We present results from MMT/Hectochelle spectroscopy of 390 red giant candidate stars along the line of sight to the recently discovered Galactic satellite Crater 2. Modeling the joint distribution of stellar positions, velocities, and metallicities as a mixture of Crater 2 and Galactic foreground populations, we identify similar to 62 members of Crater 2, for which we resolve a line-of-sight velocity dispersion of sigma(nu los) = 2.7(-0.3)(+0.3) km s(-1) and a. mean velocity of <nu(los)> = 87.5(-0.4)(+0.4) km s(-1) (solar rest frame). We also resolve a metallicity dispersion of sigma([Fe/H]) = 0.22(-0.03)(+0.04) dex and a mean of <[Fe/H]> = 1.98(-0.1)(+0.1) dex that is 0.28 +/- 0.14 dex poorer than estimated from photometry. Despite Crater 2's relatively large size (projected halflight radius R-h similar to 1 kpc) and intermediate luminosity (M-V similar to -8), its velocity dispersion is the coldest that has been resolved for any dwarf galaxy. These properties make Crater 2 the most extreme low-density outlier in dynamical as well as structural scaling relations among the Milky Way's dwarf spheroidals. Even so, under assumptions of dynamical equilibrium and negligible contamination by unresolved binary stars, the observed velocity distribution implies a gravitationally dominant dark matter halo, with a dynamical mass of. 4.4(-0.9)(+1.2) x 10(6) M-circle dot and a mass-to-light ratio of 53(-11)(+15) M-circle dot/L-V,L-circle dot enclosed within a radius of similar to 1 kpc, where the equivalent circular velocity is 4.3(-0.5)(+0.5) km s(-1).

We present the. Hubble Space Telescope (HST) Space Telescope Imaging Spectrograph (STIS) optical transmission spectroscopy of the cool Saturn-mass exoplanet WASP-39b from 0.29-1.025 mu m, along with complementary transit observations from Spitzer IRAC at 3.6 and 4.5 mu m. The low density and large atmospheric pressure scale height of WASP-39b make it particularly amenable to atmospheric characterization using this technique. We detect a Rayleigh scattering slope as well as sodium and potassium absorption features; this is the first exoplanet in which both alkali features are clearly detected with the extended wings predicted by cloud-free atmosphere models. The full transmission spectrum is well matched by a clear H-2-dominated atmosphere, or one containing a weak contribution from haze, in good agreement with the preliminary reduction of these data presented in Sing et al.. WASP-39b is predicted to have a pressure-temperature profile comparable to that of HD 189733b and WASP-6b, making it one of the coolest transiting gas giants observed in our HST STIS survey. Despite this similarity, WASP-39b appears to be largely cloud-free, while the transmission spectra of HD 189733b and WASP-6b both indicate the presence of high altitude clouds or hazes. These observations further emphasize the surprising diversity of cloudy and cloud-free gas giant planets in short-period orbits and the corresponding challenges associated with developing predictive cloud models for these atmospheres.

We report the observation and confirmation of the first group-and cluster-scale strong gravitational lensing systems found in Dark Energy Survey data. Through visual inspection of data from the Science Verification season, we identified 53 candidate systems. We then obtained spectroscopic follow-up of 21 candidates using the Gemini Multi-object Spectrograph at the Gemini South telescope and the Inamori-Magellan Areal Camera and Spectrograph at the Magellan/Baade telescope. With this follow-up, we confirmed six candidates as gravitational lenses: three of the systems are newly discovered, and the remaining three were previously known. Of the 21 observed candidates, the remaining 15 either were not detected in spectroscopic observations, were observed and did not exhibit continuum emission (or spectral features), or were ruled out as lensing systems. The confirmed sample consists of one group-scale and five galaxy-cluster-scale lenses. The lensed sources range in redshift z similar to 0.80-3.2 and in i-band surface brightness i(SB) similar to 23-25 mag arcsec(-2) (2 '' aperture). For each of the six systems, we estimate the Einstein radius theta(E) and the enclosed mass M-enc, which have ranges theta(E) similar to 5 ''-9 '' and M-enc similar to 8 x 10(12) to 6 x 10(13)M(circle dot), respectively.

We present a catalog of 11 multiplanet systems from Campaigns 1 and 2 of the K2 mission. We report the sizes and orbits of 26 planets split between seven two-planet systems and four three-planet systems. These planets stem from a systematic search of the K2 photometry for all dwarf stars observed by K2 in these fields. We precisely characterized the host stars with adaptive optics imaging and analysis of high-resolution optical spectra from Keck/HIRES and medium-resolution spectra from IRTF/SpeX. We confirm two planet candidates by mass detection and validate the remaining 24 candidates to >99% confidence. Thirteen planets were previously validated or confirmed by other studies, and 24 were previously identified as planet candidates. The planets are mostly smaller than Neptune (21/26 planets), as in the Kepler mission, and all have short periods (P < 50 days) due to the duration of the K2 photometry. The host stars are relatively bright (most have Kp < 12.5 mag) and are amenable to follow-up characterization. For K2-38, we measured precise radial velocities using Keck/HIRES and provide initial estimates of the planet masses. K2-38b is a short-period super-Earth with a radius of 1.55 +/- 0.16 R-circle plus, a mass of 12.0 +/- 2.9M(circle plus), and a high density consistent with an iron-rich composition. The outer planet K2-38c is a lower-density sub-Neptune-size planet with a radius of 2.42 +/- 0.29 R-circle plus and a mass of 9.9 +/- 4.6M(circle plus) that likely has a substantial envelope. This new planet sample demonstrates the capability of K2 to discover numerous planetary systems around bright stars.

Aims. The goal of this paper is to present complete radial-velocity data for the spectroscopically selected McCormick sample of nearby K-M dwarfs and, based on these and supplementary data, to determine the space-velocity distributions of late-type stars in the solar neighborhood. Methods. We analyzed nearly 3300 measurements of radial velocities for 1049 K-M dwarfs, that we obtained during the past decade with a CORAVEL-type instrument, with a primary emphasis on detecting and eliminating from kinematic calculations the spectroscopic binaries and binary candidates. Combining radial-velocity data with HIPPARCOS/Tycho-2 astrometry we calculated the space-velocity components and parameters of the galactic orbits in a three-component model potential for the stars in the sample, that we use for kinematical analysis and for the identification of possible candidate members of nearby stellar kinematic groups. Results. We present the catalog of our observations of radial velocities for 959 stars which are not suspected of velocity variability, along with the catalog of U, V, W velocities and Galactic orbital parameters for a total of 1088 K-M stars which are used in the present kinematic analysis. Of these, 146 stars were identified as possible candidate members of the known nearby kinematic groups and suspected subgroups. The distributions of space-velocity components, orbital eccentricities, and maximum distances from the Galactic plane are consistent with the presence of young, intermediate-age and old populations of the thin disk and a small fraction (similar to 3%) of stars with the thick disk kinematics. The kinematic structure gives evidence that the bulk of K-M type stars in the immediate solar vicinity represents a dynamically relaxed stellar population. The star MCC 869 is found to be on a retrograde Galactic orbit (V = -262 km s(-1)) of low inclination (4 degrees) and can be a member of stellar stream of some dissolved structure. The Sun's velocity with respect to the Local Standard of Rest, derived from the distributions of space-velocity components, is (U-circle dot, V-circle dot, W-circle dot) = (9.0 +/- 1.4, 13.1 +/- 0.6, 7.2 +/- 0.8) km s(-1). The radial solar motion derived via the Stromberg's relation, V-circle dot = 14.2 +/- 0.8 km s(-1), agrees within the errors with the value obtained directly from the V distribution of stars on nearly circular orbits.

Open clusters have been the focus of several exoplanet surveys, but only a few planets have so far been discovered. The Kepler spacecraft revealed an abundance of small planets around small cool stars, therefore, such cluster members are prime targets for exoplanet transit searches. Kepler's new mission, K2, is targeting several open clusters and star-forming regions around the ecliptic to search for transiting planets around their low-mass constituents. Here, we report the discovery of the first transiting planet in the intermediate-age (800 Myr) Beehive cluster (Praesepe). K2-95 is a faint (Kp = 15.5 mag) M3.0 +/- 0.5 dwarf from K2's Campaign 5 with an effective temperature of 3471 +/- 124 K, approximately solar metallicity and a radius of 0.402 +/- 0.050 R-circle dot. We detected a transiting planet with a radius of 3.47(-0.53)(+0.78)R(circle plus) and an orbital period of 10.134 days. We combined photometry, medium/high-resolution spectroscopy, adaptive optics/speckle imaging, and archival survey images to rule out any false-positive detection scenarios, validate the planet, and further characterize the system. The planet's radius is very unusual as M-dwarf field stars rarely have Neptune-sized transiting planets. The comparatively large radius of K2-95b is consistent with the other recently discovered cluster planets K2-25b (Hyades) and K2-33b (Upper Scorpius), indicating systematic differences in their evolutionary states or formation. These discoveries from K2 provide a snapshot of planet formation and evolution in cluster environments and thus make excellent laboratories to test differences between field-star and cluster planet populations.

Este trabalho apresenta a caracterização espectroscópica de dois conjuntos de vidros sódio aluminofosfatos co-dopados com Yb3+ e Tm3+, na região do visível e infravermelho, preparados em atmosfera de nitrogênio e ambiente. Nestas amostras, os íons de Yb3+ são empregados como doadores eficientes, da excitação em 980nm, com transferência de energia subseqüente para os íons Tm3+. Os resultados são discutidos em termos do conteúdo de OH- presentes em cada conjunto das amostras, e em função da concentração Tm2O3. As propriedades radiativas foram analisadas usando a teoria de Judd Ofelt, e empregando os resultados experimentais e teóricos, foram avaliadas as eficiências quântica das luminescências (h) dos diversos níveis. Os resultados indicam que as amostras preparadas em atmosfera do N2, com um conteúdo de OH- menor, apresentam propriedades superiores do que aquelas preparadas em atmosfera ambiente. Entre estas propriedades destacamos a transmissão no infravermelho, a qual é 30% mais extensa, as intensidades de emissão são mais elevadas, e a diminuição dos efeitos de supressão da luminescência, caracterizando-os como materiais potenciais para a geração do laser alta potência, bem com conversão ascendente de energia eficiente. Também foram estudados os processos de transferência de energia, usando os modelos teóricos de Förster, Dexter e Miyakawa, calculando-se os parâmetros de transferência de energia. Os processos principais de transferência de energia analisados foram: migração da energia entre íons de Yb3+, transferência de energia entre íons Yb3+ e Tm3+, e interações com radicais OH-. Os resultados indicam que transferência de energia Yb-Tm favorece a emissão em 1800 nm, e não há nenhuma evidência da supressão da luminescência até concentração de 2% de Tm2O3. / This work presents a throughout near-infrared and visible spectroscopic characterization of two sets of Yb3+ and Tm3+ codoped sodium aluminophosphate glasses, prepared in nitrogen and ambient atmospheres. In these samples, the Yb3+ ions are employed as efficient sensitizers of 0.98 µm excitation, with subsequent energy transfer to Tm3+ ions. Results are discussed in terms of the inferred OH- content in each set of samples, and as a function of Tm2O3 concentration. Radiative properties are analyzed using Judd Ofelt theory, and by employing experimental and theoretical data, the fluorescence quantum efficiencies h of several levels are evaluated. Results indicate that samples prepared in N2 atmosphere, with lower OH- content, present superior properties than those prepared in ambient atmosphere. Among these properties are a 30% more extensive infrared transmission of the host matrix, higher emission intensities, and decreased quenching effects, characterizing them as potential materials for high power laser generation, as well as efficient upconversion. Also the energy transfer processes were studied, by using Förster, Dexter and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion-ion energy transfer processes analyzed were: energy migration among Yb3+ ions, energy transfer between Yb3+ and Tm3+ ions, and interactions with OH- radicals.The results indicated that Yb®Tm energy transfer favors 1.8 ?m emission, and there is no evidence of concentration quenching up to 2% Tm2O3 doping.

A Terapia Fotodinâmica (TFD) é um método de tratamento do câncer e de outras doenças baseado no efeito conjunto de um composto fotoativo, luz da região visível ou infravermelho próximo e oxigênio molecular. O diagnóstico por fluorescência (DF) é uma técnica para o diagnóstico precoce de diversas doenças que consiste em utilizar algum composto fluorescente para distinguir tecido tumoral de tecido saudável. As porfirinas são amplamente utilizadas como fotossensibilizadores (FS) na TFD e como fluoróforos (FF) no DF. Os pontos quânticos (PQ) são novas nanoestruturas que possuem intenso e largo espectro de absorção na região espectral UV e visível, espectro de luminescência muito intenso e estreito e são fotoestáveis. Isso os torna promissores para o uso em TFD ou em DF, competindo com FS e FF orgânicos. A interação entre PQ e FS orgânicos pode aumentar a eficiência de ambos, devido aos processos de transferência de energia e/ou de carga. Durante o fototratamento os FS podem sofrer fototransformações, perdendo sua fotoatividade e formando produtos estáveis tóxicos. Isso torna importante o estudo da fototransformação dos FS. Neste trabalho, estudou-se, através da espectroscopia de absorção óptica, da fluorescência com resolução temporal e de flash-fotólise, a interação das porfirinas meso-tetrametil piridil (TMPyP) e meso-tetrasulfonatofenil (TPPS4) com o PQ de Telureto de Cádmio (CdTe) encapsulado com ácido 3-mercaptopropiônico (MPA) e sua fotólise individual e em conjunto. Os experimentos entre a TMPyP e o PQ mostraram que existe a formação de um complexo de transferência de carga entre a porfirina e o PQ. Verificou-se que a formação do complexo TMPyP-PQ aumenta a eficiência do processo de fotólise. A interação entre a p TPPS4 e o PQ em pH 4,0 (TPPS4 biprotonada) induz a transferência dos prótons para o PQ. A porfirina TPPS4 em pH 7,0 com adição de PQ não apresentou mudanças espectrais. Entretanto, em ambos os pHs, o PQ causava o aumento da velocidade de fotólise da TPPS4, sendo que o efeito do PQ foi maior em pH 4,0. Os resultados obtidos mostraram a importância da carga dos componentes, tanto na sua interação, como na eficiência de fotólise, devido à sua interação eletrostática. Também foi observado um aumento da intensidade da fluorescência de sistemas porfirina-PQ durante a fotólise. Esse efeito pode ser explicado pela redução da supressão da fluorescência devido à diminuição das concentrações dos componentes durante a fotólise. / The Photodynamic Therapy (PDT) is a method of treatment of cancer and other diseases based on combined effects of a photoactive compound, visible or near infrared light and molecular oxygen. The diagnosis by fluorescence (DF) is a technique for diagnostics of disease that consists in utilizing fluorescence compound to discern tumor tissue from a healthy one. Porphyrins are widely used as photosensitizer (PS) in PDT and as fluorophore (FP) in DF. Quantum dots (QD) are new nanostructures, which have intense and broad absorption spectrum in the UV and visible light region, intense and narrow luminescence spectrum and possess high photostability. They are considered promising for clinical application in PDT and/or DF, competing with organic PS and FP. Interaction between QD and organic PS can increase the efficiencies of both, due to the energy and/or charge transfer processes. The PS phototransformation during phototreatment may lead to loss of the PS photoactivity and formation of toxic products, that is important to study the processes of the PS phototransformation. In this work, with the support of absorption spectroscopy, steady state and time resolved fluorescence and flash-photolysis, we study interaction of meso-tetramethyl pyridyl (TMPyP) and meso-tetrakis sulfonatofenyl (TPPS4) porphyrins with CdTe QD functionalized with 3-mercaptopropionic acid (MPA) and their photolysis individual and in mutual. Experiments with TMPyP and QD demonstrate formation of a charge transfer complex between the porphyrin and the QD. We have verified that TMPyP-QD complex increases the efficiency of the porphyrin photolysis. The photolysis of the proper complex has been observed, as well. The interaction between TPPS4 and QD at pH 4.0 (biprotonated TPPS4) provokes deprotonation of the porphyrin via the proton transfer to QD. At pH 7.0 (deprotonated TPPS4) interaction of the porphyrin with the QD does not change TPPS4 spectral characteristics. Nevertheless, at both pHs QD cause increase in the TPPS4 photolysis rate, the effect being higher at pH 4.0. The observed results demonstrate the importance of the component charges both at their interaction and in photolysis efficiency, associated with their electrostatic interaction. The fluorescence intensity of the porphyrin-QD systems is enhanced during photolysis. This effect may be explained as the fluorescence quenching reduction due to decrease of the compound concentrations in the photolysis process.

Dehydrogenation is the catalytic process of removing hydrogen from a saturated hydrocarbon to produce an olefin. Olefins are important feedstocks for the petrochemical industry and can potentially be used to produce fuels through oligomerization. Alloys containing an active metal such as platinum and palladium and a non-catalytic metal offer improved selectivity towards the olefin. This body of work seeks to further the understanding of how heteroatomic bonds in alloys change the rate and selectivity of alloy catalysts used for dehydrogenation.In the first study, a series of Pt-V bimetallic catalysts are synthesized, which are highly selective propane dehydrogenation catalysts. The bimetallic nature of the nanoparticles was verified by in-situX-ray Absorption Spectroscopy(XAS)and the formation of the Pt3V alloy phase was shown by in-situ synchrotronX-ray Diffraction(XRD). A reduction-oxidation differenceXASmethod was used to examine the surface stoichiometry and found that a shell layer of the alloy phase forms when the particles are platinum rich. Electronic modification of Pt was studied by Pt L3edgeX-ray Absorption Near Edge Structure(XANES),X-ray Photoelectron Spectroscopy(XPS), Resonant Inelastic X-ray Scattering (RIXS)andDensity FunctionalTheory(DFT). The spectral changes observed were shown to be due to changes in the energy of the filled and unfilled 5d density of states, and not due to electron transfer. The electronic modifications cause a weakening of adsorbate binding and destabilization of deeply dehydrogenated hydrocarbons, which contributes to the dehydrogenation selectivity.In the second study, alloys between palladium and five different promoters were synthesized and tested as propane dehydrogenation catalysts.The structure ofthe alloy catalysts was characterized by in-situ XAS and in-situ synchrotron XRD.Zinc and indium form alloy structures with site isolated palladium, while gallium, iron and manganese do not. All of the alloys have improved propane dehydrogenation selectivity compared to monometallic palladium. The propylene production turnover rate of the alloys increased by almost an order of magnitude compared to monometallic Pd, but among the alloys the turnover ratesonly varied by a factor of two despite the different structures and electronic modifications inherent to each phase. The site isolated alloys had higher propylene selectivity than those that were not site isolated. The site isolated alloys showed strongerelectronic modification: both in binding strengths and in Pd projected Density of States (pDOS)by DFT than did the non-site isolated alloys. The commonly used computational selectivity descriptor for dehydrogenation, which is the difference in energy between alkene desorption and alkene C-H bond activation energy correctly predicts that the site isolated alloys will have high selectivity but shows weaker trends for alloys without site isolation. A modified selectivity descriptor, involving the C-C bond breaking barrier in the adsorbed alkyne more accurately reflects the high selectivity of the non-site isolated alloys.In a third study,RIXS and XPSare used to examine trends in the electronic modification of platinum alloys with transition metal and post transition metal promoters. All alloys show an increase in the energy transfer maximum, showing that alloying modifies energy the filled and unfilled density of states. The increase in the energy transfer maximum in platinum alloys with 3d metals islargerfor early transition metals, which by DFT show larger shifts in the d-band center. The post transition elements showsignificantlylarger shifts than to the transition elements, partially due to the lack of orbital overlap between the valence p orbitals and Pt 5d orbitals. Platinum has the same number of valence d electrons regardless of promoter or structure, and redistribution of the 5d electron energy brought about by heteroatomic bonds leads to the observed electronic modifications. The positive binding energy shifts measured by XPS reflect these energy changes, which occur due to changes in the Fermi energy of the alloy, initial state effects and intra and extra atomic relaxation (final state effects). The calculated initial state effect shift is correlated to descriptors of the valence d band, such as the d band center.

Este trabalho apresenta a caracterização espectroscópica de dois conjuntos de vidros sódio aluminofosfatos co-dopados com Yb3+ e Tm3+, na região do visível e infravermelho, preparados em atmosfera de nitrogênio e ambiente. Nestas amostras, os íons de Yb3+ são empregados como doadores eficientes, da excitação em 980nm, com transferência de energia subseqüente para os íons Tm3+. Os resultados são discutidos em termos do conteúdo de OH- presentes em cada conjunto das amostras, e em função da concentração Tm2O3. As propriedades radiativas foram analisadas usando a teoria de Judd Ofelt, e empregando os resultados experimentais e teóricos, foram avaliadas as eficiências quântica das luminescências (h) dos diversos níveis. Os resultados indicam que as amostras preparadas em atmosfera do N2, com um conteúdo de OH- menor, apresentam propriedades superiores do que aquelas preparadas em atmosfera ambiente. Entre estas propriedades destacamos a transmissão no infravermelho, a qual é 30% mais extensa, as intensidades de emissão são mais elevadas, e a diminuição dos efeitos de supressão da luminescência, caracterizando-os como materiais potenciais para a geração do laser alta potência, bem com conversão ascendente de energia eficiente. Também foram estudados os processos de transferência de energia, usando os modelos teóricos de Förster, Dexter e Miyakawa, calculando-se os parâmetros de transferência de energia. Os processos principais de transferência de energia analisados foram: migração da energia entre íons de Yb3+, transferência de energia entre íons Yb3+ e Tm3+, e interações com radicais OH-. Os resultados indicam que transferência de energia Yb-Tm favorece a emissão em 1800 nm, e não há nenhuma evidência da supressão da luminescência até concentração de 2% de Tm2O3. / This work presents a throughout near-infrared and visible spectroscopic characterization of two sets of Yb3+ and Tm3+ codoped sodium aluminophosphate glasses, prepared in nitrogen and ambient atmospheres. In these samples, the Yb3+ ions are employed as efficient sensitizers of 0.98 µm excitation, with subsequent energy transfer to Tm3+ ions. Results are discussed in terms of the inferred OH- content in each set of samples, and as a function of Tm2O3 concentration. Radiative properties are analyzed using Judd Ofelt theory, and by employing experimental and theoretical data, the fluorescence quantum efficiencies h of several levels are evaluated. Results indicate that samples prepared in N2 atmosphere, with lower OH- content, present superior properties than those prepared in ambient atmosphere. Among these properties are a 30% more extensive infrared transmission of the host matrix, higher emission intensities, and decreased quenching effects, characterizing them as potential materials for high power laser generation, as well as efficient upconversion. Also the energy transfer processes were studied, by using Förster, Dexter and Miyakawa theoretical models, the energy transfer parameters were calculated. The main ion-ion energy transfer processes analyzed were: energy migration among Yb3+ ions, energy transfer between Yb3+ and Tm3+ ions, and interactions with OH- radicals.The results indicated that Yb®Tm energy transfer favors 1.8 ?m emission, and there is no evidence of concentration quenching up to 2% Tm2O3 doping.