Measuring star formation in high-z massive galaxies: a mid-infrared to submillimetre study of the GOODS NICMOS Survey sample

We present measurements of the mean mid-infrared to submillimetre flux densities of massive (M_*≳ 10^11 M_⊙) galaxies at redshifts 1.7 < z < 2.9, obtained by stacking positions of known objects taken from the GOODS NICMOS Survey (GNS) catalogue on maps at 24 μm (Spitzer/MIPS); 70, 100 and 160 μm (Herschel/PACS); 250, 350 and 500 μm (BLAST); and 870 μm (LABOCA). A modified blackbody spectrum fit to the stacked flux densities indicates a median [interquartile] star formation rate (SFR) of SFR = 63[48, 81] M_⊙ yr^−1. We note that not properly accounting for correlations between bands when fitting stacked data can significantly bias the result. The galaxies are divided into two groups, disc-like and spheroid-like, according to their Sérsic indices, n. We find evidence that most of the star formation is occurring in n≤ 2 (disc-like) galaxies, with median [interquartile] SFR = 122[100, 150] M_⊙ yr^−1, while there are indications that the n > 2 (spheroid-like) population may be forming stars at a median [interquartile] SFR = 14[9, 20] M_⊙ yr^−1, if at all. Finally, we show that star formation is a plausible mechanism for size evolution in this population as a whole, but find only marginal evidence that it is what drives the expansion of the spheroid-like galaxies.

Star formation in a stellar mass-selected sample of galaxies to z=3 from the GOODS-NICMOS Survey

We present a study of the star-forming properties of a stellar mass-selected sample of galaxies in the GOODS (Great Observatories Origins Deep Survey) NICMOS Survey (GNS), based on deep Hubble Space Telescope (HST) imaging of the GOODS North and South fields. Using a stellar mass-selected sample, combined with HST/ACS and Spitzer data to measure both ultraviolet (UV) and infrared-derived star formation rates (SFRs), we investigate the star forming properties of a complete sample of ∼1300 galaxies down to log M_*= 9.5 at redshifts 1.5 < z < 3. Eight per cent of the sample is made up of massive galaxies with M_*≥ 10^11 M_⊙. We derive optical colours, dust extinctions and UV and infrared SFR to determine how the SFR changes as a function of both stellar mass and time. Our results show that SFR increases at higher stellar mass such that massive galaxies nearly double their stellar mass from star formation alone over the redshift range studied, but the average value of SFR for a given stellar mass remains constant over this ∼2 Gyr period. Furthermore, we find no strong evolution in the SFR for our sample as a function of mass over our redshift range of interest; in particular we do not find a decline in the SFR among massive galaxies, as is seen at z < 1. The most massive galaxies in our sample (log M_*≥ 11) have high average SFRs with values SFR_UV, corr= 103 ± 75 M_⊙ yr^−1, and yet exhibit red rest-frame (U−B) colours at all redshifts. We conclude that the majority of these red high-redshift massive galaxies are red due to dust extinction. We find that A_2800 increases with stellar mass, and show that between 45 and 85 per cent of massive galaxies harbour dusty star formation. These results show that even just a few Gyr after the first galaxies appear, there are strong relations between the global physical properties of galaxies, driven by stellar mass or another underlying feature of galaxies strongly related to the stellar mass.

The AGN, star-forming, and morphological properties of luminous ir-bright/optically-faint galaxies

We present the active galactic nucleus (AGN), star-forming, and morphological properties of a sample of 13 MIR-luminous (∫_24 700 μJy) IR-bright/optically-faint galaxies (IRBGs, ∫_24/f_R≲ 1000). While these z ∼ 2 sources were drawn from deep Chandra fields with >200 ks X-ray coverage, only seven are formally detected in the X-ray and four lack X-ray emission at even the 2σ level. Spitzer InfraRed Spectrograph (IRS) spectra, however, confirm that all of the sources are AGN-dominated in the mid-IR, although half have detectable polycyclic aromatic hydrocarbon (PAH) emission responsible for ∼25% of their mid-infrared flux density. When combined with other samples, this indicates that at least 30%–40% of luminous IRBGs have star formation rates in the ultraluminous infrared galaxy (ULIRG) range (∼100–2000 M_⨀ yr^−1). X-ray hardness ratios and MIR to X-ray luminosity ratios indicate that all members of the sample contain heavily X-ray obscured AGNs, 80% of which are candidates to be Compton thick. Furthermore, the mean X-ray luminosity of the sample, log L_2–10 keV(erg s^−1) ∼44.6, indicates that these IRBGs are Type 2 QSOs, at least from the X-ray perspective. While those sources most heavily obscured in the X-ray are also those most likely to display strong silicate absorption in the mid-IR, silicate absorption does not always accompany X-ray obscuration. Finally, ∼70% of the IRBGs are merger candidates, a rate consistent with that of sub-mm galaxies (SMGs), although SMGs appear to be physically larger than IRBGs. These characteristics are consistent with the proposal that these objects represent a later, AGN-dominated, and more relaxed evolutionary stage following soon after the star-formation-dominated one represented by the SMGs.

The far-infrared/submillimeter properties of galaxies located behind the Bullet cluster

The Herschel Lensing Survey (HLS) takes advantage of gravitational lensing by massive galaxy clusters to sample a population of high-redshift galaxies which are too faint to be detected above the confusion limit of current far-infrared/submillimeter telescopes. Measurements from 100-500 μm bracket the peaks of the far-infrared spectral energy distributions of these galaxies, characterizing their infrared luminosities and star formation rates. We introduce initial results from our science demonstration phase observations, directed toward the Bullet cluster (1E0657-56). By combining our observations with LABOCA 870 μm and AzTEC 1.1 mm data we fully constrain the spectral energy distributions of 19 MIPS 24 μm-selected galaxies which are located behind the cluster. We find that their colors are best fit using templates based on local galaxies with systematically lower infrared luminosities. This suggests that our sources are not like local ultra-luminous infrared galaxies in which vigorous star formation is contained in a compact highly dust-obscured region. Instead, they appear to be scaled up versions of lower luminosity local galaxies with star formation occurring on larger physical scales.

Search for first harmonic modulation in the right ascension distribution of cosmic rays detected at the Pierre Auger Observatory

We present the results of searches for dipolar-type anisotropies in different energy ranges above 2.5 x 10(17) eV with the surface detector array of the Pierre Auger Observatory, reporting on both the phase and the amplitude measurements of the first harmonic modulation in the right-ascension distribution. Upper limits on the amplitudes are obtained, which provide the most stringent bounds at present, being below 2% at 99% C.L. for EeV energies. We also compare our results to those of previous experiments as well as with some theoretical expectations. (C) 2011 Elsevier B.V. All rights reserved.

Local luminous infrared galaxies: Spatially resolved mid-infrared observations with Spitzer/IRS

Luminous Infrared (IR) Galaxies (LIRGs, L_IR=10^11-10 L_⨀) are an important cosmological class of galaxies as they are the main contributors to the co-moving star formation rate density of the universe at z=1. In this paper we present a guaranteed time observation (GTO) Spitzer InfraRed Spectrograph (IRS) program aimed to obtain spectral mapping of a sample of 14 local d<76Mpc LIRGs. The data cubes map, at least, the central 20arcsec X 20arcsec to 30 arcsec X 30 arcsec regions of the galaxies, and use all four IRS modules covering the full 5-38 μ m spectral range. The final goal of this project is to characterize fully the mid-IR properties of local LIRGs as a first step to understanding their more distant counterparts. In this paper we present the first results of this GTO program. The IRS spectral mapping data allow us to build spectral maps of the bright mid-IR emission lines (e.g., [Ne II] 12.81 μ m, [Ne III]15.56 μ m, [S III] 18.71 μ m, H_2 at 17 μ m), continuum, the 6.2 and 11.3 μ m polycyclic aromatic hydrocarbon (PAH) features, and the 9.7 μ m silicate feature, as well as to extract 1D spectra for regions of interest in each galaxy. The IRS data are used to obtain spatially resolved measurements of the extinction using the 9.7 μ m silicate feature, and to trace star forming regions using the neon lines and the PAH features. We also investigate a number of active galactic nuclei (AGN) indicators, including the presence of high excitation emission lines and a strong dust continuum emission at around 6 9.7 μ m . We finally use the integrated Spitzer/IRS spectra as templates of local LIRGs. We discuss several possible uses for these templates, including the calibration of the star formation rate of IR-bright galaxies at high redshift. We also predict the intensities of the brightest mid-IR emission lines for LIRGs as a function of redshift, and compare them with the expected sensitivities of future space IR missions.

The host galaxies and black holes of typical z~0.5-1.4 AGNs

We study the stellar and star formation properties of the host galaxies of 58 X-ray-selected AGNs in the GOODS portion of the Chandra Deep Field South (CDF-S) region at z ~ 0.5-1.4. The AGNs are selected such that their rest-frame UV to near-infrared spectral energy distributions (SEDs) are dominated by stellar emission; i.e., they show a prominent 1.6 μm bump, thus minimizing the AGN emission "contamination." This AGN population comprises approximately 50% of the X-ray-selected AGNs at these redshifts. We find that AGNs reside in the most massive galaxies at the redshifts probed here. Their characteristic stellar masses (M_* ~ 7.8 × 10^10 and M_* ~ 1.2 × 10^11 M_☉ at median redshifts of 0.67 and 1.07, respectively) appear to be representative of the X-ray-selected AGN population at these redshifts and are intermediate between those of local type 2 AGNs and high-redshift (z ~ 2) AGNs. The inferred black hole masses (M_BH ~ 2 × 10^8 M_☉) of typical AGNs are similar to those of optically identified quasars at similar redshifts. Since the AGNs in our sample are much less luminous (L_2–10 keV < 10^44 erg s^−1) than quasars, typical AGNs have low Eddington ratios (η ~ 0.01-0.001). This suggests that, at least at intermediate redshifts, the cosmic AGN "downsizing" is due to both a decrease in the characteristic stellar mass of typical host galaxies and less efficient accretion. Finally, there is no strong evidence in AGN host galaxies for either highly suppressed star formation (expected if AGNs played a role in quenching star formation) or elevated star formation when compared to mass-selected (i.e., IRAC-selected) galaxies of similar stellar masses and redshifts.

Mid-infrared spectroscopy of lensed galaxies at 1 < z < 3: The nature of sources near the MIPS confusion limit

We present Spitzer IRS mid-infrared spectra for 15 gravitationally lensed, 24 μm-selected galaxies, and combine the results with four additional very faint galaxies with IRS spectra in the literature. The median intrinsic 24 μm flux density of the sample is 130 μJy, enabling a systematic survey of the spectral properties of the very faint 24 μm sources that dominate the number counts of Spitzer cosmological surveys. Six of the 19 galaxy spectra (32%) show the strong mid-IR continuua expected of AGNs; X-ray detections confirm the presence of AGNs in three of these cases, and reveal AGNs in two other galaxies. These results suggest that nuclear accretion may contribute more flux to faint 24 μm-selected samples than previously assumed. Almost all the spectra show some aromatic (PAH) emission features; the measured aromatic flux ratios do not show evolution from z = 0. In particular, the high signal-to-noise mid-IR spectrum of SMM J163554.2+661225 agrees remarkably well with low-redshift, lower luminosity templates. We compare the rest-frame 8 μm and total infrared luminosities of star-forming galaxies, and find that the behavior of this ratio with total IR luminosity has evolved modestly from z = 2 to z = 0. Since the high aromatic-to-continuum flux ratios in these galaxies rule out a dominant contribution by AGNs, this finding implies systematic evolution in the structure and/or metallicity of infrared sources with redshift. It also has implications for the estimates of star-forming rates inferred from 24 μm measurements, in the sense that at z ~ 2, a given observed frame 24 μm luminosity corresponds to a lower bolometric luminosity than would be inferred from low-redshift templates of similar luminosity at the corresponding rest wavelength.

The SCUBA HAlf degree extragalactic survey - III. Identification of radio and mid-infrared counterparts to submillimetre galaxies

Determining an accurate position for a submillimetre (submm) galaxy (SMG) is the crucial step that enables us to move from the basic properties of an SMG sample - source counts and 2D clustering - to an assessment of their detailed, multiwavelength properties, their contribution to the history of cosmic star formation and their links with present-day galaxy populations. In this paper, we identify robust radio and/or infrared (IR) counterparts, and hence accurate positions, for over two-thirds of the SCUBA HAlf-Degree Extragalactic Survey (SHADES) Source Catalogue, presenting optical, 24-μm and radio images of each SMG. Observed trends in identification rate have given no strong rationale for pruning the sample. Uncertainties in submm position are found to be consistent with theoretical expectations, with no evidence for significant additional sources of error. Employing the submm/radio redshift indicator, via a parametrization appropriate for radio-identified SMGs with spectroscopic redshifts, yields a median redshift of 2.8 for the radio-identified subset of SHADES, somewhat higher than the median spectroscopic redshift. We present a diagnostic colour-colour plot, exploiting Spitzer photometry, in which we identify regions commensurate with SMGs at very high redshift. Finally, we find that significantly more SMGs have multiple robust counterparts than would be expected by chance, indicative of physical associations. These multiple systems are most common amongst the brightest SMGs and are typically separated by 2-6 arcsec, similar to 15-20/sin i kpc at z~ 2, consistent with early bursts seen in merger simulations.

Coding Strategies for X-ray Tomography

This work focuses on the construction and application of coded apertures to compressive X-ray tomography. Coded apertures can be made in a number of ways, each method having an impact on system background and signal contrast. Methods of constructing coded apertures for structuring X-ray illumination and scatter are compared and analyzed. Apertures can create structured X-ray bundles that investigate specific sets of object voxels. The tailored bundles of rays form a code (or pattern) and are later estimated through computational inversion. Structured illumination can be used to subsample object voxels and make inversion feasible for low dose computed tomography (CT) systems, or it can be used to reduce background in limited angle CT systems.

On the detection side, coded apertures modulate X-ray scatter signals to determine the position and radiance of scatter points. By forming object dependent projections in measurement space, coded apertures multiplex modulated scatter signals onto a detector. The multiplexed signals can be inverted with knowledge of the code pattern and system geometry. This work shows two systems capable of determining object position and type in a 2D plane, by illuminating objects with an X-ray `fan beam,' using coded apertures and compressive measurements. Scatter tomography can help identify materials in security and medicine that may be ambiguous with transmission tomography alone.

Calcium-rich gap transients: Tidal detonations of white dwarfs?

We hypothesize that at least some of the recently discovered class of calcium-rich gap transients are tidal detonation events of white dwarfs (WDs) by black holes (BHs) or possibly neutron stars. We show that the properties of the calcium-rich gap transients agree well with the predictions of the tidal detonation model. Under the predictions of this model, we use a follow-up X-ray observation of one of these transients, SN 2012hn, to place weak upper limits on the detonator mass of this system that include all intermediate-mass BHs (IMBHs). As these transients are preferentially in the stellar haloes of galaxies, we discuss the possibility that these transients are tidal detonations of WDs caused by random flyby encounters with IMBHs in dwarf galaxies or globular clusters. This possibility has been already suggested in the literature but without connection to the calcium-rich gap transients. In order for the random flyby cross-section to be high enough, these events would have to be occurring inside these dense stellar associations. However, there is a lack of evidence for IMBHs in these systems, and recent observations have ruled out all but the very faintest dwarf galaxies and globular clusters for a few of these transients. Another possibility is that these are tidal detonations caused by three-body interactions, where a WD is perturbed towards the detonator in isolated multiple star systems. We highlight a number of ways this could occur, even in lower mass systems with stellar-mass BHs or neutron stars. Finally, we outline several new observational tests of this scenario, which are feasible with current instrumentation.

The microphysics of collisionless shock waves

Collisionless shocks, that is shocks mediated by electromagnetic processes, are customary in space physics and in astrophysics. They are to be found in a great variety of objects and environments: magnetospheric and heliospheric shocks, supernova remnants, pulsar winds and their nebulæ, active galactic nuclei, gamma-ray bursts and clusters of galaxies shock waves. Collisionless shock microphysics enters at different stages of shock formation, shock dynamics and particle energization and/or acceleration. It turns out that the shock phenomenon is a multi-scale non-linear problem in time and space. It is complexified by the impact due to high-energy cosmic rays in astrophysical environments. This review adresses the physics of shock formation, shock dynamics and particle acceleration based on a close examination of available multi-wavelength or in situ observations, analytical and numerical developments. A particular emphasis is made on the different instabilities triggered during the shock formation and in association with particle acceleration processes with regards to the properties of the background upstream medium. It appears that among the most important parameters the background magnetic field through the magnetization and its obliquity is the dominant one. The shock velocity that can reach relativistic speeds has also a strong impact over the development of the micro-instabilities and the fate of particle acceleration. Recent developments of laboratory shock experiments has started to bring some new insights in the physics of space plasma and astrophysical shock waves. A special section is dedicated to new laser plasma experiments probing shock physics.

Synthèses et propriétés thermiques et photophysiques de nouveaux polymères de coordination à base de CuX (X = Cl, Br, I) et de ligands mono- ou dithioéthers

La recherche sur la conception de nouveaux matériaux, dits intelligents, est en constant progrès depuis plus de 30 ans. Historiquement, les premiers matériaux utilisés et transformés par l’homme étaient le bois, les minéraux et ses dérivés (pierre, métaux, etc.). C’est à la fin du 19e siècle que la synthèse des polymères organiques et inorganiques ainsi que leurs utilisations se développèrent. Ce progrès continue de nos jours. Ainsi, c’est dans cette direction que cette thèse fut rédigée, l’étude de polymères de coordination basés sur le cuivre(I). Elle s’orchestra en six principales sections de recherche. La première section, i.e. le chapitre 2 traite de la coordination de différents ligands monothioéthers sur du CuX (X = I, Br) pour former plusieurs types de polymères de coordination (CPs). Ainsi, le CP 1D [(Me[indice inférieur 2]S)[indice inférieur 3]{Cu[indice inférieur 2]([mu]-I)[indice inférieur 2}][indice inférieur n] est obtenu quand CuI et Sme[indice inférieur 2] réagissent ensemble dans le n-heptane, alors qu’ils entrainent la formation du CP 2D [(Me[indice inférieur 2]S) [indice inférieur 3] {Cu[indice inférieur 4]([mu]-I) [indice inférieur 4]}] [indice inférieur n] dans le MeCN. Ce dernier contient des unités de construction secondaire (SBU ; Secondary Building Units en anglais) en forme de cluster Cu[indice inférieur 4]I[indice inférieur 4] « cubane partiellement ouvert ». En faisant réagir le MeSEt avec du CuI, le CP 2D [(MeSEt) [indice inférieur 2]{Cu[indice inférieur 4] ([mu][indice inférieur 3]-I) [indice inférieur 2] ([mu][indice inférieur 2]-I) [indice inférieur 2]}(MeCN) [indice inférieur 2]] [indice inférieur n] contenant des SBUs de type Cu[indice inférieur 4]I[indice inférieur 4] « cubanes en escalier » a été isolé dans MeCN, alors qu’ils entrainent l’obtention du polymère 1D [(MeSEt) [indice inférieur 3]{Cu[indice inférieur 4] ([mu][indice inférieur 3]-I) [indice inférieur 4]}] [indice inférieur n] dans le n-heptane contenant quant à lui des clusters de types Cu[indice inférieur 4]I[indice inférieur 4] « cubanes fermés ». Alors que le traitement de MeSPr avec du CuI forme le CP 1D [(MeSPr) [indice inférieur 3]{Cu[indice inférieur 4] ([mu][indice inférieur 3]-I) [indice inférieur 4]}] [indice inférieur n], les composés [(L) [indice inférieur 4]{Cu[indice inférieur 4] ([mu][indice inférieur 3]-I) [indice inférieur 4]}] (L = EtSPr, Pr[indice inférieur 2]S) sont respectivement obtenus avec le EtSPr et le Pr[indice inférieur 2]S. À partir du [indice supérieur i]Pr[indice inférieur 2]S et de CuI, le cluster [([indice supérieur i]Pr[indice inférieur 2]S) [indice inférieur 6]{Cu[indice inférieur 8] ([mu][indice inférieur 3]-I) [indice inférieur 3]}([mu][indice inférieur 4]-I) [indice inférieur 2]}] est obtenu alors que l’on forme un CP 2D [(Cu[indice inférieur 3]Br[indice inférieur 3])(MeSEt) [indice inférieur 3]] [indice inférieur n] à partir de CuBr et MeSEt dans l’heptane. Ce dernier incorpore à la fois des Cu([mu][indice inférieur 2]-Br) [indice inférieur 2]Cu rhomboédriques et des SBUs de type Cu[indice inférieur 4]Br[indice inférieur 4] « cubanes ouverts ». Le MeSPr forme, quant à lui avec le CuBr dans l’heptane, le CP 1D [(Cu[indice inférieur 3]Br[indice inférieur 3])(MeSPr) [indice inférieur 3]] [indice inférieur n] qui, après recristallisation dans le MeCN, est converti en un CP 2D [(Cu[indice inférieur 5]Br[indice inférieur 5])([mu][indice inférieur 2]-MeSPr) [indice inférieur 3]] [indice inférieur n] incorporant des SBUs [(Cu[indice inférieur 5] ([mu][indice inférieur 4]-Br)([mu][indice inférieur 2]-Br)]. Les propriétés de stabilités thermiques et photophysiques de ces matériaux ont aussi été reportées.   Dans la section 2, i.e. au chapitre 3, les réactions entre des ligands dithioétherbutanes (1,4-bis(phénylthio)butane et 1,4-bis(cyclohexylthio)butane) avec CuX (X = Br, I) ont été étudiées. En faisant réagir les CuX avec le 1,4-bis(cyclohexylthio)butane, dans le ratio (1:1), les CPs 1D, peu luminescents, isostructuraux [(Cu[indice inférieur 2]X[indice inférieur 2])([mu]-CyS(CH[indice inférieur 2]) [indice inférieur 4])SCy) [indice inférieur 2]] [indice inférieur n] (X = Br, I) sont obtenus. Inversement, quand CuI réagit avec 1,4-bis(phénylthio)butane, dans le ratio (2:1), il se forme le préalablement reporté CP 2D [(Cu[indice inférieur 4]I[indice inférieur 4])([mu]- PhS(CH[indice inférieur 2]) [indice inférieur 4])SPh) [indice inférieur 2]] [indice inférieur n], alors qu’avec le CyS(CH[indice inférieur 2]) [indice inférieur 4])SCy, un nouveau composé luminescent est obtenu, mais sa structure n’a pas pu être résolue.(1) Les caractérisations habituelles en photophysique et en stabilité thermique ont été menées sur ces matériaux. Dans la troisième section, i.e. dans le chapitre 4, les réactions de coordination de CuX (Br, I) sur les ligands dithioétherbutènes E- et Z-PhS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])SPh, E- et Z-pTolS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])S-pTol ont été comparées. Quand les sels CuX réagissent avec E-PhS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])SPh les CP 2D [Cu[indice inférieur 2]X[indice inférieur 2]{[mu]-E-PhS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])SPh}[indice inférieur 2]] [indice inférieur n] (X = I, Br), composés isostructuraux, sont obtenus. Incorporant une structure sans-précédente, ces réseaux sont formés à partir de couches 2D en alternance ABAB, contenants des SBUs Cu[indice inférieur 2] ([mu][indice inférieur 2]-X) [indice inférieur 2] rhomboédriques. Inversement, quand l’isomère Z-PhS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])SPh réagit avec des sels de CuX, deux structures différentes sont obtenues : le CP 2D [Cu[indice inférieur 4] ([mu][indice inférieur 3]-I) [indice inférieur 4] ([mu]-Z-PhS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])SPh}[indice inférieur 2]] [indice inférieur n] contenant des SBUs de type « cubane fermé » et le complexe 0D [Cu[indice inférieur 2]Br[indice inférieur 2]{[mu]-Z-PhS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])SPh}[indice inférieur 2]]. De par la réaction de E-pTolS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])S-pTol avec CuI, le CP 2D [{Cu([mu][indice inférieur 3]-I)} [indice inférieur 2] ([mu]-E-pTolS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])S-pTol)]n contenant des rubans parallèles en escalier est obtenu, alors que la structure issue de CuBr n’a pas pu être résolue. Finalement, quand CuX réagit avec Z-pTolS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])S-pTol, les CPs 2D iso-structuraux [Cu[indice inférieur 2]X[indice inférieur 2]{[mu]-Z-pTolS(CH[indice inférieur 2]CH=CHCH[indice inférieur 2])S-pTol}[indice inférieur 2]] (X = I, Br) sont formés. Dans ce cas, contrairement, aux premières structures obtenues, les couches de ces CPs sont composées de grilles incorporant des SBUs rhomboédriques Cu[indice inférieur 2] ([mu][indice inférieur 2]-X) [indice inférieur 2] dont les distances Cu···Cu sont identiques d’une couche à l’autre. Les caractérisations habituelles en photophysique et en stabilités thermiques ont été menées sur ces matériaux. De plus, des calculs théoriques ont été réalisés afin de mieux comprendre les propriétés photophysiques de ces composés. La quatrième section, i.e. le chapitre 5, traite des réactions de CuX (Br, I, Cl) sur des ligands dithioétherbutynes (1,4-bis(pTolthio)but-2-yne et 1,4-bis(benzylthio)but-2-yne. Quand CuBr réagit avec 1,4-bis(pTolthio)but-2-yne, le CP 1D [{Cu([mu][indice inférieur 2]-Br) [indice inférieur 2]Cu}([mu]-pTolSCH[indice inférieur 2]C≡CCH[indice inférieur 2]S-pTol) [indice inférieur 2]] [indice inférieur n] est obtenu, alors que le CP 2D [{Cu[indice inférieur 4] ([mu][indice inférieur 3]-I) [indice inférieur 4]}([mu]-pTolSCH[indice inférieur 2]C≡CCH[indice inférieur 2]S-pTol) [indice inférieur 2]] [indice inférieur n], préalablement reporté, est formé.(2) La réaction des sels CuI et CuCl avec 1,4-bis(benzylthio)but-2-yne engendre la formation de complexes isomorphes 0D [{Cu([mu][indice inférieur 2]-X) [indice inférieur 2]Cu}([mu]-PhCH[indice inférieur 2]SCH[indice inférieur 2]C≡CCH[indice inférieur 2]SCH[indice inférieur 2]Ph) [indice inférieur 2]] (X = I, Br). Contrairement à l’utilisation de CuCl, qui avec PhCH[indice inférieur 2]SCH[indice inférieur 2]C≡CCH[indice inférieur 2]SCH[indice inférieur 2]Ph forme le CP 2D [{Cu[indice inférieur 2] ([mu][indice inférieur 2]-Cl)([mu] [indice inférieur 3]-Cl)}([mu]-PhCH[indice inférieur 2]SCH[indice inférieur 2]C≡CCH[indice inférieur 2]SCH[indice inférieur 2]Ph)] [indice inférieur n]. Notons que ce CP présente des propriétés de photophysique peu communes pour un dérivé chloré, car il émet de la lumière autour de 600 nm. La cinquième section, i.e. le chapitre 6, traite des réactions de CuI avec PhS(CH[indice inférieur 2]) [indice inférieur 8]SPh et pTolS(CH[indice inférieur 2]) [indice inférieur 8]S-pTol qui génèrent respectivement les CPs luminescents 1D [Cu[indice inférieur 4]I[indice inférieur 4]{[mu][indice inférieur 2]-PhS(CH[indice inférieur 2]) [indice inférieur 8]SPh}[indice inférieur 2]] [indice inférieur n] et 2D [Cu8I8{[mu]2-pTolS(CH2)8S-pTol}3(MeCN)2]n. Le CP 2D [Cu8I8{[mu]2-pTolS(CH2)8S-pTol}3 (MeCN)2]n présente un réseau qui n’avait jamais été rencontré dans la littérature auparavant, c.-à-d., des couches de polymère construites à partir de deux cubanes fermés pontés ensemble par un rhomboèdre comme SBUs. Leurs propriétés physiques et de stabilités thermiques ont été étudiées et présentent quelques différences notables. La sixième section, i.e. le chapitre 7, traite des réactions entre CuI avec le ligand flexible pTolS(CH[indice inférieur 2]) [indice inférieur 8]S-pTol dans le MeCN ou EtCN et p-[indice supérieur t]BuC[indice inférieur 6]H[indice inférieur 4]S(CH[indice inférieur 2]) [indice inférieur 8]SC[indice inférieur 6]H[indice inférieur 4]-p-[indice supérieur t]Bu L2 dans EtCN. Les synthèses issues de pTolS(CH[indice inférieur 2]) [indice inférieur 8]S-pTol permettent l’obtention de CPs 2D [Cu[indice inférieur 8]I[indice inférieur 8]{pTolS(CH[indice inférieur 2]) [indice inférieur 8]S-pTol}[indice inférieur 3] (solvant) [indice inférieur 2]] [indice inférieur n] (1•MeCN et 1•EtCN) contenant des nœuds de connexion de type Cu[indice inférieur 8]I[indice inférieur 8]. Par opposition, l’utilisation du ligand p-[indice supérieur t]BuC[indice inférieur 6]H[indice inférieur 4]S(CH[indice inférieur 2]) [indice inférieur 8]SC[indice inférieur 6]H[indice inférieur 4]-p-[indice supérieur t]Bu dans EtCN entraine la formation d’un CP 1D [Cu[indice inférieur 4]I[indice inférieur 4]{p-[indice supérieur t]BuC[indice inférieur 6]H[indice inférieur 4]S(CH[indice inférieur 2]) [indice inférieur 8]SC[indice inférieur 6]H[indice inférieur 4]-p-[indice supérieur t]Bu}[indice inférieur 2] (EtCN) [indice inférieur 2]] [indice inférieur n] incorporant les SBUs de type cubane fermé. Les CPs 2D 1•MeCN et 1•EtCN, contrairement à 2•EtCN, présentent l’habilité de pouvoir perdre le solvant initialement incorporé dans leur structure sous vide et de le readsorber ou d’adsorber un autre solvant, chose qui peut être suivie à l’aide de la variation de la luminescence, la stabilité thermique, ou encore par diffraction des rayons X sur poudre. La septième section, i.e. le chapitre 8 traite des réactions, une fois encore, entre un ligand dithioéther, contenant un pont flexible butane (EtS(CH[indice inférieur 2]) [indice inférieur 4]SEt) et les sels CuX (X = I, Br). Dans ce cas, il se forme avec le CuI un CP luminescent 2D [Cu[indice inférieur 4]I[indice inférieur 4]{[mu]-EtS(CH[indice inférieur 2]) [indice inférieur 4]SEt}[indice inférieur 2]] [indice inférieur n], alors qu’il génère avec CuBr, le CP 3D [(Cu[indice inférieur 2]Br[indice inférieur 2]){[mu]-EtS(CH[indice inférieur 2]) [indice inférieur 4]SEt}][indice inférieur n] faiblement luminescent, construit sur des couches en parallèle pontées par les soufres doublement n-donneurs. Il est intéressant de remarquer qu’une migration de l’énergie d’excitation se produit dans le CP 3D (dérivé bromé) contrairement au CP 2D (dérivé iodé) sous excitation de haute intensité. Très peu d’exemples présentent ce type de processus parmi tous les CPs ( < 10). Pour conclure, les réactions entre les sels CuX (X = Cl, Br, I) avec des ligands thioéthers de types différents (mono-, di-thio, rigide ou flexible) peuvent offrir des matériaux de structures variables (CP 0D, 1D, 2D, 3D avec et sans cavités) présentant leurs propres spécificités (luminescence, stabilité thermique, adsorption de gaz, solvatochromisme, etc.). Le résultat le plus important à noter, en comparaison avec la littérature est, qu’il est très difficile, voire impossible, de pouvoir prédire la dimensionnalité, la structure et les propriétés dont résultera la coordination des ligands thioéthers sur des sels de CuX (X = Cl, Br, I). Par conséquent, de nombreuses combinaisons et études restent encore à être menées pour mieux comprendre ces matériaux et trouver la, ou les meilleures combinaisons possibles pour concevoir des MOFs luminescents à partir de CuX.

X-ray analysis of local mid-infrared selected Compton-thick AGN candidates

Cosmic X-ray background synthesis models (Gilli 2007) require a significant fraction of obscured AGN, some of which are expected to be heavily obscured (Compton-thick), but the number density of observationally found obscured sources is still an open issue (Vignali 2010, 2014). This thesis work takes advantage of recent NuSTAR data and is based on a multiwavelength research approach. Gruppioni et al. 2016 compared the AGN bolometric luminosity, for a sample of local 12 micron Seyfert galaxies, derived from the SED decomposition to the same quantity obtained by the 2-10 keV luminosity (IPAC-NED). A difference up to two orders of magnitude resulted between these quantities for some sources. Thus, the intrinsic X-ray luminosity obtained correcting for the obscuration may be underestimated. In this thesis we have tested this hypothesis by re-analysing the X-ray spectra of three of the sources (UGC05101, NGC1194 and NGC3079), for which observations from NuSTAR and Chandra and/or XMM-Newton were available. This is meant to extend our analysis to energies above 10 keV and thus estimate the AGN column density as reliable as possible. For spectral fitting we made use of both the commonly used XSPEC package and the two very recent MYtorus and BNtorus physical models. The available wide bandpass allowed us to achieve new and more solid insights into the X-ray spectral properties of these sources. The measured absorption column densities are highly suggestive of heavy obscuration. Once corrected the X-ray AGN luminosity for the obscuration estimated through our spectral analysis, we compared the L(X) values in the 2-10 keV band with those derived from the MIR band, by means of the relation by Gandhi, 2009. As expected, the values derived from this relation are in good agreement with those we measured, indicating that the column densities were underestimated in the previous literature works.