Hydrogenation of CO on a silica surface: an embedded cluster approach

The sequential addition of H atoms to CO adsorbed on a siliceous edingtonite surface is studied with an embedded cluster approach, using density functional theory for the quantum mechanical (QM) cluster and a molecular force field for the molecular mechanical (MM) cluster. With this setup, calculated QM/MM adsorption energies are in agreement with previous calculations employing periodic boundary conditions. The catalytic effect of the siliceous edingtonite (100) surface on CO hydrogenation is assessed because of its relevance to astrochemistry. While adsorption of CO on a silanol group on the hydroxylated surface did not reduce the activation energy for the reaction with a H atom, a negatively charged defect on the surface is found to reduce the gas phase barriers for the hydrogenation of both CO and H2C = O. The embedded cluster approach is shown to be a useful and flexible tool for studying reactions on (semi-)ionic surfaces and specific defects thereon. The methodology presented here could easily be applied to study reactions on silica surfaces that are of relevance to other scientific areas, such as biotoxicity of silica dust and geochemistry

Probing Interstellar Dust with Infrared Echoes from the Cas A Supernova

We present the analysis of an IRS 5-38 {\mu}m spectrum and MIPS photometric measurements of an infrared echo near the Cassiopeia A supernova remnant observed with the Spitzer Space Telescope. We have modeled the recorded echo accounting for PAHs, quantum-heated carbon and silicate grains, as well as thermal carbon and silicate particles. Using the fact that optical light echo spectroscopy has established that Cas A originated from a type IIb supernova explosion showing an optical spectrum remarkably similar to the prototypical type IIb SN 1993J, we use the latter to construct template data input for our simulations. We are then able to reproduce the recorded infrared echo spectrum by combining the emission of dust heated by the UV burst produced at the shock breakout after the core-collapse and dust heated by optical light emitted near the visual maximum of the supernova light curve, where the UV burst and optical light curve characteristics are based on SN 1993J. We find a mean density of \sim680 H cm^{-3} for the echo region, with a size of a few light years across. We also find evidence of dust processing in the form of a lack of small PAHs with less than \sim300 carbon atoms, consistent with a scenario of PAHs destruction by the UV burst via photodissociation at the estimated distance of the echo region from Cas A. Furthermore, our simulations suggest that the weak 11 {\mu}m features of our recorded infrared echo spectrum are consistent with a strong dehydrogenated state of the PAHs. This exploratory study highlights the potential of investigating dust processing in the interstellar medium through infrared echoes.Comment: 16 pages, 14 figures, accepted for publication in the Astrophysical Journa

On the Excitation and Formation of Circumstellar Fullerenes

We compare and analyze the Spitzer mid-infrared spectrum of three fullerene-rich planetary nebulae in the Milky Way and the Magellanic Clouds; Tc1, SMP SMC16, and SMP LMC56. The three planetary nebulae share many spectroscopic similarities. The strongest circumstellar emission bands correspond to the infrared active vibrational modes of the fullerene species C60 and little or no emission is present from Polycyclic Aromatic Hydrocarbons (PAHs). The strength of the fullerene bands in the three planetary nebulae is very similar, while the ratio of the [NeIII]15.5um/[NeII]12.8um fine structure lines, an indicator of the strength of the radiation field, is markedly different. This raises questions about their excitation mechanism and we compare the fullerene emission to fluorescent and thermal models. In addition, the spectra show other interesting and common features, most notably in the 6-9um region, where a broad plateau with substructure dominates the emission. These features have previously been associated with mixtures of aromatic/aliphatic hydrocarbon solids. We hypothesize on the origin of this band, which is likely related to the fullerene formation mechanism, and compare it with modeled Hydrogenated Amorphous Carbon that present emission in this region.Comment: 13 pages, 2 tables, 7 figures, Accepted for publication in Ap

The 5.25 & 5.7 μ\mum Astronomical Polycyclic Aromatic Hydrocarbon Emission Features

Astronomical mid-IR spectra show two minor PAH features at 5.25 and 5.7 $\mu$m (1905 and 1754 cm$^{\rm - 1}$) that hitherto have been little studied, but contain information about the astronomical PAH population that complements that of the major emission bands. Here we report a study involving both laboratory and theoretical analysis of the fundamentals of PAH spectroscopy that produce features in this region and use these to analyze the astronomical spectra. The ISO SWS spectra of fifteen objects showing these PAH features were considered for this study, of which four have sufficient S/N between 5 and 6 $\mu$m to allow for an in-depth analysis. All four astronomical spectra show similar peak positions and profiles. The 5.25 $\mu$m feature is peaked and asymmetric, while the 5.7 $\mu$m feature is broader and flatter. Detailed analysis of the laboratory spectra and quantum chemical calculations show that the astronomical 5.25 and 5.7 $\mu$m bands are a blend of combination, difference and overtone bands primarily involving CH stretching and CH in-plane and CH out-of-plane bending fundamental vibrations. The experimental and computational spectra show that, of all the hydrogen adjacency classes possible on PAHs, solo and duo hydrogens consistently produce prominent bands at the observed positions whereas quartet hydrogens do not. In all, this a study supports the picture that astronomical PAHs are large with compact, regular structures. From the coupling with primarily strong CH out-of-plane bending modes one might surmise that the 5.25 and 5.7 $\mu$m bands track the neutral PAH population. However, theory suggests the role of charge in these astronomical bands might also be important.Comment: Accepted ApJ, 40 pages in pre-print, 14 figures, two onlin

Star Formation in Extreme Environments: The Effects of Cosmic Rays and Mechanical Heating

Context: Molecular data of extreme environments, such as Arp 220, but also NGC 253, show evidence for extremely high cosmic ray (CR) rates (10^3-10^4 * Milky Way) and mechanical heating from supernova driven turbulence. Aims: The consequences of high CR rates and mechanical heating on the chemistry in clouds are explored. Methods: PDR model predictions are made for low, n=10^3, and high, n=10^5.5 cm^-3, density clouds using well-tested chemistry and radiation transfer codes. Column densities of relevant species are discussed, and special attention is given to water related species. Fluxes are shown for fine-structure lines of O, C+, C, and N+, and molecular lines of CO, HCN, HNC, and HCO+. A comparison is made to an X-ray dominated region model. Results: Fine-structure lines of [CII], [CI], and [OI] are remarkably similar for different mechanical heating and CR rates, when already exposed to large amounts of UV. HCN and H2O abundances are boosted for very high mechanical heating rates, while ionized species are relatively unaffected. OH+ and H2O+ are enhanced for very high CR rates zeta > 5 * 10^-14 s^-1. A combination of OH+, OH, H2O+, H2O, and H3O+ trace the CR rates, and are able to distinguish between enhanced cosmic rays and X-rays.Comment: 13 pages, 8 figures, A&A accepte

Gas cooling within the diffuse ISM of late-type galaxies

We combine observations of spiral galaxies in the [CII] line at 158 micron, made with the Long Wavelength Spectrometer aboard ISO, with previous data from the Kuiper Airborne Observatory to study the origin of this line, which is the main coolant of the interstellar medium at relatively low temperatures. We also use HI and CO(1-0) observations of these galaxies and estimate the respective line fluxes in the same beam as the [CII] observations. We confirm the existence of a linear relation between the [CII] line intensity and the CO(1-0) line intensity, that we extend to intrinsically fainter galaxies. The dispersion around this relation is significant and due to variations in the far-UV flux, thus in the star formation rate. We find that for the least active galaxies of our sample, in terms of star formation, the rate of [CII] line emission per interstellar hydrogen atom is similar to that in the Solar neighbourhood. For those galaxies, most of the [CII] line emission comes probably from the diffuse cold atomic medium. In more active galaxies, considered globally, the average [CII] line emission is dominated by dense photodissociation regions and to some extent by the warm ionized diffuse medium. This is true in the central region of many spiral galaxies, and probably even in the interarm regions of the most actively star-forming ones.Comment: 8 pages, 6 Postscript figures, 2 Postscript tables, accepted to A&

ISOCAM observations of the Ursa Major cirrus: Evidence for large abundance variations of small dust grains

We present mid-IR imaging observations of a high Galactic latitude cirrus obtained with the ISO camera ISOCAM at 6" angular resolution. The observations were done with two filters LW2 (5-8.5 microns) and LW3 (12-18 microns) that measure respectively the aromatic carbon bands and the underlying continuum emission from small dust particles. Three 0.05 square degree images sample atomic and molecular sections in the Ursa Major cirrus. These images are compared with Hi, CO and IRAS observations. In such a cloud transparent to stellar light (Av < 0.5) the mid-infrared to 100 microns and the mid-IR emissivity per hydrogen are related to the abundance and the optical properties of small dust particles independently of any modelling of the penetration of the radiation. Within the atomic section of the cloud, the comparison between ISOCAM images and 21 cm interferometric data highlights an enhancement of the mid-IR emitters abundance by a factor ~5 in an Hi filament characterized by a large transverse velocity gradient suggestive of rotation. Furthermore, a drop in the abundance of the same mid-IR emitters is observed at the interface between the atomic and molecular cirrus sections. We propose that these abundance variations of the mid-IR emitters are related to the production of small dust particles by grain shattering in energetic grain-grain collisions generated by turbulent motions within the cirrus and inversely by their disappearance due to coagulation on large grains. At the atomic-molecular interface we also observe a decrease of the Lw2/Lw3 ratio by a factor 2 in the molecular region. This could result from a modification of the dust size distribution or of the intrinsic optical properties of the small dust particles.Comment: 11 pages, 13 figures, better resolution figures to be found in published versio

Dissociation of the benzene molecule by UV and soft X-rays in circumstellar environment

Benzene molecules, present in the proto-planetary nebula CRL 618, are ionized and dissociated by UV and X-ray photons originated from the hot central star and by its fast wind. Ionic species and free radicals produced by these processes can lead to the formation of new organic molecules. The aim of this work is to study the photoionization and photodissociation processes of the benzene molecule, using synchrotron radiation and time of flight mass spectrometry. Mass spectra were recorded at different energies corresponding to the vacuum ultraviolet (21.21 eV) and soft X-ray (282-310 eV) spectral regions. The production of ions from the benzene dissociative photoionization is here quantified, indicating that C6H6 is more efficiently fragmented by soft X-ray than UV radiation, where 50% of the ionized benzene molecules survive to UV dissociation while only about 4% resist to X-rays. Partial ion yields of H+ and small hydrocarbons such as C2H2+, C3H3+ and C4H2+ are determined as a function of photon energy. Absolute photoionization and dissociative photoionization cross sections have also been determined. From these values, half-life of benzene molecule due to UV and X-ray photon fluxes in CRL 618 were obtained.Comment: The paper contains 8 pages, 9 figures and 4 tables. Accepted to be published on MNRAS on 2008 November 2