Thermal Expansion and Response to Pressure of Double-ReO[subscript 3]-Type Fluorides NaM[superscript V]F[subscript 6] (M = Nb, Ta)
Abstract not provided
Lloyd, II, Anthony J.↗
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Results for “IV&V”
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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Co‐Doping Approach for Enhanced Electron Extraction to TiO 2 for Stable Inorganic Perovskite Solar Cells
Inorganic perovskite CsPbI 3 solar cells hold great potential for improving the operational stability of perovskite photovoltaics. However, electron extraction is limited by the low conductivity of TiO 2 , representing a bottleneck for achieving stable performance. In this study, a co‐doping strategy for TiO 2 using Nb(V) and Sn(IV), which reduces the material's work function by 80 meV compared to Nb(V) mono‐doped TiO 2 , is introduced. To gain fundamental understanding of the processes at the interfaces between the perovskite and charge‐selective layer, transient surface photovoltage measurements are applied, revealing the beneficial effect of the energetic and structural modification on electron extraction across the CsPbI 3 /TiO 2 interface. Using 2D drift‐diffusion simulations, it is found that co‐doping reduces the interface hole recombination velocity by two orders of magnitude, increasing the concentration of extracted electrons by 20%. When integrated into n–i–p solar cells, co‐doped TiO 2 enhances the projected T S80 lifetimes under continuous AM1.5G illumination by a factor of 25 compared to mono‐doped TiO 2 . This study provides fundamental insights into interfacial charge extraction and its correlation with operational stability of perovskite solar cells, offering potential applications for other charge‐selective contacts.
14 SOLAR ENERGY↗
Prediction of Redox Potentials for Ac, Th, and Pa in Aqueous Solution
Density functional theory in conjunction with small core pseudopotentials and the associated basis sets was used to calculate potentials for multiple redox couples, covering a range of oxidation states for Ac (0 to III), Th (0 to IV), and Pa (0 to V) in aqueous solution. Solvation effects were incorporated using a supermolecule-continuum approach, with 30 water molecules representing two solvation shells, and the COSMO and SMD implicit solvation models. The calculated geometries for Ac(III), Th(IV), and Pa(V) were in reasonable agreement with the available experimental data. Using the COSMO model with the B3LYP functional, the calculated redox potentials were within ± 0.2 V from experiment for most redox couples. Several pathways were explored for the Pa(V/IV) redox couple for different forms of Pa(V) and Pa(IV). Most Pa(V/IV) redox couples have very similar potentials, ranging from 0 to -0.4 V up to a pH of 1.4. At pH = 1.4, the potentials shift to values that are more negative than -0.7 V, reflecting the growing unfavorable nature of the redox process at higher pH levels. The calculated values for An(III/II) potentials were consistent with prior estimates and the available experimental data. The predicted redox potentials for An(II/I) were highly negative, as expected. For An(I/0) potentials, Th and Pa exhibited positive values, contrasting with the negative values calculated for Ac. Furthermore, the An +m /An(0) potentials agreed better with the experimental data when using the COSMO solvation model as compared to the SMD model.
Chemical calculations↗
Orbital variability in the wind of the massive X-ray binary HD 153919/4U 1700-37
A set of forty high-dispersion IUE spectra of HD 153919, the Of-type primary in the 4U 1700-37 X-ray binary system, have been examined for evidence of orbital profile variability associated with the Hatchett-McCray effect. Although the effect is negligible in the resonance lines of C IV, Si IV, and N V, some subordinate lines show clear orbital changes. The variability in the absorption profile of N IV 1718, in particular, is shown to be in agreement with model calculations. The interstellar spectrum is studied, showing that highly ionized species can be maintained by the primary's radiation field alone.
Hammerschlag-Hensberge, G.↗
Changes in the ultraviolet spectrum of the mass-losing Be star 59 Cygni
Observations of a few selected wavelength regions in the ultraviolet spectrum of the Be star 59 Cyg, obtained in 1975 November, are compared with the complete low-resolution Copernicus scan of the same star obtained in 1972 October. Changes in the spectrum between the two times are discussed and interpreted in terms of the two distinct shell episodes revealed by optical data. A wide range of ionization exists from Fe III to N V, with a range in radial velocity of approximately 1000 km/s. Changes in the Si III, Si IV, and N V absorption arising in the stellar wind show that the velocity structure of the wind may have changed, and that the ionization balance also was altered over the 3 year interim.
Marlborough, J. M.↗
Discovery of highly ionized species in the ultraviolet spectrum of Feige 24
A high-resolution ultraviolet spectrum of the nearby (90 pc) white dwarf binary Feige 24 (DA + M1-2 V) obtained with the International Ultraviolet Explorer satellite (IUE) reveals two sets of absorption features in the species C IV, Si IV, and N V. The low-velocity component (V approximately 1 km/s) arises from the local interstellar gas apparently ionized by the white dwarf. The second component, at high velocities (V approximately +83 km/s), arises in the atmosphere of the white dwarf in the Feige 24 system. The presence of this large velocity shift supplies the first strong evidence for narrow absorption cores due to high-temperature species in a white dwarf atmosphere. Observations around the orbital period will provide a direct measurement of the gravitational redshift and the mass of the white dwarf. The inferred hydrogen density is 0.008 per cu cm toward this source.
Dupree, A. K.↗
Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study
The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (Th IV O 2 , Pa IV O 2 , U IV O 2 , Pa V O 2 (OH), U V O 2 (OH), U VI O 3 , Np VI O 3 , Np VII O 3 (OH), and Pu VII O 3 (OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H 2 O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H 2 O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with An VI are a turning point in terms of favoring hydration over hydrolysis. For An VII O 3 (OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH) 7 is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. Here, the ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ultraviolet spectral morphology of the O stars - The remarkable luminosity dependence of the Si IV stellar wind effect
An extensive survey of ultraviolet O type spectra, by means of high-resolution data from the International Ultraviolet Explorer archives, shows a strong correlation between both the photospheric and stellar wind features, and the optical spectral types. In particular, the stellar wind effect in the Si IV resonance doublet displays a strong luminosity dependence which has not been completely described before: there is no effect anywhere on the main sequence, but it develops gradually through the intermediate luminosity classes into a full P Cygni profile in the supergiants. This behavior is in sharp contrast to that of the C IV and N V, which have strong P Cygni profiles throughout most of the O type domain, including the main sequence. The Si IV effect simultaneously provides a sensitive classification criterion and poses an outstanding problem for detailed astrophysical interpretation. In addition, a new emission feature at 1574 A, possibly due to N III or to N IV forbidden line, is reported.
Walborn, N. R.↗
Highly ionized atoms toward HD 93521
Results are reported from the HST High Resolution Spectrograph observations of absorption features of C IV and Si IV in the spectrum of the high-latitude O star HD 93521 (l = 183 deg; b = 62 deg). A comparison of Si IV and C IV profiles showed that the FWHM of both features is about 50 km/sec, in contrast to the 7 km/sec found for one of the several S II features. The line centers for C IV and Si IV are at v = -67 km/sec and -60 km/sec, respectively. As the interval velocity decreases from 90 to 50 km/sec, the Si IV/C IV ratio of the column density per unit velocity interval increases from about 0.2 to 0.4. The result is qualitatively consistent with a fountain model of Shapiro and Benjamin (1991) if the slower gas has cooled and recombined more than the faster gas.
Spitzer, Lyman, Jr.↗
Stellar Laboratories: New GeV and Ge VI Oscillator Strengths and their Validation in the Hot White Dwarf RE0503-289
State-of-the-art spectral analysis of hot stars by means of non-LTE model-atmosphere techniques has arrived at a high level of sophistication. The analysis of high-resolution and high-S/N spectra, however, is strongly restricted by the lack of reliable atomic data for highly ionized species from intermediate-mass metals to trans-iron elements. Especially data for the latter has only been sparsely calculated. Many of their lines are identified in spectra of extremely hot, hydrogen-deficient post-AGB stars. A reliable determination of their abundances establishes crucial constraints for AGB nucleosynthesis simulations and, thus, for stellar evolutionary theory. Aims. In a previous analysis of the UV spectrum of RE 0503-289, spectral lines of highly ionized Ga, Ge, As, Se, Kr, Mo, Sn, Te, I, and Xe were identified. Individual abundance determinations are hampered by the lack of reliable oscillator strengths. Most of these identified lines stem from Ge V. In addition, we identified Ge VI lines for the first time. We calculated Ge V and Ge VI oscillator strengths in order to reproduce the observed spectrum. Methods. We newly calculated Ge V and Ge VI oscillator strengths to consider their radiative and collisional bound-bound transitions in detail in our non-LTE stellar-atmosphere models for the analysis of the Ge IV-VI spectrum exhibited in high-resolution and high-S/N FUV (FUSE) and UV (ORFEUS/BEFS, IUE) observations of RE 0503-289. Results. In the UV spectrum of RE 0503-289, we identify four Ge IV, 37 Ge V, and seven Ge VI lines. Most of these lines are identified for the first time in any star. We can reproduce almost all Ge IV, GeV, and Ge VI lines in the observed spectrum of RE 0503-289 (T(sub eff) = 70 kK, log g = 7.5) at log Ge = -3.8 +/- 0.3 (mass fraction, about 650 times solar). The Ge IV/V/VI ionization equilibrium, that is a very sensitive T(sub eff) indicator, is reproduced well. Conclusions. Reliable measurements and calculations of atomic data are a prerequisite for stellar-atmosphere modeling. Our oscillator-strength calculations have allowed, for the first time, Ge V and Ge VI lines to be successfully reproduced in a white dwarf s (RE 0503-289) spectrum and to determine its photospheric Ge abundance.
Rauch, T.↗
Ultraviolet spectroscopy of Nova Muscae 1991
We report on a series of ultraviolet spectroscopic observations made with the IUE satellite, which sampled critical outburst stages of the soft X-ray transient Nova Muscae 1991. Continuum light curves, and a multi-epoch line analysis are presented. In addition, a single epoch optical-UV spectra obtained with the HST/FOS is discussed. The optical-UV continuum fits approximately the 'canonical' fv varies as V exp 1/3 power low expected for thermal emission from steady state accretion disk. The emission line spectrum contains prominent high ionization lines of C IV and N V. Weaker lines are seen at intermittent epochs, including some of lower ionization. The derivation of galactic reddening which has significant implications for distance estimates is discussed. Comparisons with previous SXT sources are considered.
Shrader, C. R.↗
HD 93521, zeta Ophiuchi, and the effects of rapid rotation on the atmospheres and winds of 09.5 V stars
Both low- and high-resolution IUE spectra of the rapidly rotating 09.5 V stars HD 93521 and zeta Oph are used to develop a coherent picture of the effects of rapid rotation on the atmospheres and winds of late, main-sequence O stars. The observational consequences are by far the strongest on HD 93521, most likely because it is being viewed nearly equator-on. In particular, it is shown that HD 93521 (1) a much smaller UV optical flux ratio than expected, (2) UV photospheric lines indicative of a BO supergiant, (3) an abnormally strong N v wind doublet, and (4) wind profiles suggesting that its wind has latitudinally dependent properties. Because HD 93521 has a larger observed v sin i than zeta Oph and yet its H-alpha emission is no stronger than in zeta Oph, it is speculated that zeta Oph actually rotates as fast or faster than HD 93521, but has a smaller sin i. Because zeta Oph is significantly reddened, nothing can be determined about its intrinsic UV energy distribution. However, it is shown that its UV photospheric lines are a bit peculiar and that its C IV and N V wind doublets are abnormally strong and have unusual profiles. The C IV profile agrees with models of a rotationally distorted wind similar to the one in HD 93521, except viewed at an angle i approximately 60 deg-80 deg. The spectral peculiarities of both stars are attributed to the combined effects of gravity darkening of their atmospheres and rotational distortion of their winds. The differences between their spectra are interpreted as the result of being viewed at different inclination angles. Because of the gravity darkening, atmospheric analyses of either star based on single temperature and surface gravity model atmospheres are probably unreliable. Finally, I describe how different effects conspire to make the spectroscopic signatures of gravity darkening so pronounced at 09.5 V.
Massa, Derck↗
Copernicus observations of the N v resonance doublet in 53 early-type stars
UV spectra in the wavelength interval 1170-1270 A are presented for 53 early-type stars ranging in spectral type from O6.5 V to B2.5 IV. The sample includes four Wolf-Rayet stars, seven known Oe-Be stars, and six galactic halo OB stars. A qualitative analysis of the stellar N v doublet reveals that: (1) N v is present in all stars hotter and more luminous than type B0 for the main sequence, B1 for giants, and B2 for supergiants; (2) shell components of N v and an unidentified absorption feature at 1230 A are present in about half of the stars; (3) the column density of N v is well correlated with bolometric luminosity over the spectral range O6 to B2; and (4) the ratio of emission to absorption equivalent width is a factor of 2 smaller in the main sequence stars than in supergiants, which suggests that the wind structure changes as a star evolves. For several stars, this ratio is too small to be explained by traditional wind models.
Abbott, D. C.↗
Manganese(II) complexes of 1,1'-bis[(pyridin-2-yl)methyl)]-2,2'-bipiperidine (PYBP): Synthesis, structure, catalytic properties in alkene epoxidation with hydrogen peroxide, and related mechanistic studies
In this study, several manganese(II) complexes with the stereoisomers of ligand PYBP (1,1'-bis[(pyridin-2-yl)methyl]-2,2'-bipiperidine) and different anions were prepared and characterized by X-ray diffractometry. Complex [Mn II (rac-PYBP)] 2+ (1) was found to be an efficient catalyst of alkene epoxidation by hydrogen peroxide in the presence of acetic acid in acetonitrile at room temperature. Cyclooctene was converted to its epoxide with up to 91 % yield, 99.6 % selectivity, and the turnover number of 180 within 5 min. Fast epoxidations of cyclohexene, 1-decene, styrene, and cis-stilbene were also achieved. Isomeric complex [Mn II (meso-PYBP)] 2+ (2) was catalytically inactive under the same experimental conditions. Stopped-flow spectrophotometry and freeze-quenched EPR spectra show that complex 2 is not oxidized by H 2 O 2 in the presence of acetic acid (AcOH) but instead undergoes partial ligand protonation and liberation of the Mn 2+ cations due to the relatively poor chelating ability of ligand meso-PYBP. The rac-PYBP isomer acts as a better ligand and retains the coordinated Mn center when complex 1 is treated with the H 2 O 2 /AcOH mixture in acetonitrile solution yielding a mixture of intensely colored intermediates likely involving Mn III , Mn IV , and Mn V complexes. Magnetic susceptibility measurements, UV–vis and EPR spectra suggest that dinuclear complexes [Mn III 2 (μ-O)(μ-OAc)(rac-PYBP) 2 ] 3+ and [Mn III Mn IV (μ-O) 2 (rac-PYBP) 2 ] 3+ gradually accumulate in the reaction mixture as inactivated states of the catalyst. Complex 1 also causes fast decomposition of hydrogen peroxide into O 2 gas and H 2 O, which competes with the epoxidation of alkenes and requires gradual addition of H 2 O 2 for its efficient use. The catalytic activity of complex 1 is strongly influenced by its counterions and decreases in order ClO 4 - ≈ SbF 6 - > NO 3 – > Cl - indicating that labile ligands in the coordination sphere of Mn are required for the activation of H 2 O 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
UV absorption and emission lines from highly ionized gas in the Galactic halo
The detection of highly ionized gas in the Galactic halo through UV absorption and emission lines is reported. In absorption the species under consideration include Si IV, C IV, and N V. The presence of N V absorption implies the existence of some gas with a temperature near 200,000 K. The highly ionized absorbing gas toward distant stars in direction b of less than -50 deg has simple and relatively narrow line profiles and small average LSR velocities while the gas in the direction b of greater than 50 deg reveals a complex pattern of motions with substantial inflow and outflow velocities. C IV emission brightens toward the Galactic poles and has a polar intensity of 5000 photons/sq cm s ster. In the nonequilibrium cooling of a Galactic fountain, a flow rate of 4 M sub O/yr to each side of the Galaxy is required to produce the amount of N V absorption found in the halo, while a flow rate five times larger is required to produce the observed level of C IV emission.
Savage, Blair D.↗
Experiment M-6: Bone Demineralization
Densitometric evaluations of serial radiographs of "normal" subjects have often shown rather frequent changes in bone mass within relatively short periods of time. For this reason it was decided to make two pre-flight and two post flight radiographs of the Gemini V backup crew. In comparing the changes observed preflight and post flight as the conventional os calcis scanning site between the two crews, it was found that no changes greater than 4 percent were evident in either member of the backup crew. In comparing the changes observed preflight and postflight as the conventional o calcis scanning site between the two crews, it was found that no changes greater than 4 percent were evident in either member of the backup crew. This is in contract to the 15.1 and 8.9 percent losses observed in the prime crew. It has long been known that the skeletal system experiences a general loss of mineral under immobilization or extended bed rest. However, in both Gemini IV and Gemini V studies, bone mass losses were greater in both the os calcis and phalanx than were shown by the TWU bed-rest subjects during the same period of time. Although the bone mass losses in the 8-day Gemini V flight were generally greater than in the 4-day Gemini IV flight, the information to date is still insufficient to conclude that the losses tend to progress linearly with time, or whether a form of physiological adaptation may occur in longer space flights.
Mack, Pauline B.↗
Where do flares occur in RS CVn systems? Analysis of the October 3, 1981 flare on V711 Tau = HR 1099 observed by IUE
A set of IUE observations of V711 Tau = HR 1099 (K1 IV and G2 V) in which high-resolution spectra with the SWP and LWR cameras were obtained during the luminous flare of October 3, 1981 is discussed. Multigaussian fits to the Mg II k and C IV 1548 A lines are consistent with the flare radial velocity being identical to that of the K star. Thus, the flare probably occurred on the K star. There is no evidence for flows as seen during a flare on UX Ari. The strongest emitters of UV radiation during the flare were the L alpha and Mg II lines, which emitted seven times as much energy as all the transition region lines combined. The peak luminosity of the flare in the UV emission lines is 1.5 times 10 to the 31st power ergs/sec, and the total emission in these lines during the flare was about 4 times 10 to the 35th power ergs.
Linsky, J. L.↗
Three-dimensional shock-shock interactions on the scramjet inlet
The effects of shock impingement on the inlet of a scramjet engine are investigated numerically. The impinging shock is caused by the vehicle forebody. The interaction of this forebody shock with the inlet leading edge shock results in a very complex fully three-dimensional flowfield containing local regions of high pressure and intense heating. In the present investigation, this complex flowfield is calculated by solving the thin-layer Navier-Stokes equations using a finite-volume flux splitting technique due to van Leer. For zero or small sweep angles a Type IV interaction occurs while for moderate sweep of about 25 deg, a Type V interaction occurs. Both Type IV and Type V interactions are investigated.
Singh, D. J.↗