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The chemical composition of gas in galaxies can be measured in detail from absorption spectroscopy. By studying gas in galaxies in this way, it is possible to investigate the small and faint galaxies, which are the most numerous in the universe. In particular, the chemical distribution of gas in absorbing systems gives us insight into cycles of gas in and around galaxies. Here we study chemical enrichment within 64 Damped Lyman-alpha Absorption (DLA) systems between $1.7 < z < 4.2$. We use high-resolution spectra from VLT/UVES to infer dust depletion from relative abundances of several metals. We perform a component-by-component analysis within DLAs, and characterise variations in their chemical enrichment. Unlike hydrogen, the metal columns can be characterised for individual components. We use them to derive the dust depletion ([Zn/Fe]fit), as an indicator for chemical enrichment. We find that some DLAs are chemically diverse within themselves, with [Zn/Fe]fit ranging up to 0.62 dex within a single system. This suggests that absorbing gas within these galaxies is chemically diverse. Although we do not find a clear trend of decreasing dust depletion with redshift, we do see that the most chemically enriched systems are at lower redshifts. We also observe evidence for dust-poor components at all redshifts, which may be due to the accretion of pristine gas onto galaxies. We combine the chemical and kinematic properties of the individual gas components and observe potential signatures of infalling gas, with low depletion at velocities below $\sim$100km/s, and outflows, with high depletion and velocities of $\sim$600km/s. We find over-abundances of alpha-elements (an enhancement of $\sim$0.3dex) and under-abundances of Mn in several components, which is likely a signature of core-collapse SNe nucleosythesis in the ISM. We observe these effects mostly at lower levels of chemical enrichment., 56 pages, 99 figures, Accepted for publication in A&A, Abstract abridged for arXiv

Selective reactions that combine H 2 , CO and organic electrophiles (aldehyde, ketones, isocyanide) to form hydrogenated C 3 and C 4 carbon chains are reported. These reactions proceed by CO homologation mediated by [W(CO) 6 ] and an aluminum(I) reductant, followed by functionalization and hydrogenation of the chain ends. A combination of kinetics (rates, KIEs) and DFT calculations has been used to gain insight into a key step which involves hydrogenation of a metallocarbene intermediate. These findings expand the extremely small scope of systems that combine H 2 and CO to make well-defined products with complete control over chain length and functionality.

Density functional theory has been used to optimize and to investigate the mechanical, thermal, electronic and optical properties of exohedral, endohedral and heteroatom substituted excellent host family of fullerenes. In this study, we have investigated hydrogen molecule encapsulation properties of C-20 , aluminum, silicon, gallium and germanium doped C-20 fullerenes. We also examined the electronic properties. It was observed that by heteroatom doping it is possible to manipulate the electronic properties of the studied clusters and within the doped clusters, C15Si5 shows the most effective interaction and it is the most sensitive to the presence of H-2 molecule. (C) 2021 Elsevier B.V. All rights reserved.

A new heteroleptic cationic copper(I) complex bearing two N-heterocyclic carbene (NHC) ligands has been prepared. In situ, a Cu–O­ bond can be generated which enables the complex to catalytically activate H2. The resulting complex shows activity in catalytic chemo- and stereoselective alkyne semihydrogenations as well as conjugate reductions of enones.

An active line of contemporary research is dedicated to the adsorption and storage of hydrogen on metal-doped carbon materials. Using density functional theory and van der Waals corrections we have studied molecular and dissociative adsorption of H2 on neutral and cationic C60Con complexes with n = 1–8. The Co atoms form compact clusters on the surface of the fullerene. Dissociative chemisorption of one H2 molecule is more stable than molecular adsorption on neutral C60Con, with the only exception of C60Co. When C60Con is ionized, the electronic charge deficit remains localized in the cobalt cluster. The molecular and dissociative adsorption features on cationic C60Con+ and neutral C60Con complexes are in general similar, but some differences can be highlighted. Molecular and dissociative H2 adsorption on C60Co2+ are competitive; in fact, molecular adsorption is slightly more stable as a result of the localized electronic charge deficit on the Co dimer. Another difference is that the dissociative adsorption energies on some of the neutral C60Con complexes are substantially larger than the dissociative adsorption energies on the corresponding C60Con+ cationic complexes by amounts between 0.2 and 0.5 eV. Activation barriers for dissociation of the adsorbed H2 molecule strongly depend on the charge state and cluster size. These barriers help to interpret the adsorption state (molecular or dissociated) of experimentally produced hydrogenated C60Con+ complexes. Hydrogen saturation has been studied in two cases. C60Co adsorbs three H2 units in molecular form, and C60Con adsorbs up to thirteen H2 units, four dissociated and nine in molecular form. An active line of contemporary research is dedicated to the adsorption and storage of hydrogen on metal-doped carbon materials. Using density functional theory and van der Waals corrections we have studied molecular and dissociative adsorption of H2 on neutral and cationic C60Con complexes with n = 1–8. The Co atoms form compact clusters on the surface of the fullerene. Dissociative chemisorption of one H2 molecule is more stable than molecular adsorption on neutral C60Con, with the only exception of C60Co. When C60Con is ionized, the electronic charge deficit remains localized in the cobalt cluster. The molecular and dissociative adsorption features on cationic C60Con+ and neutral C60Con complexes are in general similar, but some differences can be highlighted. Molecular and dissociative H2 adsorption on C60Co2+ are competitive; in fact, molecular adsorption is slightly more stable as a result of the localized electronic charge deficit on the Co dimer. Another difference is that the dissociative adsorption energies on some of the neutral C60Con complexes are substantially larger than the dissociative adsorption energies on the corresponding C60Con+ cationic complexes by amounts between 0.2 and 0.5 eV. Activation barriers for dissociation of the adsorbed H2 molecule strongly depend on the charge state and cluster size. These barriers help to interpret the adsorption state (molecular or dissociated) of experimentally produced hydrogenated C60Con+ complexes. Hydrogen saturation has been studied in two cases. C60Co adsorbs three H2 units in molecular form, and C60Con adsorbs up to thirteen H2 units, four dissociated and nine in molecular form. ispartof: International Journal of Hydrogen Energy vol:46 issue:39 pages:20594-20606 status: published

Present study, first time, reveals that lithium and ethylenediamine assisted Benkeser reaction enhanced the hydrogenation process where reduced graphene oxide-PANI (G-PANI) nanocomposites act as storage medium. Varying the weight ratio of graphene and PANI, several samples were synthesized and hydrogenated. The reduced graphene oxide-PANI (G-PANI) and hydrogenated reduced graphene oxide-PANI (HG-PANI) nanocomposites were characterized by high resolution transmission electron microscopy (HRTEM), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectra (FTIR) analysis and thermo gravimetric analysis (TGA). The electrical conductivity with the variation of temperature for the nanocomposites has also been studied. The reduced values of electrical conductivity and percent weight loss in TGA suggested that the hydrogenation occurs. The degree of hydrogenation of reduced graphene oxide-PANI estimated by TGA, revealed 11% (30% reduced graphene oxide-PANI) and 16.04% (50% reduced graphene oxide-PANI), hydrogen storage, which is considerably higher than the reported values of hydrogen storage in individual storage materials like, PANI, graphene and carbon nano tube.

Reproducing the observed quenched fraction of satellite galaxies has been a long-standing issue for galaxy formation models. We modify the treatment of environmental effects in our state-of-the-art GAlaxy Evolution and Assembly (GAEA) semi-analytic model to improve our modelling of satellite galaxies. Specifically, we implement gradual stripping of hot gas, ram-pressure stripping of cold gas, and an updated algorithm to account for angular momentum exchanges between the gaseous and stellar disc components of model galaxies. Our updated model is in good agreement with the observed quenched fractions for central and satellite galaxies, and their dependencies on stellar mass and halo mass. We also find consistency between model predictions and observational estimates of quenching time for satellite galaxies; HI, H$_2$ fractions of central galaxies; and deficiencies of HI, H$_2$, SFR of galaxies in cluster haloes. Analysing results from our updated model, we find that the dominant quenching mechanisms are hot-gas stripping for low-mass galaxies, and AGN feedback for massive galaxies. The Ram-pressure stripping of cold gas has a limited impact on the predicted quenched fractions, nonetheless, is needed to reproduce the observed HI deficiencies., Comment: 21 pages, 14 figures; accepted for publication in MNRAS

We present new SINFONI near-infrared integral field unit (IFU) spectroscopy and SALT optical long-slit spectroscopy characterising the history of a nearby merging luminous infrared galaxy, dubbed the Bird (IRAS19115-2114). The NIR line-ratio maps of the IFU data-cubes and stellar population fitting of the SALT spectra now allow dating of the star formation (SF) over the triple system uncovered from our previous adaptive optics data. The distinct components separate very clearly in a line-ratio diagnostic diagram. An off-nuclear pure starburst dominates the current SF of the Bird with 60-70% of the total, with a 4-7 Myr age, and signs of a fairly constant long-term star formation of the underlying stellar population. The most massive nucleus, in contrast, is quenched with a starburst age of >40 Myr and shows hints of budding AGN activity. The secondary massive nucleus is at an intermediate stage. The two major components have a population of older stars, consistent with a starburst triggered 1 Gyr ago in a first encounter. The simplest explanation of the history is that of a triple merger, where the strongly star forming component has joined later. We detect multiple gas flows in different phases. The Bird offers an opportunity to witness multiple stages of galaxy evolution in the same system; triggering as well as quenching of SF, and the early appearance of AGN activity. It also serves as a cautionary note on interpretations of observations with lower spatial resolution and/or without infrared data. At high-redshift the system would look like a clumpy starburst with crucial pieces of its puzzle hidden, in danger of misinterpretations., Submitted to MNRAS. 17 pages, 7 tables, 15 figures

Rationale Molecular hydrogen (H-2) is an important gas for atmospheric chemistry, and an indirect greenhouse gas due to its reaction with OH. The isotopic composition of H-2 (delta D) has been used to investigate its atmospheric budget; here we add a new observable, the clumped isotopic signature Delta DD, to the tools that can be used to study the global cycle of H-2. Methods A method for determining Delta DD in H-2 was developed using the high-resolution MAT 253-Ultra isotope ratio mass spectrometer (Thermo Fisher). The HH, HD and DD abundances are quantified at medium resolution (M/Delta M approximate to 6000), which is sufficient for HD+ and DD+ to be distinguished from H-3(+) and H2D+, respectively. The method involves sequential measurement of isotopologues, and DD is measured using an ion counter. For verification, catalytic Delta DD equilibration experiments were performed at temperatures of up to 850 degrees C. Results The typical precision obtained for Delta DD is 2-6 parts per thousand, close to the theoretical counting statistics limit, and adequate for detecting the expected natural variations. Compatibility and medium-term reproducibility are consistent with the precision values. The method was validated using temperature equilibration experiments, which showed a dependence of Delta DD on temperature as expected form theoretical calculations. Conclusions We have established a method for determining Delta DD in H-2 at natural isotopic abundances, with a precision that is adequate for observing the expected variations in atmospheric and other natural H-2. This method opens the road to new research on the natural H-2 cycle.

Based on HST and MUSE data, we probe the stellar and gas properties (i.e. kinematics, stellar mass, star formation rate) of the radio-loud brightest cluster galaxy (BCG) located at the centre of the X-ray luminous cool core cluster Abell 2667 (z = 0.2343). The bi-dimensional modelling of the BCG surface brightness profile reveals the presence of a complex system of substructures extending all around the galaxy. Clumps of different size and shape plunged into a more diffuse component constitute these substructures, whose intense 'blue' optical colour hints to the presence of a young stellar population. Our results depict the BCG as a massive (M_star ~ 1.38 x 10^11 M_sun) dispersion-supported spheroid (v_star < 150 km/s, sigma_0 ~ 216 km/s) hosting an active supermassive black hole (M_SMBH ~ 3.8 x 10^9 M_sun) whose optical features are typical of low ionisation nuclear emission line regions. Although the velocity pattern of the stars in the BCG is irregular, the stellar kinematics in the regions of the clumps show a positive velocity of ~ 100 km/s, similarly to the gas component. An analysis of the mechanism giving rise to the observed lines in the clumps through empirical diagnostic diagrams points out that the emission is composite, suggesting the contribution from both star formation and AGN. We conclude our analysis describing how scenarios of both chaotic cold accretion and merging with a gas-rich disc galaxy can efficaciously explain the phenomena the BCG is undergoing., Accepted for publication on the 10th of June 2019 (MNRAS)

With the recent discovery of a dozen dusty star-forming galaxies and around 30 quasars at z > 5 that are hyper-luminous in the infrared (mu L-IR > 10(13) L-circle dot, where is a lensing magnification factor), the possibility has opened up for SPICA, the proposed ESA M5 mid-/far-infrared mission, to extend its spectroscopic studies toward the epoch of reionisation and beyond. In this paper, we examine the feasibility and scientific potential of such observations with SPICA's far-infrared spectrometer SAFARI, which will probe a spectral range (35-230 mu m) that will be unexplored by ALMA and JWST. Our simulations show that SAFARI is capable of delivering good-quality spectra for hyper-luminous infrared galaxies at z = 5 - 10, allowing us to sample spectral features in the rest-frame mid-infrared and to investigate a host of key scientific issues, such as the relative importance of star formation versus AGN, the hardness of the radiation field, the level of chemical enrichment, and the properties of the molecular gas. From a broader perspective, SAFARI offers the potential to open up a new frontier in the study of the early Universe, providing access to uniquely powerful spectral features for probing first-generation objects, such as the key cooling lines of low-metallicity or metal-free forming galaxies (fine-structure and H-2 lines) and emission features of solid compounds freshly synthesised by Population III supernovae. Ultimately, SAFARI's ability to explore the high-redshift Universe will be determined by the availability of sufficiently bright targets (whether intrinsically luminous or gravitationally lensed). With its launch expected around 2030, SPICA is ideally positioned to take full advantage of upcoming wide-field surveys such as LSST, SKA, Euclid, and WFIRST, which are likely to provide extraordinary targets for SAFARI.

A network of three tall tower measurement stations was set up in 2012 across the United Kingdom to expand measurements made at the long-term background northern hemispheric site, Mace Head, Ireland. Reliable and precise in situ greenhouse gas (GHG) analysis systems were developed and deployed at three sites in the UK with automated instrumentation measuring a suite of GHGs. The UK Deriving Emissions linked to Climate Change (UK DECC) network uses tall (165–230 m) open-lattice telecommunications towers, which provide a convenient platform for boundary layer trace gas sampling. In this paper we describe the automated measurement system and first results from the UK DECC network for CO2, CH4, N2O, SF6, CO and H2. CO2 and CH4 are measured at all of the UK DECC sites by cavity ring-down spectroscopy (CRDS) with multiple inlet heights at two of the three tall tower sites to assess for boundary layer stratification. The short-term precisions (1σ on 1 min means) of CRDS measurements at background mole fractions for January 2012 to September 2015 is −1 for CO2 and −1 for CH4. Repeatability of standard injections (1σ) is −1 for CO2 and −1 for CH4 for the same time period. N2O and SF6 are measured at three of the sites, and CO and H2 measurements are made at two of the sites, from a single inlet height using gas chromatography (GC) with an electron capture detector (ECD), flame ionisation detector (FID) or reduction gas analyser (RGA). Repeatability of individual injections (1σ) on GC and RGA instruments between January 2012 and September 2015 for CH4, N2O, SF6, CO and H2 measurements were −1, −1, −1, −1 and −1, respectively. Instrumentation in the network is fully automated and includes sensors for measuring a variety of instrumental parameters such as flow, pressures, and sampling temperatures. Automated alerts are generated and emailed to site operators when instrumental parameters are not within defined set ranges. Automated instrument shutdowns occur for critical errors such as carrier gas flow rate deviations. Results from the network give good spatial and temporal coverage of atmospheric mixing ratios within the UK since early 2012. Results also show that all measured GHGs are increasing in mole fraction over the selected reporting period and, except for SF6, exhibit a seasonal trend. CO2 and CH4 also show strong diurnal cycles, with night-time maxima and daytime minima in mole fractions.

With the recent discovery of a dozen dusty star-forming galaxies and around 30 quasars at z>5 that are hyper-luminous in the infrared ($��$$L_{\rm IR}>10^{13}$ L$_{\odot}$, where $��$ is a lensing magnification factor), the possibility has opened up for SPICA, the proposed ESA M5 mid-/far-infrared mission, to extend its spectroscopic studies toward the epoch of reionization and beyond. In this paper, we examine the feasibility and scientific potential of such observations with SPICA's far-infrared spectrometer SAFARI, which will probe a spectral range (35-230 $��$m) that will be unexplored by ALMA and JWST. Our simulations show that SAFARI is capable of delivering good-quality spectra for hyper-luminous infrared galaxies (HyLIRGs) at z=5-10, allowing us to sample spectral features in the rest-frame mid-infrared and to investigate a host of key scientific issues, such as the relative importance of star formation versus AGN, the hardness of the radiation field, the level of chemical enrichment, and the properties of the molecular gas. From a broader perspective, SAFARI offers the potential to open up a new frontier in the study of the early Universe, providing access to uniquely powerful spectral features for probing first-generation objects, such as the key cooling lines of low-metallicity or metal-free forming galaxies (fine-structure and H2 lines) and emission features of solid compounds freshly synthesized by Population III supernovae. Ultimately, SAFARI's ability to explore the high-redshift Universe will be determined by the availability of sufficiently bright targets (whether intrinsically luminous or gravitationally lensed). With its launch expected around 2030, SPICA is ideally positioned to take full advantage of upcoming wide-field surveys such as LSST, SKA, Euclid, and WFIRST, which are likely to provide extraordinary targets for SAFARI., 24 pages, 8 figures, accepted for publication in PASA (SPICA special issue)

Photometry of the nebulae LDN1780, LDN1642 and LBN406 is used to derive scattering properties of dust and to investigate the presence of UV fluorescence emission by molecular hydrogen and the extended red emission (ERE). We used multi-wavelength optical photometry and imaging at ground-based telescopes and archival imaging and spectroscopic UV data from the spaceborn GALEX and SPEAR/FIMS instruments. We used Monte Carlo RT and both observational data and synthetic models for the ISRF in the solar neighbourhood. The line-of-sight extinctions through the clouds have been determined using near infrared excesses of background stars and the 200/250um far infrared emission by dust measured using the ISO and Herschel space observatories. The optical surface brightness of the target clouds can be explained in terms of scattered light. The dust albedo ranges from 0.58 at 3500A to 0.72 at 7500A. The SED of LDN1780 is explained in terms of optical depth and background scattered light effects instead of ERE. The FUV surface brightness of LDN 1780 cannot be explained by scattered light only. In LDN1780 H2 fluorescent emission in the wavelength range 1400A-1700A has been detected and analysed. Our albedo values agree with the predictions of the dust model of Weingartner and Draine and with the THEMIS CMM model for evolved core-mantle grains. The H2 fluorescent emission in LDN1780 shows a pronounced dichotomy with a preference for its southern side where enhanced illumination impinges from the Sco OB2 association and the O star zeta Oph. A good correlation is found between the H2 fluorescence and a previously mapped 21-cm excess emission. The H2 fluorescence emission in LDN1780 has been modelled using a PDR code; the resulting values for H2 column density and the total gas density are consistent with the estimates derived from CO observations and optical extinction along the line of sight., Comment: 30 pages, 21 figures, Astronomy and Astrophysics in press

Within a Lambda Cold Dark Matter (LCDM) scenario, we use high resolution cosmological simulations spanning over four orders of magnitude in galaxy mass to understand the deficit of dwarf galaxies in observed velocity functions. We measure velocities in as similar a way as possible to observations, including generating mock HI data cubes for our simulated galaxies. We demonstrate that this apples-to-apples comparison yields an "observed" velocity function in agreement with observations, reconciling the large number of low-mass halos expected in a LCDM cosmological model with the low number of observed dwarfs at a given velocity. We then explore the source of the discrepancy between observations and theory, and conclude that the dearth of observed dwarf galaxies is primarily explained by two effects. The first effect is that galactic rotational velocities derived from the HI linewidth severely underestimate the maximum halo velocity. The second effect is that a large fraction of halos at the lowest masses are too faint to be detected by current galaxy surveys. We find that cored dark matter density profiles can contribute to the lower observed velocity of galaxies, but only for galaxies in which the velocity is measured interior to the size of the core (~3 kpc)., Comment: updated after acceptance for publication in ApJ

It is not well known what drives the chemistry of a protostellar envelope, in particular the role of the stellar mass and the outflows on its chemical enrichment. We study the chemical structure of NGC 1333 IRAS 4A in order to (i) investigate the influence of the outflows on the chemistry, (ii) constrain the age of our object, (iii) compare it with a typical high-mass protostellar envelope. In our analysis we use JCMT line mapping and HIFI pointed spectra. To study the influence of the outflow on the degree of deuteration, we compare JCMT maps of HCO+ and DCO+ with non-LTE (RADEX) models in a region that spatially covers the outflow activity of IRAS 4A. To study the envelope chemistry, we derive empirical molecular abundance profiles for the observed species using the radiative transfer code (RATRAN) and adopting a 1D dust density/temperature profile from the literature. We compare our best-fit observed abundance profiles with the predictions from the time dependent gas grain chemical code (ALCHEMIC). The CO, HCN, HNC and CN abundance require an enhanced UV field which points towards an outflow cavity. The abundances (wrt H2) are 1 to 2 orders of magnitude lower than those observed in the high mass protostellar envelope (AFGL 2591), while they are found to be similar within factors of a few with respect to CO. Differences in UV radiation may be responsible for such chemical differentiation, but temperature differences seem a more plausible explanation. The CH3OH modeled abundance profile points towards an age of > 4x10^4 yrs for IRAS 4A. The spatial distribution of H2D+ differs from that of other deuterated species, indicating an origin from a foreground colder layer (, 26 pages, 23 Figures, 6 tables, accepted for publication in A&A

2-(Dialkylamino) phenylboranes containing the BXZ group, where X, Z = C6F5, Cl, and H, were prepared in a few synthetic steps and demonstrated the cleavage of H-2 under mild conditions. Depending on the nature of the dialkylamino group, X, and Z, the stability of the produced zwitterionic H-2 adducts varies from isolated solids indefinitely stable in an inert atmosphere to those quickly equilibrating with the initial aminoborane and H-2. Using a combined experimental/computational approach on a series of isostructural aminoboranes (dialkylamino = 2,2,6,6-tetramethylpiperid-1-yl), it was demonstrated that the electro-negativity and the steric effect of the substituents generally follow the trend C6F5 similar to Cl >> H. This observation is useful for designing new FLPs for practical applications. As an example, we demonstrated the hydrogenation of alkynes to cis-alkenes under mild conditions that was catalyzed by a chloro-analogue of the C6F5-substituted aminoborane developed previously. The presence of a BHCl group in the amino-chloroboranes or in their H-2 adducts features facile redistribution of the H and Cl atoms and the formation of polychloro and polyhydrido species.

We present neutral hydrogen observations for a sample of eight nearby, late-type, edge-on galaxies. All of the galaxies have been well resolved in the radial direction, while six have also been well resolved in the vertical direction. We find that each of the galaxies has approximately the same maximum surface brightness temperature throughout its disc. We argue that self-absorption is the main cause of this phenomenon and that subsequent decompositions will require a treatment of this.

The discovery in 2004 that graphene can be produced by micromechanical exfoliation brought forth a plethora of unique electronic, mechanical, thermal and optical properties of this first stable two dimensional (2-D) material ever isolated, which afforded the Nobel Prize to Andrei Geim and Konstantin Novoselov in 2010. One of the peculiarities of graphene is its extremely high specific surface area, which in combination with its low weight, robustness and chemical inertness places it among the most suitable materials for hydrogen storage devices. In this review we discuss the experimental and theoretical approaches applied so far to harness graphene and its derivatives as main building blocks for hydrogen uptake and storage; the potential of each approach for future applications in the hydrogen economy will also be examined. (C) 2013 The Electrochemical Society. All rights reserved.

This work reassesses the global atmospheric budget of H2 with the TM5 model. The recent adjustment of the calibration scale for H2 translates into a change in the tropospheric burden. Furthermore, the ECMWF Reanalysis-Interim (ERA-Interim) data from the European Centre for Medium-Range Weather Forecasts (ECMWF) used in this study show slower vertical transport than the operational data used before. Consequently, more H2 is removed by deposition. The deposition parametrization is updated because significant deposition fluxes for snow, water, and vegetation surfaces were calculated in our previous study. Timescales of 1-2h are asserted for the transport of H2 through the canopies of densely vegetated regions. The global scale variability of H2 and [DH2] is well represented by the updated model. H2 is slightly overestimated in the Southern Hemisphere because too little H2 is removed by dry deposition to rainforests and savannahs. The variability in H2 over Europe is further investigated using a high-resolution model subdomain. It is shown that discrepancies between the model and the observations are mainly caused by the finite model resolution. The tropospheric burden is estimated at 165 +/- 8TgH2. The removal rates of H2 by deposition and photochemical oxidation are estimated at 53 +/- 4 and 23 +/- 2TgH2/yr, resulting in a tropospheric lifetime of 2.2 +/- 0.2year.

The parahydrogen-induced polarization (PHIP) phenomenon, observed when parahydrogen is used in H-2 addition processes, provides a means for substantial NMR signal enhancements and mechanistic studies of chemical reactions. Commonly, noble metal complexes are used for parahydrogen activation, whereas metal-free activation is rare. Herein, we report a series of unimolecular metal-free frustrated Lewis pairs based on an ansa-aminoborane (AAB) moiety in the context of PHIP. These molecules, which have a "molecular tweezers'' structure, differ in their substituents at the boryl site (-H, -Ph, -o-iPr-Ph, and -Mes). PHIP effects were observed for all the AABs after exposing their solutions to parahydrogen in a wide temperature range, and experimental measurements of their kinetic and thermodynamic parameters were performed. A theoretical analysis of their nuclear spin polarization effects is presented, and the roles of chemical exchange, chemical equilibrium and spin dynamics are discussed in terms of the key dimensionless parameters. The analysis allowed us to formulate the prerequisites for achieving strong polarization effects with AAB molecules, which can be applied for further design of efficient metal-free tweezers-like molecules for PHIP. Mechanistic (chemical and physical) aspects of the observed effects are discussed in detail. In addition, we performed quantum chemical calculations, which confirmed that the J-coupling between the parahydrogen-originated protons in AAB-H-2 molecules is mediated through dihydrogen bonding.

Contemporary society demands innovative answers to the environmental and energetic issue. A remarkably promising and widely discussed route to achieve this intent is based on artificial photosynthesis, i.e. the conversion of light into fuels by molecules that mimic the natural photosystems. The main aim of this thesis is the design, synthesis and characterization of new metal-chromophore supramolecular conjugates for photocatalytic applications, with specific focus on the homogeneous generation of molecular hydrogen. Particular attention was given to water soluble noble-metal-free systems, in order to meet both environment and cost requirements. Herein are described manifold applications of metallo-porphyrins for hydrogen photoreduction: as photosensitizer units in multi-component photoactive systems, as chromophores in antenna systems, and as catalysts, while offering at the same time a variety of structural handles for the assembling of the active partners.

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their stable isotopic composition and isotope fractionation constants, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For δD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended.

Electron beam induced deposition (EBID) is a direct-write lithographic technique that utilizes the dissociation of volatile precursors by a focused electron beam in a low vacuum environment to create nanostructures. Notable advantages of EBID over competing lithographic techniques are that it is a single step process that allows three-dimensional free-standing structures to be created, including features with single-nanometer scale dimensions. However, despite the inherent advantages of EBID, scientific and technological issues are impeding its development as an industrial nanofabrication tool. Perhaps the greatest single limitation of EBID is that metal-containing nanostructures deposited from organometallic precursors typically possess unacceptable levels of organic contamination which adversely affects the material's properties. In addition to the issue of purity, there is also a lack of understanding and quantitative information on the fundamental surface reactions and reaction cross-sections that are responsible for EBID. In this prospective, we describe how surface analytical techniques have begun to provide mechanistic and kinetic insights into the molecular level processes associated with EBID. This has been achieved by observing the effect of electron irradiation on nanometer thick films of organometallic precursors adsorbed onto solid substrates at low temperatures (

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For dD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended.

This paper introduces a new disk code, called ProDiMo, to calculate the thermo-chemical structure of protoplanetary disks and to interpret gas emission lines from UV to sub-mm. We combine frequency-dependent 2D dust continuum radiative transfer, kinetic gas-phase and UV photo-chemistry, ice formation, and detailed non-LTE heating & cooling balance with the consistent calculation of the hydrostatic disk structure. We include FeII and CO ro-vibrational line heating/cooling relevant for the high-density gas close to the star, and apply a modified escape probability treatment. The models are characterized by a high degree of consistency between the various physical, chemical and radiative processes, where the mutual feedbacks are solved iteratively. In application to a T Tauri disk extending from 0.5AU to 500AU, the models are featured by a puffed-up inner rim and show that the dense, shielded and cold midplane (z/r, 24 pages, 14 figures, 120 equations, accepted by A&A, download a high-resolution version from http://www.roe.ac.uk/~ptw/prodimo1_article.pdf

Context. Emission lines from protoplanetary disks originate mainly in the irradiated surface layers, where the gas is generally warmer than the dust. Therefore, interpreting emission lines requires detailed thermo-chemical models, which are essential to converting line observations into understanding disk physics.Aims. We aim at hydrostatic disk models that are valid from 0.1AU to 1000 AU to interpret gas emission lines from UV to sub-mm. In particular, our interest lies in interpreting far IR gas emission lines, such as will be observed by the Herschel observatory, related to the Gasps open time key program. This paper introduces a new disk code called ProDIMo.Methods. We combine frequency-dependent 2D dust continuum radiative transfer, kinetic gas-phase and UV photo-chemistry, ice formation, and detailed non-LTE heating & cooling with the consistent calculation of the hydrostatic disk structure. We include Fe II and CO ro-vibrational line heating/cooling relevant to the high-density gas close to the star, and apply a modified escape-probability treatment. The models are characterised by a high degree of consistency between the various physical, chemical, and radiative processes, where the mutual feedbacks are solved iteratively.Results. In application to a T Tauri disk extending from 0.5 AU to 500 AU, the models show that the dense, shielded and cold midplane (z/r less than or similar to 0.1, T(g) approximate to T(d)) is surrounded by a layer of hot (T(g) approximate to 5000 K) and thin (n() approximate to 10(7) to 10(8) cm(-3)) atomic gas that extends radially to about 10 AU and vertically up to z/r approximate to 0.5. This layer is predominantly heated by the stellar UV (e. g. PAH-heating) and cools via Fe II semi-forbidden and OI 630 nm optical line emission. The dust grains in this "halo" scatter the starlight back onto the disk, which affects the photochemistry. The more distant regions are characterised by a cooler flaring structure. Beyond r greater than or similar to 100 AU, T(g) decouples from T(d) even in the midplane and reaches values of about T(g) approximate to 2T(d).Conclusions. Our models show that the gas energy balance is the key to understanding the vertical disk structure. Models calculated with the assumption T(g) = T(d) show a much flatter disk structure. The conditions in the close regions () approximate to 10(8) to 10(15) cm(-3) resemble those of cool stellar atmospheres and, thus, the heating and cooling is more like in stellar atmospheres. The application of heating and cooling rates known from PDR and interstellar cloud research alone can be misleading here, so more work needs to be invested to identify the leading heating and cooling processes.

Many present-day galaxies are known to harbor supermassive, >10^6 Mo, black holes. These central black holes must have grown through accretion from less massive seeds in the early universe. The molecules CO and H2 can be used to trace this young population of accreting massive black holes through the X-ray irradiation of ambient gas. The X-rays drive a low-metallicity ion-molecule chemistry that leads to the formation and excitation of CO and H2 in 10015 and H2 S(0) & S(1) emission is found that allows one to constrain ambient conditions. Comparable line strengths cannot be produced by FUV or cosmic ray irradiation. Weak, but perhaps detectable, H3+ (2,2) - (1,1) emission is found and discussed. The models predict that black hole masses larger than 10^5 Mo can be detected with ALMA, over a redshift range of 5-20, provided that the black holes radiate close to Eddington., Comment: 12 pages, 3 figures, ApJL accepted; minor typographical changes

Hydrogen physisorption on porous high surface materials is investigated for the purpose of hydrogen storage and hydrogen separation, because of its simplicity and intrinsic reversibility. For these purposes, the understanding of the binding of dihydrogen to materials, of the structure of the adsorbed phase and of the ortho–para conversion during thermal and pressure cycles are crucial for the development of new hydrogen adsorbents. We report the direct observation by IR spectroscopic methods of structured hydrogen adsorption on a porous titanosilicate (ETS-10), with resolution of the kinetics of the ortho–para transition, and an interpretation of the structure of the adsorbed phase based on classical atomistic simulations. Distinct infrared signals of o- and p-H2 in different adsorbed states are measured, and the conversion of o- to p-H2 is monitored over a timescale of hours, indicating the presence of a catalyzed reaction. Hydrogen adsorption occurs in three different regimes characterized by well separated IR manifestations: at low pressures ordered 1 : 1 adducts with Na and K ions exposed in the channels of the material are formed, which gradually convert into ordered 2 : 1 adducts. Further addition of H2 occurs only through the formation of a disordered condensed phase. The binding enthalpy of the Na+−H2 1 : 1 adduct is of −8.7 ± 0.1 kJ mol−1, as measured spectroscopically. Modeling of the weak interaction of H2 with the materials requires an accurate force field with a precise description of both dispersion and electrostatics. A novel three body force field for molecular hydrogen is presented, based on the fitting of an accurate PES for the H2–H2 interaction to the experimental dipole polarizability and quadrupole moment. Molecular mechanics simulations of hydrogen adsorption at different coverages confirm the three regimes of adsorption and the structure of the adsorbed phase.

The ISO spectra of the bilobal planetary nebula Hb 5 are presented. These spectra are combined with the spectra in the visual wavelength region to obtain a complete, extinction corrected, spectrum. The chemical composition of the nebula is then calculated in several ways. First by directly calculating and adding individual ion abundances, assuming that all the ionic lines are formed in an ionized region surrounding the ionizing star. Secondly by building an "end-to-end model" nebula in which we have included a neutral region and a photodissociation region (PDR) beyond the ionized nebula. In this way we attempt to interpret the molecular hydrogen lines observed by ISO in a more self-consistent way. In the final analysis, the model is found to be basically heuristic, but gives new insights about the PDR and the PN. The implications of these are discussed.

The kinetics of E' centers induced in silica by 4.7eV laser irradiation was investigated observing in situ their optical absorption band at 5.8 eV. After exposure the defects decay due to reaction with diffusing molecular hydrogen of radiolytic origin. Hydrogen-related annealing is active also during exposure and competes with the photo-induced generation of the centers until a saturation is reached. The concentrations of E' and H2 at saturation are proportional, so indicating that the UV-induced generation processes of the two species are correlated. These results are consistent with a model in which E' and hydrogen are generated from a common precursor Si-H., Comment: 13 pages, 3 figures, 1 table

We present Infrared Space Observatory mid- and far-infrared spectroscopy of the merging galaxy NGC 6240, an object presenting many aspects of importance for the role of star formation and AGN activity in [ultra]luminous infrared galaxies. The mid-infrared spectrum shows starburst indicators in the form of low excitation fine-structure line emission and aromatic `PAH' features. A strong high excitation [OIV] line is observed which most likely originates in the Narrow Line Region of an optically obscured AGN. NGC 6240 shows extremely powerful emission in the pure rotational lines of molecular hydrogen. We argue that this emission is mainly due to shocks in its turbulent central gas component and its starburst superwind. The total shock cooling in infrared emission lines accounts for ~0.6% of the bolometric luminosity, mainly through rotational H_2 emission and the [OI] 63micron line. We analyse several ways of estimating the luminosities of the starburst and the AGN in NGC 6240 and suggest that the contributions to its bolometric luminosity are most likely in the range 50-75% starburst and 25-50% AGN., 5 figures. Accepted for publication in A&A

The low-frequency electrical conductivity of strongly nonideal hydrogen, helium, and xenon plasmas was measured in the megabar range of pressures. The plasmas in question were generated by the method of multiple shock compression in planar and cylindrical geometries, whereby it was possible to reduce effects of irreversible heating and to implement a quasi-isentropic regime. As a result, plasma states at pressures in the megabar range were realized, where the electron concentration could be as high as n(e) approximate to 2 x 10(23) cm(-3), which may correspond to either a degenerate or a Boltzmann plasma characterized by a strong Coulomb (Gamma(D) = 1-10) and a strong interatomic (Gamma(a) = r(a)n(a)(1/3) similar to 1) interaction. A sharp increase (by three to five orders of magnitude) in the electrical conductivity of a strongly nonideal plasma due to pressure-produced ionization was recorded, and theoretical models were invoked to describe this increase. Experimental data available in this region and theoretical models proposed by various authors are analyzed. The possibility of a first-order "phase transition" in a strongly nonideal plasma is indicated. (C) 2003 MAIK "Nauka / Interperiodica".

Graphene rippled at the nanoscale level is gathering attention for advanced applications, especially in the field of nanoelectronics and hydrogen storage. Convexity enhanced reactivity toward H was demonstrated on naturally corrugated graphene grown by Si evaporation on SiC, which makes this system a platform for fundamental studies on the effects of rippling. In this work, we report a density functional theory study on a model system specifically designed to mimic graphene on SiC. We first study the supercell geometry and configuration that better reproduce the corrugated monolayer. The relatively low computational cost of this model system allows a systematic study of the dependence of stability, structure, and electronic properties of graphene subject to different levels of stretching and corrugation. The most representative structure is then progressively hydrogenated, imitating the exposure to atomic hydrogen, and stability, structural and electronic properties are evaluated as a function of hydrogenation. Our results quantitatively reproduce the measured evolution of electronic properties as a function of hydrogenation, offering the possibility of evaluating the coverage by means of STS measurements. The dependence of hydrogen binding energy on coverage extends our previous results on reactivity of corrugated graphene, including the effect of H clustering. This work reports quantitative results directly comparable with experimental measurements performed on epitaxial graphene on SiC and reveals the quantitative interplay between local structure, electronic properties and reactivity to hydrogen, which could be used to design devices for flexible nanoelectronics and for H storage.

We present a first-principles computational study of solid He-4 at T = 0 K and pressures up to similar to 160 GPa. Our computational strategy consists in using van der Waals density functional theory (DFT-vdW) to describe the electronic degrees of freedom in this material, and the diffusion Monte Carlo (DMC) method to solve the Schrodinger equation describing the behavior of the quantum nuclei. For this, we construct an analytical interaction function based on the pairwise Aziz potential that closely matches the volume variation of the cohesive energy calculated with DFT-vdW in dense helium. Interestingly, we find that the kinetic energy of solid He-4 does not increase appreciably with compression for P >= 85 GPa. Also, we show that the Lindemann ratio in dense solid He-4 amounts to 0.10 almost independently of pressure. The reliability of customary quasiharmonic DFT (QH DFT) approaches in describing quantum nuclear effects in solids is also studied. We find that QH DFT simulations, although provide a reasonable equation of state in agreement with experiments, are not able to reproduce correctly these critical effects in compressed He-4. In particular, we disclose huge discrepancies of at least similar to 50% in the calculated He-4 kinetic energies using both the QH DFT and present DFT-DMC methods.

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflectionabsorption spectroscopy (IRAS) as a function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than similar to 15 ML from the vacuum interface, CO oxidation to CO2 dominates over the sequential hydrogenation of CO to methanol (CH3OH), consistent with previous observations. At its highest yield, CO2 accounts for similar to 45% of all the reacted CO. Another oxidation product is identified as the formate anion (HCO2). In contrast, for CO buried more than similar to 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate is not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on preirradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone, resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.

Inelastic neutron scattering (INS) has been employed to investigate the quantum dynamics of water molecules permanently entrapped inside the cages of C60 fullerene molecules. This study of the supramolecular complex, H2O@C60, provides the unique opportunity to study isolated water molecules in a highly symmetric environment. Free from strong interactions, the water molecule has a high degree of rotational freedom enabling its nuclear spin isomers, ortho-H2O and para-H2O to be separately identified and studied. The INS technique mediates transitions between the ortho and para spin isomers and using three INS spectrometers, the rotational levels of H2O have been investigated, correlating well with the known levels in gaseous water. The slow process of nuclear spin conversion between ortho-H2O and para-H2O is revealed in the time dependence of the INS peak intensities over periods of many hours. Of particular interest to this study is the observed splitting of the ground state of ortho-H2O, raising the three-fold degeneracy into two states with degeneracy 2 and 1 respectively. This is attributed to a symmetry-breaking interaction of the water environment.

The dust-Hi correlation is used to characterize the emission properties of dust in the diffuse interstellar medium (ISM) from far infrared wavelengths to microwave frequencies. The field of this investigation encompasses the part of the southern sky best suited to study the cosmic infrared and microwave backgrounds. We cross-correlate sky maps from Planck, the Wilkinson Microwave Anisotropy Probe (WMAP), and the diffuse infrared background experiment (DIRBE), at 17 frequencies from 23 to 3000 GHz, with the Parkes survey of the 21 cm line emission of neutral atomic hydrogen, over a contiguous area of 7500 deg2 centred on the southern Galactic pole. We present a general methodology to study the dust-H i correlation over the sky, including simulations to quantify uncertainties. Our analysis yields four specific results. (1) We map the temperature, submillimetre emissivity, and opacity of the dust per H-atom. The dust temperature is observed to be anti-correlated with the dust emissivity and opacity. We interpret this result as evidence of dust evolution within the diffuse ISM. The mean dust opacity is measured to be (7.1 ± 0.6) × 10-27 cm2 H-1 × (v/353 GHz) 1.53 ± 0.03for 100 ≤ v ≤ 353 GHz. This is a reference value to estimate hydrogen column densities from dust emission at submillimetre and millimetre wavelengths. (2) We map the spectral index βmm of dust emission at millimetre wavelengths (defined here as v ≤ 353GHz), and find it to be remarkably constant at βmm = 1.51 ± 0.13. We compare it with the far infrared spectral index βFIR derived from greybody fits at higher frequencies, and find a systematic difference, βmm -βFIR = -0.15, which suggests that the dust spectral energy distribution (SED) flattens at v ≤ 353 GHz. (3) We present spectral fits of the microwave emission correlated with Hi from 23 to 353 GHz, which separate dust and anomalous microwave emission (AME). We show that the flattening of the dust SED can be accounted for with an additional component with a blackbody spectrum. This additional component, which accounts for (26 ± 6)% of the dust emission at 100GHz, could represent magnetic dipole emission. Alternatively, it could account for an increasing contribution of carbon dust, or a flattening of the emissivity of amorphous silicates, at millimetre wavelengths. These interpretations make different predictions for the dust polarization SED. (4) We analyse the residuals of the dust-Hi correlation. We identify a Galactic contribution to these residuals, which we model with variations of the dust emissivity on angular scales smaller than that of our correlation analysis. This model of the residuals is used to quantify uncertainties of the CIB power spectrum in a companion Planck paper.© ESO 2014., The Planck Collaboration acknowledges support from: ESA; CNES and CNRS/INSU-IN2P3-INP (France); ASI, CNR, and INAF (Italy); NASA and DoE (USA); STFC and UKSA (UK); CSIC, MICINN and JA (Spain); Tekes, AoF and CSC (Finland); DLR and MPG (Germany); CSA (Canada); DTU Space (Denmark); SER/SSO (Switzerland); RCN (Norway); SFI (Ireland); FCT/MCTES (Portugal); and PRACE (EU). The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) / ERC grant agreement nº 267934.

Low-energy (100 eV) electron-stimulated reactions in layered H 2O/CO/H2O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10-50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations. © 2014 AIP Publishing LLC.

We report results from a Hubble Space Telescope (HST) and Near-Infrared Camera and Multiobject Spectrometer (NICMOS) program to study the distribution of hot neutral (molecular hydrogen) and ionized circumstellar material in the young planetary nebulae NGC 7027. HST/NICMOS provided very high spatial resolution imaging in line and continuum emission, and the stability and large dynamic range needed for investigating detailed structures in the circumstellar material. We present dramatic new images of NGC 7027 that have led to a new understanding of the structure in this important planetary nebula. The central star is clearly revealed, providing near-infrared fluxes that are used to directly determine the stellar temperature very accurately (T* = 198,000 K). It is found that the photodissociation layer as revealed by near-infrared molecular hydrogen emission is very thin (Delta R similar to 6 x 10(15) cm) and is biconical in shape. The interface region is structured and filamentary, suggesting the existence of hydrodynamic instabilities. We discuss evidence for the presence of one or more highly collimated, off-axis jets that might be present in NGC 7027. The NICMOS data are combined with earlier Hubble Space Telescope data to provide a complete picture of NGC 7027 using the highest spatial resolution data to date. The evolutionary future of NGC 7027 is discussed.

We present high-angular-resolution, far-infrared images of the Small Magellanic Cloud (SMC). The images were reconstructed from data obtained with the Infrared Astronomical Satellite (IRAS), using the Pyramid Maximum Entropy algorithm. The angular resolutions of the images are 1 arcmin at 12, 25 and 60 mu m, and 1.7 arcmin at 100 mu m, which provides an excellent complement to the recent neutral hydrogen (H I) survey from the Australia Telescope Compact Array, which has a resolution of 1.6 arcmin. We use the 60- and 100-mu m data, together with a standard dust model, to derive a temperature map and a dust column density distribution. Dust temperatures range from 23 to 45 K, which is, on average, warmer than for the Galaxy, although there is a deficit of warm, very small dust grains in the SMC. The total amount of cool dust in the SMC is 1.8(-0.2)(+1.3) x 10(4) M.. There is a significant variation of the observed dust-to-gas ratio across the SMC. This may be caused by corresponding variations in metallicity, but this explanation is not supported by the limited available data in the literature. Alternatively, there may be a large amount of molecular hydrogen (H(2)) in the SMC, similar to 8 x 10(8) M., and/or a large amount (similar to 10(6) M.) of cold dust (less than or equal to 15 K) not seen by IRAS or COBE/DIRBE. The average dust-to-atomic gas ratio is, by mass, 8.2 x 10(-5), which is a factor of similar to 30 below the Galactic value. The spatial power spectrum of the dust column density image can be approximated by P(d)(k) proportional to k(-3.1), which shows that, as with the H I power spectrum, there is no preferred scale size for dust clouds. A spatial coherence analysis shows that, over a wide range of spatial scales (greater than or similar to 50 pc), H I and dust are well correlated (> 60 per cent).

ORFEUS far UV echelle spectra have been used to investigate HI, Hz and CO absorption lines along the line of sight towards LH 10:3120 in the LMC, extending the study presented by de Beer et al. (1998). While Hz absorption is clearly visible, no CO absorption at LMC velocities is detected, but an upper limit of N(CO) less than or equal to 3.3 x 10(13) cm(-2) for the CO column density is derived for the C-X band near 1088 Angstrom. The detected Hz absorption features were used to determine a limit for the H-2/CO ratio of N(H-2)/N((CO)-C-12) greater than or equal to 2.0 X 10(5) for the LMC gas along this individual line of sight. Generally, the fraction of gas in molecular form in the LMC is low compared to interstellar gas in the Milky Way with the same total gas quantity. We compare the absorption spectroscopy with SEST CO emission line measurements. It is found that most of the CO emission comes from gas behind LH 10:3120. We discuss our results in view of the possible scenario, in which the low dust content limits the amount of molecular hydrogen in the diffuse LMC gas.

We present the results of ISO SWS and LWS spectroscopy of the young binary system T Tau. The spectrum shows absorption features due to H2O ice, CO2 ice, gas-phase CO and amorphous silicate dust, which we attribute to the envelope of T Tau S. We derive an extinction of A(V) = 17(m)4 +/- O(m)6 towards this source. Detected emission lines from H I arise in the same region which is also responsible for the optical Hr lines of T Tau N. These lines most likely arise in a partially ionized wind. Emission from the infrared fine-structure transitions of [S I], [ArII], [Ne II], [Fe 11], [Si II], [O I] and [C II] was also detected, which we explain as arising in a approximate to 100 km s(-1) dissociative shock in a fairly dense(5 x 10(4) cm(-3)) medium. Pure rotational and rovibrational emission from molecular hydrogen was detected as well. We show the H-2 emission lines to be due to two thermal components, of 440 and 1500 K respectively, which we attribute to emission from the dissociative shock also responsible for the atomic fine-structure lines and a much slower (approximate to 35 km s(-1)) non-dissociative shock. The 1500 K component shows clear evidence for fluorescent UV excitation. Additionally, we found indications for the presence of a deeply embedded (A(V) > 40 degrees) source of warm Ha emission. We suggest that this component might be due to a shock, caused by either the outflow from T Tau S or by the infall of matter on the circumstellar disk of T Tau S.