Methanol and ethanol electro-oxidation on Pt-SnO(2) and Pt-Ta(2)O(5) sol-gel-modified boron-doped diamond surfaces

The search for more efficient anode catalyst than platinum to be used in direct alcohol fuel cell systems is an important challenge. In this study, boron-doped diamond film surfaces were modified with Pt, Pt-SnO(2) and Pt-Ta(2)O(5) nano-crystalline deposits by the sol-gel method to study the methanol and ethanol electro-oxidation reactions in acidic medium. Electrochemical experiments carried out in steady-state conditions demonstrate that the addition of SnO(2) to Pt produces a very reactive electrocatalyst that possibly adsorbs and/or dissociate ethanol more efficiently than pure Pt changing the onset potential of the reaction by 190 mV toward less positive potentials. Furthermore, the addition of Ta(2)O(5) to Pt enhances the catalytic activity toward the methanol oxidation resulting in a negative shift of the onset potential of 170 mV. These synergic effects indicate that the addition of these co-catalysts inhibits the poisoning effect caused by strongly adsorbed intermediary species. Since the SnO(2) catalyst was more efficient for ethanol oxidation, it could probably facilitate the cleavage of the C-C bond of the adsorbed intermediate fragments of the reaction. (C) 2009 Elsevier B.V. All rights reserved.

O enigmático problema das gigantes ricas em Lítio e as perspectivas com o satélite Kepler

Lithium (Li) is a chemical element with atomic number 3 and it is among the lightest known elements in the universe. In general, the Lithium is found in the nature under the form of two stable isotopes, the 6Li and 7Li. This last one is the most dominant and responds for about 93% of the Li found in the Universe. Due to its fragileness this element is largely used in the astrophysics, especially in what refers to the understanding of the physical process that has occurred since the Big Bang going through the evolution of the galaxies and stars. In the primordial nucleosynthesis in the Big Bang moment (BBN), the theoretical calculation forecasts a Li production along with all the light elements such as Deuterium and Beryllium. To the Li the BNB theory reviews a primordial abundance of Log log ǫ(Li) =2.72 dex in a logarithmic scale related to the H. The abundance of Li found on the poor metal stars, or pop II stars type, is called as being the abundance of Li primordial and is the measure as being log ǫ(Li) =2.27 dex. In the ISM (Interstellar medium), that reflects the current value, the abundance of Lithium is log ǫ(Li) = 3.2 dex. This value has great importance for our comprehension on the chemical evolution of the galaxy. The process responsible for the increasing of the primordial value present in the Li is not clearly understood until nowadays. In fact there is a real contribution of Li from the giant stars of little mass and this contribution needs to be well streamed if we want to understand our galaxy. The main objection in this logical sequence is the appearing of some giant stars with little mass of G and K spectral types which atmosphere is highly enriched with Li. Such elevated values are exactly the opposite of what could happen with the typical abundance of giant low mass stars, where convective envelops pass through a mass deepening in which all the Li should be diluted and present abundances around log ǫ(Li) ∼1.4 dex following the model of stellar evolution. In the Literature three suggestions are found that try to reconcile the values of the abundance of Li theoretical and observed in these rich in Li giants, but any of them bring conclusive answers. In the present work, we propose a qualitative study of the evolutionary state of the rich in Li stars in the literature along with the recent discovery of the first star rich in Li observed by the Kepler Satellite. The main objective of this work is to promote a solid discussion about the evolutionary state based on the characteristic obtained from the seismic analysis of the object observed by Kepler. We used evolutionary traces and simulation done with the population synthesis code TRILEGAL intending to evaluate as precisely as possible the evolutionary state of the internal structure of these groups of stars. The results indicate a very short characteristic time when compared to the evolutionary scale related to the enrichment of these stars

Mechanistic insights into the reaction between VO2+ and propene based on a DFT study

Calculations based on density functional theory have been carried out to investigate the free energy profiles at singlet and triplet electronic states associated with the gas-phase ion/molecule reactions of VO2++ ((1)A(1)/(3)A) with propene. The complex potential energy Surfaces, including Six reaction pathways (three dehydrogenation and three oxygen transfer processes), have been explored and analyzed. Along dehydrogenation reactive channels, three final products can be obtained: V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and allene (path Dehl), being the most kinetically and thermodynamically favorable reaction pathway, V(OH)(2)(+) ((1)Sigma(+)/(3)Sigma(-)) and propyne (path Deh2),and VO2+ ((1)A(1)/(3)A) and H-2 plus allene (path Deh3). The oxyoenation processes can yield its final products Vo(+) ((1)Delta/(3)Sigma) and acetone (path Ox1), VO+ ((1)Delta/(3)Sigma 2) and propanaldehyde (path Ox2), and VO+ ((1)Delta/(3)Sigma) and H-2 and propenaldehyde (path Ox3). Both paths Deh1 and Deh2 are associated with two consecutive hydrogen transfer processes from carbon atoms of the propene fragment to vanadyl oxygen atoms, while in path Deh3 the second hydrogen migration takes place to the vanadiurn atorn followed by the formation ola hydrogen molecule. Both paths Ox1 and Ox2 comprise an intramolecular hydrogen transfer between the ethylenic moiety of the propene fragment, while two consecutive hydrogen transfer processes take place from the propene fragment to oxygen and vanadium atoms of the vanadyl moiety along path Ox3. Three crossing points between both electronic states take place along path Deh1 (CP-Deh1) and path Deh2 (CP-Deh2) and in the entrance channel of oxidation processes (CP-Ox). A comparison with previous works on related reactions VO2+ + C2H4, VO2 + C2H6, and VO2+ + C3H8 allows us to rationalize the different reactivity patterns.

Desenvolvimento de um método simples, limpo e rápido para a determinação de fluoroquinolonas em formulações farmacêuticas

Pós-graduação em Química - IQ

The influence of different co-catalysts in Pt-based ternary and quaternary electro-catalysts on the electro-oxidation of methanol and ethanol in acid media

One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

Exploring the intrinsic polar [4?+?2+] cycloaddition reactivity of gaseous carbosulfonium and carboxonium ions

Gas-phase reactions of model carbosulfonium ions (CH3-S+?=?CH2; CH3CH2-S+?=?CH2 and Ph-S+?=?CH2) and an O-analogue carboxonium ion (CH3-O+?=?CH2) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311?G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4?+?2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S-analogues, CH3-O+?=?CH2 (as well as C2H5-O+?=?CH2 and Ph-O+?=?CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2?=?CH-O+?=?CH2 ion forms an abundant [4?+?2+] cycloadduct with isoprene, but similar to the behavior of such alpha,beta-unsaturated carboxonium ions in solution, seems to occur across the C?=?C bond. Copyright (c) 2012 John Wiley & Sons, Ltd.

Untersuchungen zu ionenchemischen Reaktionen und Mobilitätsmessungen an schweren Elementen in einer Puffergaszelle

Untersuchungen zu ionenchemischen Reaktionen und Mobilitätsmessungen an schweren Elementen in einer Puffergaszelle Die vorgelegte Arbeit beschreibt vorbereitende Untersuchungen zu ionenchemischen Reaktionen und Mobilitätsmessungen schwerer Elemente (Z>100) in einer mit Argon gefüllten Puffergaszelle. Dazu wurden am Element Erbium (Z=68), dem chemischen Homolog von Fermium (Z=100), zunächst in einem Fourier-Transformations-Massenspektrometer (FT/MS) Reaktionen mit Sauerstoff (O₂), Methan (CH₄) und Butylen (C₄H₈) untersucht und deren Reaktionskonstanten zu k(Er+O2)=(3,6±0,3)•10^-10cm³/s, k(Er+C4H8)=(1,3±0,1)•10^-10cm³/s gemessen. Für die Reaktion Er⁺+CH₄ wurde eine Obergrenze der Reaktionskonstante von k(Er+CH4)?,3•10^-15cm³/s bestimmt. Dieselben Reaktionen wurden anschließend in einer mit 60 mbar Argon gefüllten Puffergaszelle am Tandembeschleuniger des Max-Planck-Instituts für Kernphysik in Heidelberg studiert.Das in die Zelle eingeschossene Erbium wurde nach der Thermalisierung in einem zweistufigen Laserprozess resonant ionisiert. Diese Messungen führten zu gleichen Ergebnissen wie die FT/MS-Messungen (k(Er+O2)=3,3±0,4)•10^-10cm³/s, k(Er+CH4)?2•10^-17cm³/s). Die Reaktion von Erbium mit Butylen wurde ebenfalls beobachtet, eine Reaktionskonstante konnte jedoch nicht bestimmt werden. Die Reaktion von Erbium mit Sauerstoff wurde auch mit den direkt in die Puffergaszelle eingeschossenen Ionen ohne Laserionisation untersucht. Eine reproduzierbare Reaktionskonstante konnte nicht bestimmt werden, mögliche Ursachen werden diskutiert.Aus der Driftzeit der Ionen im Puffergas können Ionenmobilitäten bestimmt werden. Dies erlaubt Rückschlüsse auf die Ionenradien und damit auch auf Bindungslängen in Molekülen. Zwischen Plutonium und Americium wurde bei einer Driftzeit von (1,88±0,01) ms ein Driftzeitunterschied von (0,07±0,02) ms gemessen und daraus eine relative Verringerung des Ionenradius von Americium gegenüber dem von Plutonium um (3,1±1,3)% bestimmt. Relativistische Rechnungen sagen für den atomaren Radius von Americium gegenüber Plutonium eine Kontraktion in gleicher Größenordnung voraus; für Ionenradien existieren zur Zeit noch keine Rechnungen. Aus den gemessenen Driftzeiten des Plutoniums von (1,85±0,01) ms und Plutoniumoxids von (2,38±0,01) ms wurde eine Zunahme des Ionenradius des Plutoniumoxids gegenüber dem Plutonium um (28±2)% bestimmt.Außerdem wurden Reaktionen von Ruthenium (Z=44) und Osmium (Z=76), beides chemische Homologe von Hassium (Z=108), mit Sauerstoff in der FT/MS-Apparatur untersucht, mit dem Ziel widersprüchliche Messungen der Reaktionskonstanten aufzuklären.

Hydrodynamical simulations of early-type galaxies: effects of galaxy shape and stellar dynamics on hot coronae

Early-Type galaxies (ETGs) are embedded in hot (10^6-10^7 K), X-ray emitting gaseous haloes, produced mainly by stellar winds and heated by Type Ia supernovae explosions, by the thermalization of stellar motions and occasionally by the central super-massive black hole (SMBH). In particular, the thermalization of the stellar motions is due to the interaction between the stellar and the SNIa ejecta and the hot interstellar medium (ISM) already residing in the ETG. A number of different astrophysical phenomena determine the X-ray properties of the hot ISM, such as stellar population formation and evolution, galaxy structure and internal kinematics, Active Galactic Nuclei (AGN) presence, and environmental effects. With the aid of high-resolution hydrodynamical simulations performed on state-of-the-art galaxy models, in this Thesis we focus on the effects of galaxy shape, stellar kinematics and star formation on the evolution of the X-ray coronae of ETGs. Numerical simulations show that the relative importance of flattening and rotation are functions of the galaxy mass: at low galaxy masses, adding flattening and rotation induces a galactic wind, thus lowering the X-ray luminosity; at high galaxy masses the angular momentum conservation keeps the central regions of rotating galaxies at low density, whereas in non-rotating models a denser and brighter atmosphere is formed. The same dependence from the galaxy mass is present in the effects of star formation (SF): in light galaxies SF contributes to increase the spread in Lx, while at high galaxy masses the halo X-ray properties are marginally sensitive to SF effects. In every case, the star formation rate at the present epoch quite agrees with observations, and the massive, cold gaseous discs are partially or completely consumed by SF on a time-scale of few Gyr, excluding the presence of young stellar discs at the present epoch.

Study of molecules of astrochemical, astrophysical and atmospheric interest by means of High - Resolution Infrared Spectroscopy

The spectroscopic investigation of the gas-phase molecules relevant for the chemistry of the atmosphere and of the interstellar medium has been performed. Two types of molecules have been studied, linear and symmetric top. Several experimental high-resolution techniques have been adopted, exploiting the spectrometers available in Bologna, Venezia, Brussels and Wuppertal: Fourier-Transform-Infrared Spectroscopy, Cavity-Ring-Down Spectroscopy, Cavity-Enhanced-Absorption Spectroscopy, Tunable-Diode-Laser Spectroscopy. Concerning linear molecules, the spectra of a number of isotopologues of acetylene, 12C2D2, H12C13CD, H13C12CD, 13C12CD2, of DCCF and monodeuterodiacetylene DC4H, have been studied, from 320 to 6800 cm-1. This interval covers bending, stretching, overtone and combination bands, the focus on specific ranges depending on the molecule. In particular, the analysis of the bending modes has been performed for 12C2D2 (450-2200 cm-1), 13C12CD2 (450-1700 cm-1), DCCF (320-850cm-1) and DC4H (450-1100 cm-1), of the stretching-bending system for 12C2D2 (450-5500 cm-1) and of the 2nu1 and combination bands up to four quanta of excitation for H12C13CD, H13C12CD and 13C12CD2 (6130-6800 cm-1). In case of symmetric top molecules, CH3CCH has been investigated in the 2nu1 region (6200-6700 cm-1), which is particularly congested due to the huge network of states affected by Coriolis and anharmonic interactions. The bending fundamentals of 15ND3 (450-2700 cm-1) have been studied for the first time, characterizing completely the bending states, v2 = 1 and v4 = 1, whereas the analysis of the stretching modes, which evidenced the presence of several perturbations, has been started. Finally, the fundamental band nu4 of CF3Br in the 1190-1220 cm-1 region has been investigated. Transitions belonging to the CF379Br and CF381Br molecules have been identified since the spectra were recorded using a sample containing the two isotopologues in natural abundance. This allowed the characterization of the v4 = 1 state for both isotopologues and the evaluation of the bromine isotopic splitting.

Microfluidic microbial fuel cell fabrication and rapid screening of electrochemically microbes

The demand for novel renewable energy sources, together with the new findings on bacterial electron transport mechanisms and the progress in microbial fuel cell design, have raised a noticeable interest in microbial power generation. Microbial fuel cell (MFC) is an electrochemical device that converts organic substrates into electricity via catalytic conversion by microorganism. It has represented a continuously growing research field during the past few years. The great advantage of this device is the direct conversion of the substrate into electricity and in the future, MFC may be linked to municipal waste streams or sources of agricultural and animal waste, providing a sustainable system for waste treatment and energy production. However, these novel green technologies have not yet been used for practical applications due to their low power outputs and challenges associated with scale-up, so in-depth studies are highly necessary to significantly improve and optimize the device working conditions. For the time being, the micro-scale MFCs show great potential in the rapid screening of electrochemically active microbes. This thesis presents how it will be possible to optimize the properties and design of the micro-size microbial fuel cell for maximum efficiency by understanding the MFC system. So it will involve designing, building and testing a miniature microbial fuel cell using a new species of microorganisms that promises high efficiency and long lifetime. The new device offer unique advantages of fast start-up, high sensitivity and superior microfluidic control over the measured microenvironment, which makes them good candidates for rapid screening of electrode materials, bacterial strains and growth media. It will be made in the Centre of Hybrid Biodevices (Faculty of Physical Sciences and Engineering, University of Southampton) from polymer materials like PDMS. The eventual aim is to develop a system with the optimum combination of microorganism, ion exchange membrane and growth medium. After fabricating the cell, different bacteria and plankton species will be grown in the device and the microbial fuel cell characterized for open circuit voltage and power. It will also use photo-sensitive organisms and characterize the power produced by the device in response to optical illumination.

Study of 3 Lambda H and 4 Lambda H in the reaction of 6 Li + 12 C at 2 A GeV

Die Produktion von Hyperkernen wurde in peripheren Schwerionenreaktionen untersucht, bei denen eine Kohlenstofffolie mit $^6$Li Projektilen mit einer Strahlenergie von $2 A$~GeV bestrahlt wurde. Es konnten klare Signale f{"{u}}r $Lambda$, $^3_{Lambda}$H, $^4_{Lambda}$H in deren jeweiligen invarianten Massenverteilungen aus Mesonenzerfall beobachtet werden.rnrnIn dieser Arbeit wird eine unabh{"{a}}ngige Datenauswertung vorgelegt, die eine Verifizierung fr"{u}herer Ergebnisse der HypHI Kollaboration zum Ziel hatte. Zu diesem Zweck wurde eine neue Track-Rekonstruktion, basierend auf einem Kalman-Filter-Ansatz, und zwei unterschiedliche Algorithmen zur Rekonstruktion sekund"{a}rer Vertices entwickelt.rn%-Rekonstruktionsalgorithmen .rnrnDie invarianten Massen des $Lambda$-Hyperon und der $^3_{Lambda}$H- und $^4_{Lambda}$H-Hyperkerne wurden mit $1109.6 pm 0.4$, $2981.0 pm 0.3$ und $3898.1 pm 0.7$~MeV$/c^2$ und statistischen Signifikanzen von $9.8sigma$, $12.8sigma$ beziehungsweise $7.3sigma$ bestimmt. Die in dieser Arbeit erhaltenen Ergebnisse stimmen mit der fr{"{u}}heren Auswertung {"{u}}berein.rnrnDas Ausbeutenverh{"{a}}ltnis der beiden Hyperkerne wurde als $N(^3_{Lambda}$H)/$N(^4_{Lambda}$H)$ sim 3$ bestimmt. Das deutet darauf hin, dass der Produktionsmechanismus f{"{u}}r Hyperkerne in Schwerionen-induzierten Reaktionen im Projektil-Rapidit{"{a}}tsbereich nicht allein durch einen Koaleszenzmechanismus beschrieben werden kann, sondern dass auch sekund{"{a}}re Pion-/Kaon-induzierte Reaktionen und Fermi-Aufbruch involviert sind.rn

Massenspektrometrische Wasserdampfmessung in der oberen Troposphäre und unteren Stratosphäre

Diese Arbeit beschreibt die Entwicklung des flugzeuggetragenen Atmosphärischen Ionisations-Massenspektrometers AIMS-H2O zur Messung von Wasserdampf in der oberen Troposphäre und unteren Stratosphäre (UTLS) und erste Flugzeugmessungen mit dem Instrument. Wasserdampf beeinflusst das Klima in der UTLS aufgrund seiner Strahlungseigenschaften und agiert als wichtiger Parameter bei der Bildung von Zirruswolken und Kondensstreifen. Deshalb sind genaue Wasserdampfmessungen für das Verständnis vieler atmosphärischer Prozesse unerlässlich. Instrumentenvergleiche wie sie im SPARC Report No. 2 und dem Bericht der AUQAVIT Kampagne zusammengefasst sind, haben gezeigt, dass große Abweichungen zwischen einzelnen Methoden und Instrumenten bestehen. Diese Unsicherheiten limitieren das Verständnis des Einflusses von Wasserdampf auf die Dynamik und die Strahlungseigenschaften in der UTLS. Die in dieser Arbeit vorgestellte Entwicklung einer neuen Messmethode für Wasserdampf mit dem Massenspektrometer AIMS-H2O ist deshalb auf die genaue Messung niedriger Wasserdampfkonzentrationen in der UTLS fokussiert. Mit AIMS H2O wird Umgebungsluft in einer neu entwickelten Gasentladungsquelle ionisiert. Durch eine Reihe von Ionen-Molekül-Reaktionen entstehen H3O+(H2O) und H3O+(H2O)2 Ionen. Diese Ionen werden genutzt, um die Wasserdampfkonzentration in der Atmosphäre zu bestimmen. Um die erforderliche hohe Genauigkeit zu erzielen, wird AIMS H2O im Flug kalibriert. In dem zu diesem Zweck aufgebauten Kalibrationsmodul wird die katalytische Reaktion von Wasserstoff und Sauerstoff auf einer Platinoberfläche genutzt, um definierte Wasserdampfkonzentrationen für die Kalibration im Flug zu erzeugen. Bei ersten Messungen auf der Falcon während der Kampagne CONCERT 2011 konnte dabei eine Genauigkeit von 8 bis 15% für die Messung der Wasserdampfkonzentration in einem Messbereich von 0,5 bis 250 ppmv erreicht werden. Die Messfrequenz betrug 4 Hz, was einer räumlichen Auflösung von etwa 50 m entspricht. Der Vergleich der Messung des Massenspektrometers mit dem Laserhygrometer Waran zeigt eine sehr gute Übereinstimmung im Rahmen der Unsicherheiten. Anhand zweier Fallstudien werden die Messungen von AIMS H2O während CONCERT 2011 detailliert analysiert. In der ersten Studie werden zwei Flüge in eine stratosphärische Intrusion über Nordeuropa untersucht. In dieser Situation wurde stratosphärische Luft bis hinunter auf 6 km Höhe transportiert und war dadurch mit der Falcon erreichbar. Es konnte gezeigt werden, dass AIMS-H2O sehr gut für die genaue Messung niedriger Wasserdampfkonzentrationen, in diesem Fall bis etwa 3,5 ppmv, geeignet ist. Der Vergleich der Messung mit Analysen des ECMWF Integrated Forecast Systems zeigt eine gute Übereinstimmung der gemessenen Wasserdampfstrukturen mit der dynamischen Tropopause. Unterschiede tauchen dagegen beim Vergleich der Wasserdampfkonzentrationen in der unteren Stratosphäre auf. Hier prognostiziert das Modell deutlich höhere Feuchten. Die zweite Fallstudie beschäftigt sich mit der Verteilung der relativen Feuchte in jungen Kondensstreifen im Vergleich zu ihrer direkten Umgebung. Dabei wurde für drei Messsequenzen im Abgasstrahl von Flugzeugen beobachtet, dass die relative Feuchte innerhalb des Kondensstreifens im Vergleich zur Umgebung sowohl bei unter- als auch übersättigten Umgebungsbedingungen in Richtung Sättigung verschoben ist. Die hohe Anzahl an Eispartikeln und die damit verbundene große Eisoberfläche in jungen Kondensstreifen führt also zu einer schnellen Relaxation von Gasphase und Eis in Richtung Gleichgewicht. In der Zukunft soll AIMS-H2O auch auf HALO für die genaue Messung von Wasserdampf bei ML-CIRRUS und weiteren Kampagnen eingesetzt werden.

Brown Dwarf Binaries

Nearly 500 brown dwarfs have been discovered in recent years. The majority of these brown dwarfs exist in the solar neighborhood, yet determining their fundamental properties (mass, age, temperature & metallicity) has proved to be quite difficult, with current estimates relying heavily on theoretical models. Binary brown dwarfs provide a unique opportunity to empirically determine fundamental properties, which can then be used to test model predictions. In addition, the observed binary fractions, separations, mass ratios, & orbital eccentricities can provide insight into the formation mechanism of these low-mass objects. I will review the results of various brown dwarf multiplicity studies, and will discuss what we have learned about the formation and evolution of brown dwarfs by examining their binary properties as a function of age and mass.

The Extremely Red, Young L Dwarf PSO J318.5338-22.8603: a Free-Floating Planetary-Mass Analog to Directly Imaged Young Gas-Giant Planets

We have discovered using Pan-STARRS1 an extremely red late-L dwarf, which has (J - K)(MKO) = 2.78 and (J - K) (2MASS) = 2.84, making it the reddest known field dwarf and second only to 2MASS J1207-39b among substellar companions. Near-IR spectroscopy shows a spectral type of L7 +/- 1 and reveals a triangular H-band continuum and weak alkali (K I and Na I) lines, hallmarks of low surface gravity. Near-IR astrometry from the Hawaii Infrared Parallax Program gives a distance of 24.6 +/- 1.4 pc and indicates a much fainter J-band absolute magnitude than field L dwarfs. The position and kinematics of PSO J318.5-22 point to membership in the beta Pic moving group. Evolutionary models give a temperature of 1160(-40)(+30) K and a mass of 6.5(-1.0)(+1.3) M-Jup, making PSO J318.5-22 one of the lowest mass free-floating objects in the solar neighborhood. This object adds to the growing list of low-gravity field L dwarfs and is the first to be strongly deficient in methane relative to its estimated temperature. Comparing their spectra suggests that young L dwarfs with similar ages and temperatures can have different spectral signatures of youth. For the two objects with well constrained ages (PSO J318.5-22 and 2MASS J0355+11), we find their temperatures are approximate to 400 K cooler than field objects of similar spectral type but their luminosities are similar, i.e., these young L dwarfs are very red and unusually cool but not "underluminous." Altogether, PSO J318.5-22 is the first free-floating object with the colors, magnitudes, spectrum, luminosity, and mass that overlap the young dusty planets around HR 8799 and 2MASS J1207-39

Infrared Parallaxes of Young Field Brown Dwarfs and Connections to Directly Imaged Gas-Giant Exoplanets

We have measured high-precision infrared parallaxes with the Canada-France-Hawaii Telescope for a large sample of candidate young (approximate to 10-100 Myr) and intermediate-age (approximate to 100-600 Myr) ultracool dwarfs, with spectral types ranging from M8 to T2.5. These objects are compelling benchmarks for substellar evolution and ultracool atmospheres at lower surface gravities (i.e., masses) than most of the field population. We find that the absolute magnitudes of our young sample can be systematically offset from ordinary (older) field dwarfs, with the young late-M objects being brighter and the young/dusty mid-L (L3-L6.5) objects being fainter, especially at J band. Thus, we conclude the "underluminosity" of the young planetary-mass companions HR 8799b and 2MASS J1207-39b compared to field dwarfs is also manifested in young free-floating brown dwarfs, though the effect is not as extreme. At the same time, some young objects over the full spectral type range of our sample are similar to field objects, and thus a simple correspondence between youth and magnitude offset relative to the field population appears to be lacking. Comparing the kinematics of our sample to nearby stellar associations and moving groups, we identify several new moving group members, including the first free-floating L dwarf in the AB Dor moving group, 2MASS J0355+11. Altogether, the effects of surface gravity (age) and dust content on the magnitudes and colors of substellar objects appear to be degenerate. (C) 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim