Results for “point absorber” — Page 25

NASA NTRSDate not supplied

Why Developing A Full-Sun UV Spectrograph Sounding Rocket Is Difficult but Necessary

For a conference focused on a 20-year perspective of where we have been and where we are going, this talk will highlight specifically why we need a sounding rocket to lead the way in obtaining high-resolution UV spectroscopy of our sun-as-a-star. The currently available data is either sparse or at a much lower resolution when compared with Hubble (HST) spectra of other stars. Because of this, we cannot say with certainty if our Sun’s variability is typical. This limitation is hindering our quest to place our Sun in it’s rightful place on our star-charts. Ultraviolet light is a key component in determining this. Elements such as Hydrogen and Iron have strong emission lines here, and from them we can determine many things about the star from which they originate. The width of these spectral features can tell us about the relative plasma activity on the surface of the star, the abundance of those elements, and of course the temperatures. This has of course been done with many instruments that have very narrow field of views and/or narrow bandwidths. The only way to directly compare our Sun’s UV ”fingerprint” with other stars is to take an image of it in the same manner by which HST does: as a point source object. Our team’s aim has been to develop a sounding rocket capable of doing just that. Along the way, the many challenges we face are producing many solutions. A unique take on the traditional Rowland circle spectrograph will allow us to cover a large range of UV spectra with minimal moving parts. A novel in-situ gain calibration technique will be used in order to maintain the high level of radiometric accuracy desired. Naturally, complications arise when one takes UV measurements as you are flying out of earth’s atmosphere and back into it. Though it may be minor, the absorbed UV spectra from the atmosphere will have to be accounted for. In preparing for this, we have stumbled across a way in which those ”telluric” absorption lines may prove useful for spectral calibration purposes. In addition, raw data from previous sounding rocket missions may have hidden within them useful information for the atmospheric-physics community. In this talk, we will highlight the unique calibration problems and solutions we have faced, and how those are of greater importance to the greater heliophysics and atmospheric communities. With these amazing developments at hand, the future of heliophysics instrumentation is looking bright. This material is based upon work supported by the NSF EPSCoR RII-Track-1.2a (Non-invasive plasma diagnostics for LTP) Cooperative Agreement OIA-1655280. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.

NASA, UAH, MSU, Sounding Rocket, Aeronomy, Instrum↗

NASA NTRS2007

The Suzaku Observation of the Nucleus of the Radio Loud Active Galaxy Centaurus A: Constraints on Abundances in the Accreting Material

A Suzaku observation of the nucleus of the radio-loud AGN Centaurus A in 2005 has yielded a broadband spectrum spanning 0.3 to 250 keV. The hard X-rays are fit by two power laws, absorbed by columns of 1.5 and 7 x 10(exp 23) per square centimeter. The dual power-laws are consistent with previous suggestions that the powerlaw components are X-ray emission from the sub-pc VLBI jet and from Bondi accretion at the core, or are consistent with a partial covering interpretation. The soft band is dominated by thermal emission from the diffuse plasma and is fit well by a two-temperature VAPEC model, plus a third power-law component to account for scattered nuclear emission, kpc-scale jet emission, and emission from X-ray Binaries and other point sources. Narrow fluorescent emission lines from Fe, Si, S, Ar, Ca and Ni are detected. The width of the Fe Ka line yields a 200 light-day lower limit on the distance from the black hole to the line-emitting gas. K-shell absorption edges due to Fe, Ca, and S are detected. Elemental abundances are constrained via the fluorescent lines strengths, absorption edge depths and the diffuse plasma emission lines. The high metallicity ([Fe/H]=+0.l) of the circumnuclear material compared to that in the metal-poor outer halo suggests that the accreting material could not have originated in the outer halo unless enrichment by local star formation has occurred. Relative abundances are consistent with enrichment from Type II and Ia supernovae.

Markowitz, A.↗

DOE OSTI2020

Exciton valley depolarization in monolayer transition-metal dichalcogenides

The valley degree of freedom is a sought-after quantum number in monolayer transition-metal dichalcogenides. Similar to optical spin orientation in semiconductors, the helicity of absorbed photons can be relayed to the valley (pseudospin) quantum number of photoexcited electrons and holes. Also similar to the quantum-mechanical spin, the valley quantum number is not a conserved quantity. Valley depolarization of excitons in monolayer transition-metal dichalcogenides due to long-range electron-hole exchange typically takes a few ps at low temperatures. Exceptions to this behavior are monolayers MoSe 2 and MoTe 2 wherein the depolarization is much faster. Here, we elucidate the enigmatic anomaly of these materials, finding that it originates from Rashba-induced coupling of the dark and bright exciton branches next to their degeneracy point. When photoexcited excitons scatter during their energy relaxation between states next to the degeneracy region, they reach the light cone after losing the initial helicity. The valley depolarization is not as fast in monolayers WSe 2 , WS 2 , and MoS 2 , wherein the degeneracy is absent resulting in negligible Rashba-induced coupling between bright and dark excitons.

25 ENERGY STORAGE↗

NASA NTRS2012

Intercomparison of MODIS Albedo Retrievals and In Situ Measurements Across the Global FLUXNET Network

Surface albedo is a key parameter in the Earth's energy balance since it affects the amount of solar radiation directly absorbed at the planet surface. Its variability in time and space can be globally retrieved through the use of remote sensing products. To evaluate and improve the quality of satellite retrievals, careful intercomparisons with in situ measurements of surface albedo are crucial. For this purpose we compared MODIS albedo retrievals with surface measurements taken at 53 FLUXNET sites that met strict conditions of land cover homogeneity. A good agreement between mean yearly values of satellite retrievals and in situ measurements was found (R(exp 2)= 0.82). The mismatch is correlated to the spatial heterogeneity of surface albedo, stressing the relevance of land cover homogeneity when comparing point to pixel data. When the seasonal patterns of MODIS albedo is considered for different plant functional types, the match with surface observation is extremely good at all forest sites. On the contrary, in non-forest sites satellite retrievals underestimate in situ measurements across the seasonal cycle. The mismatch observed at grasslands and croplands sites is likely due to the extreme fragmentation of these landscapes, as confirmed by geostatistical attributes derived from high resolution scenes.

Cescatti, Alessandro↗

DOE OSTI2022

Techno-Economic Implications of Electrical Machine Scaling for Wave Energy Converters: Preprint

The sizing of an electrical machine for a Wave Energy Converter (WEC) can have a substantial impact on the overall sizing, cost, and rating of the device. An electrical generator is typically part of the power take-off (PTO) system, which is the mechanism by which the energy absorbed by the prime mover is transformed into useable electrical. For practically all WECs, the rate of change of actuation is predominantly determined by the wave resource (i.e., the wave height and frequency) and devices will see a sinusoidally varying velocity according to the wave conditions. The same can then be said for both directly and indirectly coupled PTOs with electrical generators. This techno-economic study investigates electrical machine scaling and associated cost implications through core machine design theory, manufacturer data, supporting literature, and the DOE sponsored Reference Model Project (RMP). The RMP was a partnered effort to develop open-source marine energy (ME) point designs as reference models (RMs) to benchmark ME technology performance and costs, methods for design and analysis of ME technologies, estimations for capital costs, operational costs, and levelized costs of energy (LCOE). The results from this study show torque is directly related to (1) the physical size of the machine required to increase the airgap sheer stresses, (2) the amount of active material, (3) the support structure, (4) bearing size and rating, and (5) offshore cable rating, all of which have a significant effect on overall system costs in terms of both CAPEX and OPEX. This paper aims to be a critical benchmark in helping determine an “optimal” nameplate rating for wave energy devices and their associated PTO. With an optimized rating and sizing process, WEC costs can be reduced, and overall performance can be improved.

cables↗

DOE OSTI2022

Techno-Economic Implications of Electrical Machine Scaling for Wave Energy Converters

The sizing of an electrical machine for a Wave Energy Converter (WEC) can have a substantial impact on the overall sizing, cost, and rating of the device. An electrical generator is typically part of the power take-off (PTO) system, which is the mechanism by which the energy absorbed by the prime mover is transformed into useable electrical. For practically all WECs, the rate of change of actuation is predominantly determined by the wave resource (i.e., the wave height and frequency) and devices will see a sinusoidally varying velocity according to the wave conditions. The same can then be said for both directly and indirectly coupled PTOs with electrical generators. This techno-economic study investigates electrical machine scaling and associated cost implications through core machine design theory, manufacturer data, supporting literature, and the DOE sponsored Reference Model Project (RMP). The RMP was a partnered effort to develop open-source marine energy (ME) point designs as reference models (RMs) to benchmark ME technology performance and costs, methods for design and analysis of ME technologies, estimations for capital costs, operational costs, and levelized costs of energy (LCOE). The results from this study show torque is directly related to (1) the physical size of the machine required to increase the airgap sheer stresses, (2) the amount of active material, (3) the support structure, (4) bearing size and rating, and (5) offshore cable rating, all of which have a significant effect on overall system costs in terms of both CAPEX and OPEX. This paper aims to be a critical benchmark in helping determine an “optimal” nameplate rating for wave energy devices and their associated PTO. With an optimized rating and sizing process, WEC costs can be reduced, and overall performance can be improved.

cables↗

DOE OSTI2026

Galactic Rain: Cool Gas Inflows in Red Geyser Galaxies and Their Connection to Active Galactic Nuclei Activity and Interactions

Red geysers are a population of massive (logM/M ⊙ ~ 10.5), quiescent galaxies with large-scale but weak, bisymmetric ionized gas outflows, interpreted as signatures of ongoing, low-level active galactic nucleus (AGN) feedback. We investigate the kinematics and prevalence of cool (T ∼ 100–1000 K) neutral gas traced by Na I D absorption, and its connection to galaxy environment and AGN activity. Using 140 red geyser galaxies from the Sloan Digital Sky Survey-IV Mapping Nearby Galaxies at Apache Point Observatory (or MaNGA), we measure spatially resolved velocities and dispersions via double-Gaussian fits to the Na I D doublet. We find that ∼70% of the cool gas is inflowing, with a median velocity of ∼47 km s −1 (∼10% of the expected freefall velocity), and that it also exhibits kinematically ordered motions with σ NaD /σ* ∼ 0.4. Additionally, the Na I D absorption is more prevalent in red geysers than in a matched control sample, with a higher detection fraction (63% versus 40%) and reservoir areas ∼1.6 times larger. Acceleration (∼1 Myr) and accretion (∼20 Myr) timescales indicate that the Na I D-absorbing clouds are likely young and short-lived. Another intriguing result is that radio-detected red geysers (30% of the sample) show inflowing gas reservoirs ∼7 times larger than in non-radio systems. Similarly, galaxies subject to environmental effects host inflowing gas reservoirs ∼2.7 times larger than isolated red geysers. We take this as evidence that galaxy environments play a key role in replenishing the cool gas reservoirs of red geysers, fueling central AGN activity, sustaining radio emission, and regulating long-term quiescence. These findings reveal that quiescent systems are governed by cycles of inflow, feedback, and regulation.

Moghni, Arian [Univ. of California, Santa Cruz, CA↗

NASA NTRS2006

The Exploration Water Recovery System

The Exploration Water Recovery System is designed towards fulfillment of NASA s Vision for Space Exploration, which will require elevation of existing technologies to higher levels of optimization. This new system, designed for application to the Exploration infrastructure, presents a novel combination of proven air and water purification technologies. The integration of unit operations is modified from that of the current state-of-the-art water recovery system so as to optimize treatment of the various waste water streams, contaminant loads, and flow rates. Optimization is achieved primarily through the removal of volatile organic contaminants from the vapor phase prior to their absorption into the liquid phase. In the current state-of-the-art system, the water vapor in the cabin atmosphere is condensed, and the volatile organic contaminants present in that atmosphere are absorbed into the aqueous phase. Removal of contaminants the5 occurs via catalytic oxidation in the liquid phase. Oxidation kinetics, however, dictate that removal of volatile organic contaminants from the vapor phase can inherently be more efficient than their removal from the aqueous phase. Taking advantage of this efficiency reduces the complexity of the water recovery system. This reduction in system complexity is accompanied by reductions in the weight, volume, power, and resupply requirements of the system. Vapor compression distillation technology is used to treat the urine, condensate, and hygiene waste streams. This contributes to the reduction in resupply, as incorporation of vapor compression distillation technology at this point in the process reduces reliance on the expendable ion exchange and adsorption media used in the current state-of-the-art water recovery system. Other proven technologies that are incorporated into the Exploration Water Recovery System include the Trace Contaminant Control System and the Volatile Removal Assembly.

ORourke, Mary Jane E.↗

NASA NTRSDate not supplied

To Biocide or not to Biocide? Exploring the "No Biocide" Option in Spacecraft Potable Water Systems

Residual biocide has been used to protect against microbial growth in spacecraft potable water systems since the Gemini program. Iodine, the biocide currently used on the International Space Station (ISS) has a long history of use but presents a few challenges for exploration: it must be removed using a consumable absorbent before crew consumption and is known to lose its biocidal concentration due to interactions with wetted components, especially during periods of dormancy. Biocidal silver is being considered for exploration missions as it is safe for crew consumption, but it too has challenges with proper material design to maintain sufficient disinfection residuals. An idea proposed by some in the Environmental Control and Life Support System (ECLSS) community has been that the biocide does not provide a true barrier against microbial growth, and therefore, perhaps the challenges of maintaining a residual biocide in the system could be best overcome by removing the biocide altogether. In this argument, they point to the regenerative water treatment system on the ISS which produces high purity water that theoretically meets the microbiological requirements before the iodine is added. Exploration water processing systems are expected to have similar water processing capabilities. This paper will discuss the role that residual biocide may play in controlling microbial growth and presents perspectives on the potential risks associated with removing it from exploration water systems.

biocide↗

NASA NTRSDate not supplied

To Biocide or not to Biocide? Exploring the "No Biocide" Option in Spacecraft Potable Water Systems

Residual biocide has been used to protect against microbial growth in spacecraft potable water systems since the Gemini program. Iodine, the biocide currently used on the International Space Station (ISS) has a long history of use but presents a few challenges for exploration: it must be removed using a consumable absorbent before crew consumption and is known to lose its biocidal concentration due to interactions with wetted components, especially during periods of dormancy. Biocidal silver is being considered for exploration missions as it is safe for crew consumption, but it too has challenges with proper material design to maintain sufficient disinfection residuals. An idea proposed by some in the Environmental Control and Life Support System (ECLSS) community has been that the biocide does not provide a true barrier against microbial growth, and therefore, perhaps the challenges of maintaining a residual biocide in the system could be best overcome by removing the biocide altogether. In this argument, they point to the regenerative water treatment system on the ISS which produces high purity water that theoretically meets the microbiological requirements before the iodine is added. Exploration water processing systems are expected to have similar water processing capabilities. This paper will discuss the role that residual biocide may play in controlling microbial growth and presents perspectives on the potential risks associated with removing it from exploration water systems.

biocide↗

NASA NTRSDate not supplied

To Biocide or Not to Biocide? Exploring the "No Biocide" Option in Spacecraft Potable Water Systems

Residual biocide has been used to protect against microbial growth in spacecraft potable water systems since the Gemini program. Iodine, the biocide currently used on the International Space Station (ISS) has a long history of use but presents a few challenges for exploration: it must be removed using a consumable absorbent before crew consumption and is known to lose its biocidal concentration due to interactions with wetted components, especially during periods of dormancy. Biocidal silver is being considered for exploration missions as it is safe for crew consumption, but it too has challenges with proper material design to maintain sufficient disinfection residuals. An idea proposed by some in the Environmental Control and Life Support System (ECLSS) community has been that the biocide does not provide a true barrier against microbial growth, and therefore, perhaps the challenges of maintaining a residual biocide in the system could be best overcome by removing the biocide altogether. In this argument, they point to the regenerative water treatment system on the ISS which produces high purity water that theoretically meets the microbiological requirements before the iodine is added. Exploration water processing systems are expected to have similar water processing capabilities. This paper will discuss the role that residual biocide may play in controlling microbial growth and presents perspectives on the potential risks associated with removing it from exploration water systems.

biocide↗

NASA NTRSDate not supplied

To Biocide or Not to Biocide? Exploring the "No Biocide" Option in Spacecraft Potable Water Systems

Residual biocide has been used to protect against microbial growth in spacecraft potable water systems since the Gemini program. Iodine, the biocide currently used on the International Space Station (ISS) has a long history of use but presents a few challenges for exploration: it must be removed using a consumable absorbent before crew consumption and is known to lose its biocidal concentration due to interactions with wetted components, especially during periods of dormancy. Biocidal silver is being considered for exploration missions as it is safe for crew consumption, but it too has challenges with proper material design to maintain sufficient disinfection residuals. An idea proposed by some in the Environmental Control and Life Support System (ECLSS) community has been that the biocide does not provide a true barrier against microbial growth, and therefore, perhaps the challenges of maintaining a residual biocide in the system could be best overcome by removing the biocide altogether. In this argument, they point to the regenerative water treatment system on the ISS which produces high purity water that theoretically meets the microbiological requirements before the iodine is added. Exploration water processing systems are expected to have similar water processing capabilities. This paper will discuss the role that residual biocide may play in controlling microbial growth and presents perspectives on the potential risks associated with removing it from exploration water systems.

biocide↗

DOE OSTI2022

To grind or not to grind? The influence of mechanical and thermal treatments on the $\mathrm{Cu/Zn}$ disorder in $\mathrm{Cu}$ 2 $\mathrm{ZnSn}$($\mathrm{S}$ x $\mathrm{Se}$ 1-x ) 4 monograins

We report that Kesterite-type based thin film solar cell technologies are mainly based on polycrystalline absorber layers. A promising low cost alternative technology uses Cu 2 ZnSn(S x Se 1-x ) 4 (CZTSSe) monograins (single crystals of 20–100 μm size) which are fixed in a polymer matrix to form a flexible solar cell. The Cu/Zn disorder is discussed as a possible reason for band tailing causing voltage losses limiting the efficiency of CZTSSe-based devices. The experimental determination of the order parameter Q which is a quantitative measure of Cu/Zn disorder, requires a differentiation between the isoelectronic cations Cu + and Zn 2+ . An in-depth analysis of neutron diffraction data allows the determination of type and concentration of intrinsic point defects including a distinction between Cu and Zn. Neutron diffraction requires large sample volumes, thus monograins offer the unique possibility to correlate structural disorder in CZTSSe with device performance parameters. In this study we tackle the influence of grinding the monograins on stoichiometry deviations, the Cu/Zn disorder as well as intrinsic point defects and optoelectronic properties of CZTSSe monograins. Moreover, an easy methodology based on Raman scattering spectroscopy is proposed for the assessment of Cu/Zn disorder in the CZTSSe compounds.

14 SOLAR ENERGY↗

NASA NTRS2003

A New Look into the Effect of Large Drops on Radiative Transfer Process

Recent studies indicate that a cloudy atmosphere absorbs more solar radiation than any current 1D or 3D radiation model can predict. The excess absorption is not large, perhaps 10-15 W/sq m or less, but any such systematic bias is of concern since radiative transfer models are assumed to be sufficiently accurate for remote sensing applications and climate modeling. The most natural explanation would be that models do not capture real 3D cloud structure and, as a consequence, their photon path lengths are too short. However, extensive calculations, using increasingly realistic 3D cloud structures, failed to produce photon paths long enough to explain the excess absorption. Other possible explanations have also been unsuccessful so, at this point, conventional models seem to offer no solution to this puzzle. The weakest link in conventional models is the way a size distribution of cloud particles is mathematically handled. Basically, real particles are replaced with a single average particle. This "ensemble assumption" assumes that all particle sizes are well represented in any given elementary volume. But the concentration of larger particles can be so low that this assumption is significantly violated. We show how a different mathematical route, using the concept of a cumulative distribution, avoids the ensemble assumption. The cumulative distribution has jumps, or steps, corresponding to the rarer sizes. These jumps result in an additional term, a kind of Green's function, in the solution of the radiative transfer equation. Solving the cloud radiative transfer equation with the measured particle distributions, described in a cumulative rather than an ensemble fashion, may lead to increased cloud absorption of the magnitude observed.

Marshak, Alexander↗

NASA NTRS1992

Development of high resolution imaging detectors for x ray astronomy

This final report summarizes our past activities and discusses the work performed over the period of 1 April 1990 through 1 April 1991 on x-ray optics, soft x-ray (0.1 - 10 KeV) imaging detectors, and hard x-ray (10 - 300 KeV) imaging detectors. If microchannel plates (MCPs) can be used to focus x-rays with a high efficiency and good angular resolution, they will revolutionize the field of x-ray optics. An x-ray image of a point source through an array of square MCP pores compared favorably with our ray tracing model for the MCP. Initial analysis of this image demonstrates the feasibility of MCPs for soft x-rays. Our work continues with optimizing the performance of our soft x-ray MCP imaging detectors. This work involves readout technology that should provide improved MCP readout devices (thin film crossed grid, curved, and resistive sheets), defect removal in MCPs, and photocathode optimization. In the area of hard x-ray detector development we have developed two different techniques for producing a CsI photocathode thickness of 10 to 100 microns, such that it is thick enough to absorb the high energy x-rays and still allow the photoelectrons to escape to the top MCP of a modified soft x-ray imaging detector. The methods involve vacuum depositing a thick film of CsI on a strong back, and producing a converter device that takes the place of the photocathode.

Murray, S. S.↗

NASA NTRS1994

Consequences of impacts of small asteroids and comets with Earth

The fragmentation of a small asteroid in the atmosphere greatly increases its cross sections for aerodynamic braking and energy dissipation. At a typical impact velocity of 22 km/s, the atmosphere absorbs more than half the kinetic energy of stony meteoroids with diameters, D(sub m), less than 220 m and iron meteoroids with D(sub m) less than 80 m. The corresponding diameter for comets with impact velocity 50 km/s is D(sub m) less than 1600 m. Most of the atmospheric energy dissipation occurs in a fraction of a scale height, so large meteors appear to 'explode' or 'flare' at the end of their visible paths. This dissipation of energy in the atmosphere protects the earth from direct impact damage (e.g., craters), but it produces a blast wave that can do considerable damage. The area of destruction around the impact point in which the over-pressure in the blast wave exceeds 4 lb/sq in = 2.8 x 10(exp 5) dynes/cu cm, which is enough to knock over trees and destroy buildings, increases rapidly from zero for chondritic meteoroids less than 56 m in diameter (15 megatons) to about 200 sq km for those 80 m in diameter (48 megatons); the probable diameter of the tunguska impactor of 1908 is about 80 m. Crater formation and earthquakes are not significant in land impacts by stony asteroids less than about 200 m in diameter because of the air protection. A tsunami is probably the most devastating type of damage for asteroids 200 m to 1 km in diameter. An impact by an asteroid this size anywhere in the Atlantic would devastate coastal areas on both sides of the ocean. An asteroid a few kilometers across would produce a tsunami that would reach the foothills of the Appalachian Mountains in the upper half of the East Coast of the United States. Most of Florida is protected from a tsunami by the gradual slope of the ocean off its coast, which causes most of the tsunami energy to be reflected back into the Atlantic. The atmosphere plume produced by asteroids with diameters exceeding about 120 m cannot be contained by the atmosphere, so this bubble of high-temperature gas forms a new layer on top of the atmosphere. The dust entrapped in this hot gas is likely to have optical depths exceeding tau = 10 for asteroids with diameters exceeding about 0.5 to 1 km. The optical flux from asteroids 60 m or more in diameter is enough to ignite pine forests. However, the blast wave from an impacting asteroid goes beyond the radius in which the fire starts. The blast wave tends to blow out the fire, so it is likely that the impact will char the forest, as at Tunguska, but the impact will not produce a sustained fire. Because comets dissipate their energy much higher in the atmosphere than asteroids, they illuminate a much larger region and their blast wave is weaker. So they are much more effective in producing large fires. This suggests that the KT impactor was a comet rather than an asteroid.

Hills, J. G.↗

DOE OSTI2024

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab) 3 ](PF 6 ) 2 , where dab is 4,4′-dicarbaldehyde-2,2′-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH 3 CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M –1 cm –1 ) and an infrared (IR) band at 1712 cm –1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕ PL = 0.048, and an excited state lifetime, τ ο = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, k r = 9.1 × 10 4 s –1 and knr = 1.8 × 10 6 s –1 . Pulsed visible light excitation yielded transient UV–vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH 3 CN solution with 0.1 M TBAPF 6 electrolyte revealed a quasi-reversible oxidation, E°(Ru III/II ) = +1.25 V vs. Fc +/0 , and three sequential one-electron reductions at −1.10, −1.25, and −1.54 V vs. Fc +/0 . Here, an excited state reduction potential of E°(Ru *2+/+ ) = +0.89 V vs. Fc +/0 was estimated with the Rehm–Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD 3 CN solution of [Ru(dab) 3 ](PF 6 ) 2 resulted in significant shifts in the aldehyde H atom and 3,3′-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which K eq = 460 M –1 was extracted, increasing to 5800 M –1 when the solvent was changed to acetone-d 6 . Iodide titrations resulted in a significant quenching of the [Ru(dab) 3 ] *2+ lifetime and quantum yield in both CH 3 CN and acetone solvents. In CH 3 CN, the quenching was mainly dynamic and well described by the Stern–Volmer model, from which a quenching rate constant, k q , of 4.5 × 10 10 M –1 s –1 and an equilibrium constant, K eq , of 8.3 × 10 3 M –1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a K eq of 1.2 × 10 4 M –1 and a higher k q of 9.2 × 10 10 M –1 s –1 .

Aldehydes↗

NASA NTRS1989

The correlated-k method for radiation calculations in nonhomogeneous atmospheres

The accuracy of the correlated-k method, which is a technique for radiation calculations with spectrally averaged data in nonhomogeneous atmospheres, is investigated. Comparisons are made for scattering and absorbing atmospheres containing CO2, H2O, and O3, and it is concluded that: (1) the errors in correlated-k are generally of order of magnitude 1 percent, (2) much larger errors occur only when a radiative quantity is very much smaller than its average value, (3) errors do not depend systematically on the gas molecule, the distributions of gases and aerosols, or on the aerosol optical properties, and (4) errors do not systematically increase with the order of differencing. It is shown that the multiplication property for transmission by overlapping bands can be incorporated into correlated-k, that temperature effects can be interpolated on a coarse grid, and that 10 quadrature points are often sufficient to average over complex spectral intervals containing thousands of lines.

Goody, Richard↗