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Register a new userPhotolysis-induced scrambling of PAHs as a mechanism for deuterium storage
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Aim. We investigate the role of PAHs as a sink for deuterium in the interstellar medium and study UV photolysis as a potential process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologues of D-enriched, protonated anthracene and phenanthrene ions was recorded in a FTICR mass spectrometer. IRMPD spectroscopy using FELIX provided the IR spectra that were compared to DFT vibrational spectra; reaction barriers and rates were also calculated and related to the product abundances. Results. The mass spectra for both UV and IRMPD photolysis show the loss of H from [D-C$_{14}$H$_{10}$]$^+$, whereas [H-C$_{14}$D$_{10}$]$^+$ shows a strong preference for D loss. Calculations reveal facile 1,2-H and -D shift reactions, with barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes in the 2 PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The $sim$0.1 eV difference in zero-point energy between C-H and C-D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D. Conclusion. Scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to an aromatic site, protecting it from elimination. This could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C-HD group on solo sites might be responsible for the majority of aliphatic C-D stretching bands seen in astronomical spectra.
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Interstellar polycyclic aromatic hydrocarbons (PAHs) are expected to be strongly processed by vacuum ultraviolet photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C24H12), ovalene (C32H14) and hexa-peri-hexabenzocoronene (HBC; C42H18) cations by exposure to synchrotron radiation in the range of 8--40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs, fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium are briefly discussed.
Recent analyses of Gaia data have provided direct evidence that most young stellar clusters are in a state of expansion, with velocities of the order of ~0.5 km/s. Traditionally, expanding young clusters have been pictured as entities that became unbound due to the lack of gravitational binding once the gas from the parental cloud that formed the cluster has been expelled by the stellar radiation of the massive stars in the cluster. In the present contribution, we used radiation-magnetohydrodynamic numerical simulations of molecular cloud formation and evolution to understand how stellar clusters form and disperse. We found that the ionising feedback from the newborn massive stars expels the gas from the collapse centre, flipping-up the gravitational potential as a consequence of the mass removal from the inside-out. Since neither the parental clouds nor the formed shells are distributed symmetrically around the HII region, net forces pulling out the stars are present, accelerating them towards the edges of the cavity. We call this mechanism ``gravitational feedback, in which the gravity from the expelled gas appears to be the crucial mechanism producing unbound clusters that expand away from their formation centre in an accelerated way in young stellar clusters. This mechanism naturally explains the Hubble flow-like expansion observed in several young clusters.
We study the PAH emission from protoplanetary disks. First, we discuss the dependence of the PAH band ratios on the hardness of the absorbed photons and the temperature of the stars. We show that the photon energy together with a varying degree of the PAH hydrogenation accounts for most of the observed PAH band ratios without the need to change the ionization degree of the molecules. We present an accurate treatment of stochastic heated grains in a vectorized three dimensional Monte Carlo dust radiative transfer code. The program is verified against results using ray tracing techniques. Disk models are presented for T Tauri and Herbig Ae stars. Particular attention is given to the photo-dissociation of the molecules. We consider beside PAH destruction also the survival of the molecules by vertical mixing within the disk. By applying typical X-ray luminosities the model accounts for the low PAH detection probability observed in T Tauri and the high PAH detection statistics found in Herbig Ae disks. Spherical halos above the disks are considered. We show that halos reduce the observed PAH band-to-continuum ratios when observed at high inclination. Finally, mid-IR images of disks around Herbig Ae disks are presented. We show that they are easier to resolve when PAH emission dominate.
We constructed two new models for deuterium and spin-state chemistry for the purpose of modeling the low-temperature environment prevailing in starless and pre-stellar cores. The fundamental difference between the two models is in the treatment of ion-molecule proton-donation reactions of the form $rm XH^+ + Y longrightarrow X + YH^+$, which are allowed to proceed either via full scrambling or via direct proton hop, i.e., disregarding proton exchange. The choice of the reaction mechanism affects both deuterium and spin-state chemistry, and in this work our main interest is on the effect on deuterated ammonia. We applied the new models to the starless core H-MM1, where several deuterated forms of ammonia have been observed. Our investigation slightly favors the proton hop mechanism over full scrambling because the ammonia D/H ratios are better fit by the former model, although neither model can reproduce the observed $rm NH_2D$ ortho-to-para ratio of 3 (the models predict a value of $sim$2). Extending the proton hop scenario to hydrogen atom abstraction reactions yields a good agreement for the spin-state abundance ratios, but greatly overestimates the deuterium fractions of ammonia. However, one can find a reasonably good agreement with the observations with this model by increasing the cosmic-ray ionization rate over the commonly-adopted value of $sim$$10^{-17},rm s^{-1}$. We also find that the deuterium fractions of several other species, such as $rm H_2CO$, $rm H_2O$, and $rm CH_3$, are sensitive to the adopted proton-donation reaction mechanism. Whether the full scrambling or proton hop mechanism dominates may be dependent on the reacting system, and new laboratory and theoretical studies for various reacting systems are needed to constrain chemical models.
IR emission bands at 3.3, 6.2, 7.7, 8.6 and 11.3 um are generally attributed to IR fluorescence from (mainly) FUV pumped PAHs. As such, they trace the FUV stellar flux and are a measure of star formation. We examined the IR spectral characteristics of Galactic star forming regions, normal and starburst galaxies, AGNs and ULIRGs. The goal is to analyze if PAH bands are a good qualitative and/or quantitative tracer of star formation and hence the application of PAH bands as a diagnostic in order to identify the dominant processes contributing to the IR emission from Seyferts and ULIRGs. We develop a MIR/FIR diagnostic and compare it to known diagnostics, with these also applied to the Galactic sample. This diagnostic is based on the FIR normalized 6.2 um PAH flux and the FIR normalized 6.2 um continuum flux. The Galactic sources form a sequence spanning a range of 3 orders of magnitude, from embedded compact HII regions to exposed PDRs and the (D)ISM. The variation in the 6.2 um PAH/continuum ratio is relative small. Normal and starburst galaxies ressemble exposed PDRs. While Seyfert-2s coincide with the starburst trend, Seyfert-1s are displaced by at least a factor 10 in 6.2 um continuum flux. ULIRGs show a diverse spectral appearance (AGN hot dust continuum, starburst-like or strong dust obscuration in the nucleus). ULIRGs also seems to have more prominent FIR emission than either starburst galaxies or AGNs. We discuss the observed variation in the Galactic sample in view of the evolutionary state and the PAH/dust abundance and the use of PAHs as quantitative tracers of star formation activity. We find that PAHs may be better suited as a tracer of B stars, which dominate the Galactic stellar energy budget, than as a tracer of massive star formation (O stars).
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