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Register a new userMolecular hydrogen formation on interstellar PAHs through Eley-Rideal abstraction reactions
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We present experimental data on H2 formation processes on gas-phase polycyclic aromatic hydrocarbon (PAH) cations. This process was studied by exposing coronene radical cations, confined in a radio-frequency ion trap, to gas phase H atoms. Sequential attachment of up to 23 hydrogen atoms has been observed. Exposure to atomic D instead of H allows one to distinguish attachment from competing abstraction reactions, as the latter now leave a unique fingerprint in the measured mass spectra. Modeling of the experimental results using realistic cross sections and barriers for attachment and abstraction yield a 1:2 ratio of abstraction to attachment cross sections. The strong contribution of abstraction indicates that H2 formation on interstellar PAH cations is an order of magnitude more relevant than previously thought.
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Molecular hydrogen is the most abundant molecule in the Universe. It is thought that a large portion of H2 forms by association of hydrogen atoms to polycyclic aromatic hydrocarbons (PAHs). We model the influence of PAHs on total H2 formation rates in photodissociation regions (PDRs) and assess the effect of these formation rates on the total cloud structure. We set up a chemical kinetic model at steady state in a PDR environment and included adiative transfer to calculate the chemistry at different depths in the PDR. This model includes known dust grain chemistry for the formation of H2 and a H2 formation mechanism on PAHs. Since H2 formation on PAHs is impeded by thermal barriers, this pathway is only efficient at higher temperatures (T > 200 K). At these temperatures the conventional route of H2 formation via H atoms physisorbed on dust grains is no longer feasible, so the PAH mechanism enlarges the region where H2 formation is possible. We find that PAHs have a significant influence on the structure of PDRs. The extinction at which the transition from atomic to molecular hydrogen occurs strongly depends on the presence of PAHs, especially for PDRs with a strong external radiation field. A sharp spatial transition between fully dehydrogenated PAHs on the outside of the cloud and normally hydrogenated PAHs on the inside is found. As a proof of concept, we use coronene to show that H2 forms very efficiently on PAHs, and that this process can reproduce the high H2 formation rates derived in several PDRs.
Silicon monosulfide is an important silicon bearing molecule detected in circumstellar envelopes and star forming regions. Its formation and destruction routes are not well understood, partially due to the lack of a detailed knowledge on the involved reactions and their rate coefficients. In this work we have calculated and modeled the potential energy surface (PES) of the HSiS system employing highly accurate multireference electronic structure methods. After obtaining an accurate analytic representation of the PES, which includes long-range energy terms in a realistic way via the DMBE method, we have calculated rate coefficients for the Si+SH$rightarrow$SiS+H reaction over the temperature range of 25-1000K. This reaction is predicted to be fast, with a rate coefficient of $sim 1times 10^{-10}rm cm^3, s^{-1}$ at 200K, which substantially increases for lower temperatures (the temperature dependence can be described by a modified Arrhenius equation with $alpha=0.770times 10^{-10}rm cm^3,s^{-1}$, $beta=-0.756$ and $gamma=9.873, rm K$). An astrochemical gas-grain model of a shock region similar to L1157-B1 shows that the inclusion of the Si+SH reaction increases the SiS gas-phase abundance relative to ce{H2} from $5times 10^{-10}$ to $1.4times 10^{-8}$, which perfectly matches the observed abundance of $sim 2times 10^{-8}$.
We consider the possibility that solid molecular hydrogen is present in interstellar space. If so cosmic-rays and energetic photons cause ionisation in the solid leading to the formation of H6+. This ion is not produced by gas-phase reactions and its radiative transitions therefore provide a signature of solid H2 in the astrophysical context. The vibrational transitions of H6+ are yet to be observed in the laboratory, but we have characterised them in a quantum-theoretical treatment of the molecule; our calculations include anharmonic corrections, which are large. Here we report on those calculations and compare our results with astronomical data. In addition to the H6+ isotopomer, we focus on the deuterated species (HD)3+ which is expected to dominate at low ionisation rates as a result of isotopic condensation reactions. We can reliably predict the frequencies of the fundamental bands for five modes of vibration. For (HD)3+ all of these are found to lie close to some of the strongest of the pervasive mid-infrared astronomical emission bands, making it difficult to exclude hydrogen precipitates on observational grounds. By the same token these results suggest that (HD)3+ could be the carrier of the observed bands. We consider this possibility within the broader picture of ISM photo-processes and we conclude that solid hydrogen may indeed be abundant in astrophysical environments.
The high interstellar abundances of polycyclic aromatic hydrocarbons (PAHs) and their size distribution are the result of complex chemical processes implying dust, UV radiation, and the main gaseous components (H, C+, and O). These processes must explain the high abundance of relatively small PAHs in the diffuse interstellar medium (ISM) and imply the continuous formation of some PAHs that are small enough (number of carbon atoms NC <~ 35-50) to be completely dehydrogenated by interstellar UV radiation. The carbon clusters Cn thus formed are constantly exposed to the absorption of ~10-13.6 eV UV photons, allowing isomerization and favoring the formation of the most stable isomers. They might tend to form irregular carbon cages. The frequent accretion of interstellar C+ ions could favor further cage isomerization, as is known in the laboratory for C60, possibly yielding most stable fullerenes, such as C40, C44, and C50. These fullerenes are expected to be very stable in the diffuse ISM because C2 ejection is not possible by single UV photon absorption, but could need rare two-photon absorption. It is possible that at least one of these fullerenes or its cation is as abundant as C60 or C60+ in the diffuse ISM, although this abundance is limited by the lack of observed matching features in observed mid-infrared spectra. B3LYP calculations of the visible spectrum for a number of fullerene isomers with 40 <~ NC <~ 50 show that they generally have a few spectral bands in the visible range, with f-values in the range of a few 10-2. This could make such fullerenes interesting candidates for the carriers of some diffuse interstellar bands.
We present the detection and analysis of molecular hydrogen emission toward ten interstellar regions in the Large Magellanic Cloud. We examined low-resolution infrared spectral maps of twelve regions obtained with the Spitzer infrared spectrograph (IRS). The pure rotational 0--0 transitions of H$_2$ at 28.2 and 17.1${,rm mu m}$ are detected in the IRS spectra for ten regions. The higher level transitions are mostly upper limit measurements except for three regions, where a 3$sigma$ detection threshold is achieved for lines at 12.2 and 8.6${,rm mu m}$. The excitation diagrams of the detected H$_2$ transitions are used to determine the warm H$_2$ gas column density and temperature. The single-temperature fits through the lower transition lines give temperatures in the range $86-137,{rm K}$. The bulk of the excited H$_2$ gas is found at these temperatures and contributes $sim$5-17% to the total gas mass. We find a tight correlation of the H$_2$ surface brightness with polycyclic aromatic hydrocarbon and total infrared emission, which is a clear indication of photo-electric heating in photodissociation regions. We find the excitation of H$_2$ by this process is equally efficient in both atomic and molecular dominated regions. We also present the correlation of the warm H$_2$ physical conditions with dust properties. The warm H$_2$ mass fraction and excitation temperature show positive correlations with the average starlight intensity, again supporting H$_2$ excitation in photodissociation regions.
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