Models of very-low-mass stars, brown dwarfs and exoplanets Allard, F.; Homeier, D.; Freytag, B.
Philosophical transactions of the Royal Society of London. Series A: Mathematical, physical, and engineering sciences,
06/2012, Letnik:
370, Številka:
1968
Journal Article
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Within the next few years, GAIA and several instruments aiming to image extrasolar planets will be ready. In parallel, low-mass planets are being sought around red dwarfs, which offer more favourable ...conditions, for both radial velocity detection and transit studies, than solar-type stars. In this paper, the authors of a model atmosphere code that has allowed the detection of water vapour in the atmosphere of hot Jupiters review recent advances in modelling the stellar to substellar transition. The revised solar oxygen abundances and cloud model allow the photometric and spectroscopic properties of this transition to be reproduced for the first time. Also presented are highlight results of a model atmosphere grid for stars, brown dwarfs and extrasolar planets.
An efficient and direct method of catalytic conversion of methane to liquid methanol and other oxygenates would be of considerable practical value. However, it remains an unsolved problem in ...catalysis, as typically it involves expensive or corrosive oxidants or reaction media that are not amenable to commercialization. Although methane can be directly converted to methanol using molecular oxygen under mild conditions in the gas phase, the process is either stoichiometric (and therefore requires a water extraction step) or is too slow and low-yielding to be practical. Methane could, in principle, also be transformed through direct oxidative carbonylation to acetic acid, which is commercially obtained through methane steam reforming, methanol synthesis, and subsequent methanol carbonylation on homogeneous catalysts. However, an effective catalyst for the direct carbonylation of methane to acetic acid, which might enable the economical small-scale utilization of natural gas that is currently flared or stranded, has not yet been reported. Here we show that mononuclear rhodium species, anchored on a zeolite or titanium dioxide support suspended in aqueous solution, catalyse the direct conversion of methane to methanol and acetic acid, using oxygen and carbon monoxide under mild conditions. We find that the two products form through independent pathways, which allows us to tune the conversion: three-hour-long batch-reactor tests conducted at 150 degrees Celsius, using either the zeolite-supported or the titanium-dioxide-supported catalyst, yield around 22,000 micromoles of acetic acid per gram of catalyst, or around 230 micromoles of methanol per gram of catalyst, respectively, with selectivities of 60-100 per cent. We anticipate that these unusually high activities, despite still being too low for commercial application, may guide the development of optimized catalysts and practical processes for the direct conversion of methane to methanol, acetic acid and other useful chemicals.
The photospheres of the coolest helium-atmosphere white dwarfs are characterized by fluidlike densities. Under those conditions, standard approximations used in model atmosphere codes are no longer ...appropriate. Unfortunately, the majority of cool He-rich white dwarfs show no spectral features, giving us no opportunities to put more elaborate models to the test. In the few cases where spectral features are observed (such as in cool DQ or DZ stars), current models completely fail to reproduce the spectroscopic data, signaling shortcomings in our theoretical framework. In order to fully trust parameters derived solely from the energy distribution, it is thus important to at least succeed in reproducing the spectra of the few coolest stars exhibiting spectral features, especially since such stars possess even less extreme physical conditions due to the presence of heavy elements. In this paper, we revise every building block of our model atmosphere code in order to eliminate low-density approximations. Our updated white dwarf atmosphere code incorporates state-of-the-art constitutive physics suitable for the conditions found in cool helium-rich stars (DC and DZ white dwarfs). This includes new high-density metal-line profiles, nonideal continuum opacities, an accurate equation of state, and a detailed description of the ionization equilibrium. In particular, we present new ab initio calculations to assess the ionization equilibrium of heavy elements (C, Ca, Fe, Mg, and Na) in a dense helium medium and show how our improved models allow us to achieve better spectral fits for two cool DZ stars, Ross 640 and LP 658-2.
The opacity of alkali atoms, most importantly of Na and K, plays a crucial role in the atmospheres of brown dwarfs and exoplanets. We present a comprehensive study of Na–H2 collisional profiles at ...temperatures from 500 to 3000 K, the temperatures prevailing in the atmosphere of brown dwarfs and Jupiter-mass planets. The relevant H2 perturber densities reach several 1019 cm−3 in hot (Teff ≳ 1500 K) Jupiter-mass planets and can exceed 1020 cm−3 for more massive or cooler objects. Accurate pressure-broadened profiles that are valid at high densities of H2 should be incorporated into spectral models. Unified profiles of sodium perturbed by molecular hydrogen were calculated in the semi-classical approach using up-to-date molecular data. New Na–H2 collisional profiles and their effects on the synthetic spectra of brown dwarfs and hot Jupiters computed with petitCODE are presented.
Atmospheric compositions can provide powerful diagnostics of formation and migration histories of planetary systems. We investigate constraints on atmospheric abundances of H2O, Na, and K, in a ...sample of transiting exoplanets using the latest transmission spectra and new H2 broadened opacities of Na and K. Our sample of 19 exoplanets spans from cool mini-Neptunes to hot Jupiters, with equilibrium temperatures between ∼300 and 2700 K. Using homogeneous Bayesian retrievals we report atmospheric abundances of Na, K, and H2O, and their detection significances, confirming 6 planets with strong Na detections, 6 with K, and 14 with H2O. We find a mass-metallicity trend of increasing H2O abundances with decreasing mass, spanning generally substellar values for gas giants and stellar/superstellar for Neptunes and mini-Neptunes. However, the overall trend in H2O abundances, from mini-Neptunes to hot Jupiters, is significantly lower than the mass-metallicity relation for carbon in the solar system giant planets and similar predictions for exoplanets. On the other hand, the Na and K abundances for the gas giants are stellar or superstellar, consistent with each other, and generally consistent with the solar system metallicity trend. The H2O abundances in hot gas giants are likely due to low oxygen abundances relative to other elements rather than low overall metallicities, and provide new constraints on their formation mechanisms. The differing trends in the abundances of species argue against the use of chemical equilibrium models with metallicity as one free parameter in atmospheric retrievals, as different elements can be differently enhanced.
We report that the addition of alkali ions (sodium or potassium) to gold on KLTL-zeolite and mesoporous MCM-41 silica stabilizes mononuclear gold in Au-O(OH)x-(Na or K) ensembles. This single-site ...gold species is active for the low-temperature (<200°C) water-gas shift (WGS) reaction. Unexpectedly, gold is thus similar to platinum in creating–O linkages with more than eight alkali ions and establishing an active site on various supports. The intrinsic activity of the single-site gold species is the same on irreducible supports as on reducible ceria, iron oxide, and titania supports, apparently all sharing a common, similarly structured gold active site. This finding paves the way for using earth-abundant supports to disperse and stabilize precious metal atoms with alkali additives for the WGS and potentially other fuel-processing reactions.
We present an analysis of 1023 DBZ/DZ(A) and 319 DQ white dwarf stars taken from the Montreal White Dwarf Database. This represents a significant increase over the previous comprehensive studies on ...these types of objects. We use new trigonometric parallax measurements from the Gaia second data release, together with photometry from the Sloan Digital Sky Survey, Pan-STARRS, Gaia, or BVRI from the literature, which allow the determination of the mass for the majority of the objects in our sample. We use the photometric and spectroscopic techniques with our recently improved model atmospheres code, which include high-density effects, to accurately determine the effective temperature, surface gravity, and heavy-element abundances for each object. We study the abundance of hydrogen in DBZ/DZ white dwarfs and the properties of the accreted planetesimals. We explore the nature of the second sequence of DQ stars using proper motions from Gaia and highlight evidence of crystallization in massive DQ stars. We also present mass distributions for both spectral types. Finally, we discuss the implications of our findings in the context of the spectral evolution of white dwarfs and provide the atmospheric parameters for each star.
While it has long been known that different types of support oxides have different capabilities to anchor metals and thus tailor the catalytic behavior, it is not always clear whether the support is ...a mere carrier of the active metal site, itself not participating directly in the reaction pathway. We report that catalytically similar single-atom-centric Pt sites are formed by binding to sodium ions through −O ligands, the ensemble being equally effective on supports as diverse as TiO2, L-zeolites, and mesoporous silica MCM-41. Loading of 0.5 wt % Pt on all of these supports preserves the Pt in atomic dispersion as Pt(II), and the Pt–O(OH) x – species catalyzes the water-gas shift reaction from ∼120 to 400 °C. Since the effect of the support is “indirect,” these findings pave the way for the use of a variety of earth-abundant supports as carriers of atomically dispersed platinum for applications in catalytic fuel-gas processing.
Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface ...active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.
Summary Background Traumatic spinal cord injury is a serious disorder in which early prediction of ambulation is important to counsel patients and to plan rehabilitation. We developed a reliable, ...validated prediction rule to assess a patient's chances of walking independently after such injury. Methods We undertook a longitudinal cohort study of adult patients with traumatic spinal cord injury, with early (within the first 15 days after injury) and late (1-year follow-up) clinical examinations, who were admitted to one of 19 European centres between July, 2001, and June, 2008. A clinical prediction rule based on age and neurological variables was derived from the international standards for neurological classification of spinal cord injury with a multivariate logistic regression model. Primary outcome measure 1 year after injury was independent indoor walking based on the Spinal Cord Independence Measure. Model performances were quantified with respect to discrimination (area under receiver-operating-characteristics curve AUC). Temporal validation was done in a second group of patients from July, 2008, to December, 2009. Findings Of 1442 patients with spinal cord injury, 492 had available outcome measures. A combination of age (<65 vs ≥65 years), motor scores of the quadriceps femoris (L3), gastrocsoleus (S1) muscles, and light touch sensation of dermatomes L3 and S1 showed excellent discrimination in distinguishing independent walkers from dependent walkers and non-walkers (AUC 0·956, 95% CI 0·936–0·976, p<0·0001). Temporal validation in 99 patients confirmed excellent discriminating ability of the prediction rule (AUC 0·967, 0·939–0·995, p<0·0001). Interpretation Our prediction rule, including age and four neurological tests, can give an early prognosis of an individual's ability to walk after traumatic spinal cord injury, which can be used to set rehabilitation goals and might improve the ability to stratify patients in interventional trials. Funding Internationale Stiftung für Forschung in Paraplegie.
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