Cloud observations in Switzerland using hemispherical sky cameras

We present observations of total cloud cover and cloud type classification results from a sky camera network comprising four stations in Switzerland. In a comprehensive intercomparison study, records of total cloud cover from the sky camera, long-wave radiation observations, Meteosat, ceilometer, and visual observations were compared. Total cloud cover from the sky camera was in 65–85% of cases within ±1 okta with respect to the other methods. The sky camera overestimates cloudiness with respect to the other automatic techniques on average by up to 1.1 ± 2.8 oktas but underestimates it by 0.8 ± 1.9 oktas compared to the human observer. However, the bias depends on the cloudiness and therefore needs to be considered when records from various observational techniques are being homogenized. Cloud type classification was conducted using the k-Nearest Neighbor classifier in combination with a set of color and textural features. In addition, a radiative feature was introduced which improved the discrimination by up to 10%. The performance of the algorithm mainly depends on the atmospheric conditions, site-specific characteristics, the randomness of the selected images, and possible visual misclassifications: The mean success rate was 80–90% when the image only contained a single cloud class but dropped to 50–70% if the test images were completely randomly selected and multiple cloud classes occurred in the images.

A spectroscopy study of nearby late-type stars, possible members of stellar kinematic groups

Context. Nearby late-type stars are excellent targets for seeking young objects in stellar associations and moving groups. The origin of these structures is still misunderstood, and lists of moving group members often change with time and also from author to author. Most members of these groups have been identified by means of kinematic criteria, leading to an important contamination of previous lists by old field stars. Aims. We attempt to identify unambiguous moving group members among a sample of nearby-late type stars by studying their kinematics, lithium abundance, chromospheric activity, and other age-related properties. Methods. High-resolution echelle spectra (R ~ 57 000) of a sample of nearby late-type stars are used to derive accurate radial velocities that are combined with the precise Hipparcos parallaxes and proper motions to compute galactic-spatial velocity components. Stars are classified as possible members of the classical moving groups according to their kinematics. The spectra are also used to study several age-related properties for young late-type stars, i.e., the equivalent width of the lithium Li i 6707.8 Å line or the R'_HK index. Additional information like X-ray fluxes from the ROSAT All-Sky Survey or the presence of debris discs is also taken into account. The different age estimators are compared and the moving group membership of the kinematically selected candidates are discussed. Results. From a total list of 405 nearby stars, 102 have been classified as moving group candidates according to their kinematics. i.e., only ~25.2% of the sample. The number reduces when age estimates are considered, and only 26 moving group candidates (25.5% of the 102 candidates) have ages in agreement with the star having the same age as an MG member.

Recherche et analyse d'étoiles naines blanches chimiquement stratiées dans le Sloan Digital Sky Survey

Ce mémoire présente une recherche détaillée et une analyse des étoiles naines blanches hybrides chimiquement stratifiées dans le Sloan Digital Sky Survey (SDSS). Une seule étoile stratifiée, PG 1305-017, était connue avant notre recherche. L'objectif principal est de confirmer l'existence de plusieurs nouvelles étoiles stratifiées. Pour ce faire, il a fallu dans un premier temps développer une nouvelle génération de modèles d'atmosphère à partir de ceux de Bergeron et al. (1991) et Tremblay & Bergeron (2009). Nous y avons ajouté l'opacité de toutes les raies d'hélium et les calculs nécessaires pour tenir compte de la stratification chimique de l'atmosphère, où une mince quantité d’hydrogène flotte en équilibre diffusif au-dessus d’une enveloppe massive d’hélium. En parallèle, nous avons aussi calculé des modèles standards, chimiquement homogènes. Ensuite, nous avons sélectionné des naines blanches chaudes (Teff > 30,000 K) de type spectral hybride (traces d'hélium et d'hydrogène) parmi les ~38,000 naines blanches répertoriées dans le SDSS. Un total de 52 spectres d'étoile a été retenu dans notre échantillon final. La technique spectroscopique, c'est-à-dire l'ajustement des raies spectrales des modèles sur un spectre observé, a été appliquée à toutes les étoiles de notre échantillon. Nous avons ainsi mesuré la température effective, la gravité de surface et la composition chimique de l'atmosphère de ces étoiles. Par l'ajustement simultané de modèles stratifiés et homogènes, nous avons aussi pu déterminer si les étoiles étaient stratifiées ou non. Nous identifions ainsi 14 naines blanches stratifiées. Nous tirons de ces résultats plusieurs conclusions sur les processus physiques expliquant la présence d'hélium dans l'atmosphère.

Recherche et analyse d'étoiles naines blanches chimiquement stratiées dans le Sloan Digital Sky Survey

Ce mémoire présente une recherche détaillée et une analyse des étoiles naines blanches hybrides chimiquement stratifiées dans le Sloan Digital Sky Survey (SDSS). Une seule étoile stratifiée, PG 1305-017, était connue avant notre recherche. L'objectif principal est de confirmer l'existence de plusieurs nouvelles étoiles stratifiées. Pour ce faire, il a fallu dans un premier temps développer une nouvelle génération de modèles d'atmosphère à partir de ceux de Bergeron et al. (1991) et Tremblay & Bergeron (2009). Nous y avons ajouté l'opacité de toutes les raies d'hélium et les calculs nécessaires pour tenir compte de la stratification chimique de l'atmosphère, où une mince quantité d’hydrogène flotte en équilibre diffusif au-dessus d’une enveloppe massive d’hélium. En parallèle, nous avons aussi calculé des modèles standards, chimiquement homogènes. Ensuite, nous avons sélectionné des naines blanches chaudes (Teff > 30,000 K) de type spectral hybride (traces d'hélium et d'hydrogène) parmi les ~38,000 naines blanches répertoriées dans le SDSS. Un total de 52 spectres d'étoile a été retenu dans notre échantillon final. La technique spectroscopique, c'est-à-dire l'ajustement des raies spectrales des modèles sur un spectre observé, a été appliquée à toutes les étoiles de notre échantillon. Nous avons ainsi mesuré la température effective, la gravité de surface et la composition chimique de l'atmosphère de ces étoiles. Par l'ajustement simultané de modèles stratifiés et homogènes, nous avons aussi pu déterminer si les étoiles étaient stratifiées ou non. Nous identifions ainsi 14 naines blanches stratifiées. Nous tirons de ces résultats plusieurs conclusions sur les processus physiques expliquant la présence d'hélium dans l'atmosphère.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.