increased warming may not be adequately represented in the model but could change this conclusion in the real world.

Brody, Ezra (ORCID:000900030008681X)↗

Ozone Correction for AM0 Calibrated Solar Cells for the Aircraft Method

The aircraft solar cell calibration method has provided cells calibrated to space conditions for 37 years. However, it is susceptible to systematic errors due to ozone concentrations in the stratosphere. The present correction procedure applies a 1 percent increase to the measured I(sub SC) values. High band-gap cells are more sensitive to ozone absorbed wavelengths (0.4 to 0.8 microns) so it becomes important to reassess the correction technique. This paper evaluates the ozone correction to be 1+O3xFo, where O3 is the total ozone along the optical path, and Fo is 29.8 x 10(exp -6)/du for a Silicon solar cell, 42.6 x 10(exp -6)/du for a GaAs cell and 57.2 x 10(exp -6)/du for an InGaP cell. These correction factors work best to correct data points obtained during the flight rather than as a correction to the final result.

Snyder, David B.↗

Orbit Maintenance and Navigation of Human Spacecraft at Cislunar Near Rectilinear Halo Orbits

Multiple studies have concluded that Earth-Moon libration point orbits are attractive candidates for staging operations. The Near Rectilinear Halo Orbit (NRHO), a member of the Earth-Moon halo orbit family, has been singularly demonstrated to meet multi-mission architectural constraints. In this paper, the challenges associated with operating human spacecraft in the NRHO are evaluated. Navigation accuracies and human vehicle process noise effects are applied to various station keeping strategies in order to obtain a reliable orbit maintenance algorithm. Additionally, the ability to absorb missed burns, construct phasing maneuvers to avoid eclipses and conduct rendezvous and proximity operations are examined.

Davis, Diane↗

Performance of High-Resolution Mo/Cu Transition Edge Sensors Fabricated Using a Lift-Off Process

The soft X-ray band below ≈0.5 keV is expected to provide rich information on metallicity, temperature, and distribution of hot gas in our galaxy and the intergalactic medium. Resolving these densely spaced emission lines requires energy resolution on the order of 1--2 eV. The low count rates from diffuse astrophysical sources also necessitate large collection areas, particularly for a sounding rocket instrument with short exposure times and limited resources. This translates to large pixel sizes (about 1 mm 2 ) for a reasonable number of read-out channels. To achieve the required energy resolution with 200 nm thin Au absorbers (heat capacity C about 1 pJ/K), we are developing TES microcalorimeters with very high temperature sensitivity (αI), low enough current sensitivity (βI), and minimal excess noise (M). Out of the various fabrication approaches for the TES bilayer we have explored, the lift-off approach (as pioneered for Mo/Au TES by Joel Weber at NIST) so far is the simplest to execute. The simple square TES geometries we have tested to date show promising results for αI and βI. Measured complex impedance and noise for bare devices without absorbers are well described by two-body thermal models and their excess noise is found to be consistent with predictions for mixed-down Johnson noise by Wessels et al. More sensitive measurements with larger heat capacity are planned to accurately determine excess noise. In this paper, we give an overview of the process and summarize results of our detailed characterization measurements for thermal conductance G, αI, βI, and noise for several devices across a range of bias points.

Felix T Jaeckel↗

Gigaflop (billion floating point operations per second) performance for computational electromagnetics

Accurate and rapid evaluation of radar signature for alternative aircraft/store configurations would be of substantial benefit in the evolution of integrated designs that meet radar cross-section (RCS) requirements across the threat spectrum. Finite-volume time domain methods offer the possibility of modeling the whole aircraft, including penetrable regions and stores, at longer wavelengths on today's gigaflop supercomputers and at typical airborne radar wavelengths on the teraflop computers of tomorrow. A structured-grid finite-volume time domain computational fluid dynamics (CFD)-based RCS code has been developed at the Rockwell Science Center, and this code incorporates modeling techniques for general radar absorbing materials and structures. Using this work as a base, the goal of the CFD-based CEM effort is to define, implement and evaluate various code development issues suitable for rapid prototype signature prediction.

Shankar, V.↗

Electron scattering by highly polar molecules. I - KI

Electron-impact energy-loss spectra of KI were studied experimentally in the 15- to 130-deg angular range at impact energies of 6.7, 15.7, and 60 eV. The spectra reveal a number of excitation features which have not been detected previously and indicate that KI is a strong photon absorber in the vacuum-UV region. From the spectra, differential and integral electronically elastic and inelastic cross sections have been obtained by normalizing the experimental data to theoretical results at low scattering angles. Rotational excitation cross sections corresponding to delta j = 0, plus or minus 1, have been calculated using a dipole-plus-repulsive-core interaction potential and the distorted-wave approximation. For comparison, the rotational excitation cross sections have also been calculated in the Born point-dipole approximation.

Rudge, M. R. H.↗

Volcanic CO2 Abundance of Kilauea Plume Retrieved by Meand of AVIRIS Data

Absorbing the electromagnetic radiation in several regions of the solar spectrum, CO2 plays an important role in the Earth radiation budget since it produces the greenhouse effect. Many natural processes in the Earth s system add and remove carbon dioxide. Overall, measurements of atmospheric carbon dioxide at different sites around the world show an increased carbon dioxide concentration in the atmosphere. At Mauna Loa Observatory (Hawaii) the measured carbon dioxide increased from 315 to 365 ppm, in the period 1958 2000 [Keeling et al., 2001]. While at the large scale, the relationship between CO2 increase and global warming is established [IPCC, 1996], at the local scale, many studies are still needed to understand regional and local sources of carbon dioxide, such as volcanoes. The volcanic areas are particularly rich in carbon dioxide; this is due to magma degassing in the summit craters region of active volcanoes, and to the presence of fractures and active faults [Giammanco et al., 1998]. Several studies estimate a global flux of volcanic CO2 (34+/-24)10(exp 6) tons/day from effusive volcanic emissions, such as the tropospheric volcanic plume (Table 1) [McClelland et al., 1989]. Plumes are a turbulent mixture of gases, solid particles and liquid droplets, emitted continuously at high temperature from summit craters, fumarolic fields or during eruptive episodes. Inside the plume, water vapour represents 70 90% of the volcanic gases. The main gaseous components are CO2, SO2, HCl, H2, H2S, HF, CO, N2 and CH4. Other plume components are volcanic ash, aqueous and acid droplets and solid sulphur-derived particles [Sparks et al., 1997]. Volcanic gases and aerosols are evidences of volcanic activity [Spinetti et al., 2003] and they have important climatic and environmental effects [Fiocco et al., 1994]. For example, Etna volcano is one of the world s major volcanic gas sources [Allard et al., 1991]. New studies on volcanic gaseous emissions have pointed out that a variation of the gas ratio CO2/SO2 is related to eruptive episodes [Caltabiano et al., 1994]. However, measurements and monitoring of volcanic carbon dioxide are difficult and often hazardous, due to the high background presence of atmospheric CO2 and the inaccessibility of volcanic sites. Hyperspectral remote sensing is a suitable technique to overcome the difficulties of ground measurement. It permits a rapid, comprehensive view of volcanic plumes and their evolution over time, detection of all gases with absorption molecular lines within the sensor s multispectral range and, in general, measurement of all the volatile components evolving from craters. The molecular and particle plume components scatter and absorb incident solar radiation. The integral of the radiation difference composes the signal measured by the remote spectrometer. The inversion technique consists of retrieving the plume component concentrations, hence decomposing the signal into the different contributions. The accuracy of remote sensing techniques depends primarily on the sensor capability and sensitivity.

Spinetti, C.↗

Quantum Mechanical Evaluation of CZTS Properties for Photovoltaic Applications

As a quaternary semiconductor, CZTS (Cu 2 ZnSnS 4 ) shows promise as a thin-film solar cell material. The constituent elements in CZTS are abundant and non-toxic, and CZTS has an ideal band gap (~1.5 eV) for solar cell applications, which produces a large absorption coefficient. Unfortunately, the low efficiencies and difficulties in synthesizing the desired crystallographic phase (kesterite) and the associated formation of antisite defects limit its deployment. Using theoretical and computational tools, we investigated these current limitations, explored strategies to resolve these issues, and developed design guidelines to improve the efficiency of CZTS-based sunlight absorbers. We first sought to understand the challenges associated with synthesizing the kesterite phase and proposed ways to favor kesterite growth, thus adding to the understanding of CZTS photovoltaics. We also analyzed the major limitations at the atomic scale lowering the efficiency of CZTS: the low open-circuit voltage (V oc ) and the short carrier lifetime, thus addressing the technical effectiveness of CZTS photovoltaics. We believe the latter is due to Shockley-Read-Hall (SRH) recombination centers associated with point defects. We also studied the electronic structure of interfaces and defects introducing such recombination centers, and explored doping strategies to reduce SRH recombination. Ultimately, these efforts will benefit the public by contributing to the development of cheap and efficient solar energy conversion technologies made from abundant, non-toxic materials.

14 SOLAR ENERGY↗

Magnetic sheath adjacent to absorbing surfaces.

Major attention is given to the existence and structure of a 'magnetic sheath' adjacent to perfectly absorbing solid surfaces. The basic equations for a two-field continuum model are presented, and the quasi-neutral approximation and Bohm's criterion are briefly reviewed. The infinite conductivity MHD equations are recovered by invoking the small magnetic Debye length approximation. This approximation is relaxed, and the appropriate 'boundary layer' equation for the magnetic sheath is presented. The first magnetic sheath criterion is derived, which states that the conditions at the edge of the sheath, as characterized by a point in the Friedrichs diagram, must be located in certain restricted regions in order for a magnetic sheath to exist. The second magnetic sheath criterion is discussed.

Lam, S. H.↗

3D Printing of Inconel 718 with Enhanced Boron Composition as a Novel Solar Absorber Tube Material in the Concentrated Solar Power (CSP) System

The growing demands for elevated efficiency in the solar energy industry led researchers to focus on the development of functional solar absorber tube material in concentrated solar power (CSP) systems, when molten salts are adopted as the heat transfer fluid. In this study, the typical solar absorber tube material, Inconel 718, was enhanced with boron to achieve a higher solar absorptivity in the visible light spectrum. Combined with an additive manufacturing (AM) method, the boron composition exceeded the traditional manufacturing limit of 60 ppm without microstructural defects. The boron-enhanced Inconel 718 exhibited a high solar absorptivity of nearly 90 % while maintaining a high thermal cycle fatigue resistance after thermal cycling treatment between 550°C and 720°C. The boron composition was increased to the manufacturing failure point, and the effects of different boron compositions on mechanical properties, microstructure, and optical properties were studied. The provided microstructure-property map in this study delivers high potentials of functional AM-printed alloy material in CSP applications.

13 HYDRO ENERGY↗

Fast two-stream method for computing diurnal-mean actinic flux in vertically inhomogeneous atmospheres

Based on a derivation of the two-stream daytime-mean equations of radiative flux transfer, a method for computing the daytime-mean actinic fluxes in the absorbing and scattering vertically inhomogeneous atmosphere is suggested. The method applies direct daytime integration of the particular solutions of the two-stream approximations or the source functions. It is valid for any duration of period of averaging. The merit of the method is that the multiple scattering computation is carried out only once for the whole averaging period. It can be implemented with a number of widely used two-stream approximations. The method agrees with the results obtained with 200-point multiple scattering calculations. The method was also tested in runs with a 1-km cloud layer with optical depth of 10, as well as with aerosol background. Comparison of the results obtained for a cloud subdivided into 20 layers with those obtained for a one-layer cloud with the same optical parameters showed that direct integration of particular solutions possesses an 'analytical' accuracy. In the case of the source function interpolation, the actinic fluxes calculated above the one-layer and 20-layer clouds agreed within 1%-1.5%, while below the cloud they may differ up to 5% (in the worst case). The ways of enhancing the accuracy (in a 'two-stream sense') and computational efficiency of the method are discussed.

Filyushkin, V. V.↗

A study of the aerothermal environment for the Pioneer Venus multiprobe mission

In December 1978, four Pioneer Venus probe spacecraft are scheduled for almost simultaneous entry into the Venusian atmosphere at widely dispersed points about the planet. In this study, both detailed and approximate flow field analyses are used to define the entry aerothermal environment for the forebody of each of the four probes. The results show that approximate analyses can be used to predict inviscid radiative and laminar convective heating rates with acceptable accuracy. However, the radiative heating rates obtained with inviscid analyses are significantly greater than those obtained with a nonablating viscous-shock-layer (VSL) analysis, because the VSL analysis includes a strongly absorbing boundary layer. Also, the results show that the radiative heating is sensitive to small variations in atmospheric gas composition while the convective heating is not affected. With carbon-phenolic injection, the convective heating is reduced substantially while the overall radiative heating reduction is very small. Most of the radiative blockage occurs in the atomic line transitions which is significant only in the stagnation region.

Moss, J. N.↗

Density measurement in air with a saturable absorbing seed gas

A method for making density measurements in a compressible flow by using off resonance laser induced fluorescence is studied. The seed molecule chosen for study is the iodine molecule which is excited with the 514.5 nm line of the argon ion laser whose output is frequency tuned, by as much as 3 GHz, relative to a strong iodine transition using an intracavity etalon. The theory which was developed to analyze the effect will be used in conjunction with two experiments being conducted to further study the method an acoustic resonance tube in which controlled perturbations about a uniform state are produced, and a small supersonic jet in which the conditions of the flow vary widely from point to point.

Baganoff, D.↗

Characterizing laser preheat for laser-driven magnetized liner inertial fusion using soft x-ray emission

Laser heating of a gas in a cylindrical liner held in by a thin foil window is a critical process in the MagLIF (magnetized liner inertial fusion) concept. Window burn-through and gas heating for OMEGA scale MagLIF cylinders as a function of time have been determined using spectrally integrated soft x-ray diagnostics. Window laser absorption is classified in terms of the emitted x-rays from the window plasma as a function of laser energy, and shows that laser energy absorbed is weakly dependent on incident intensity. Radiation-hydrodynamic simulations overestimate the amount of laser energy absorbed by the window as evidenced by the increase in x-ray radiation across several photon energy bands compared to experiments. Gas temperatures inferred from soft x-ray emission from the front 1 mm of the liner are shown to evolve in time in a similar manner to simulation predictions. In conclusion, soft x-ray emission from the gas within the region of the liner that is normally imploded is shown to meet the 100 eV requirements set by the initial point design for laser-driven MagLIF.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Photo-Switching of Protein Dynamical Collectivity

We examine changes in the picosecond structural dynamics with irreversible photobleaching of red fluorescent proteins (RFP) mCherry, mOrange2 and TagRFP-T. Measurements of the protein dynamical transition using terahertz time-domain spectroscopy show in all cases an increase in the turn-on temperature in the bleached state. The result is surprising given that there is little change in the protein surface, and thus, the solvent dynamics held responsible for the transition should not change. A spectral analysis of the measurements guided by quasiharmonic calculations of the protein absorbance reveals that indeed the solvent dynamical turn-on temperature is independent of the thermal stability/photostate however the protein dynamical turn-on temperature shifts to higher temperatures. This is the first demonstration of switching the protein dynamical turn-on temperature with protein functional state. The observed shift in protein dynamical turn-on temperature relative to the solvent indicates an increase in the required mobile waters necessary for the protein picosecond motions, that is, these motions are more collective. Melting-point measurements reveal that the photobleached state is more thermally stable, and structural analysis of related RFP’s shows that there is an increase in internal water channels as well as a more uniform atomic root mean squared displacement. These observations are consistent with previous suggestions that water channels form with extended light excitation providing O2 access to the chromophore and subsequent fluorescence loss. We report that these same channels increase internal coupling enhancing thermal stability and collectivity of the picosecond protein motions. The terahertz spectroscopic characterization of the protein and solvent dynamical onsets can be applied generally to measure changes in collectivity of protein motions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neutrinos and Gamma Rays from Seyfert Galaxies Constrain the Properties of Coronal Turbulence

The TeV neutrino signal observed by IceCube from the active galactic nucleus NGC 1068 can probe its innermost coronal regions. If these neutrinos originate from hadrons accelerated within a magnetized turbulent corona, their intensity and spectrum depend on the turbulent magnetic field strength and turbulence coherence scale. The gamma rays accompanying neutrino production are absorbed in this optically thick environment, in a way that depends sensitively on the size of the corona. By a joint fit of the IceCube and Fermi-LAT observations, we translate the multimessenger signal from NGC 1068 and the tentative signal from NGC 7469 into quantitative constraints on coronal properties. NGC 1068, with a significant TeV neutrino excess, favors a compact, strongly magnetized corona with a large turbulence coherence length relative to the coronal size. NGC 7469, with two ∼100 TeV neutrino events, points instead to a somewhat larger corona with much smaller coherence length and high magnetization, but a very small fraction of energy in nonthermal protons. We obtain the diffuse flux from a population of Seyfert galaxies identical to either NGC 1068 or NGC 7469. Finally, we consider a third scenario, motivated by the spectral break observed in the diffuse neutrino flux at tens of TeV, with coronal properties intermediate between the two point-source-inspired models. To enable detailed comparisons with the IceCube and electromagnetic observations, we release our model predictions in a GitHub repository.

Testagrossa, Federico [Deutsches Elektronen-Synchr↗

A color gradient in the soft X-ray diffuse background

It is shown that the deviations of the soft X-ray diffuse background B band to C band intensity ratio from a constant value can be described as a simple dipole-like variation across the sky. In terms of the observed Wisconsin B/C band intensity ratio, the mean value is 0.355, the dipole magnitude is 0.106, and the positive dipole axis points toward l = 168.7 deg, b = 11.2 deg, almost in the galactic anticenter direction. This gradient in the spectral hardness can be due to several causes; the simplest is a temperature gradient in the X-ray emitting plasma of the local cavity from about 10 exp 6.2 K toward the galactic center to about 10 exp 5.9 K in the anticenter direction. While the physical origin of such a temperature gradient is uncertain, the alignment of the dipole with the higher temperature (and absorbed) Loop I region may be significant.

Snowden, S. L.↗