The role of the charge state of PAHs in ultraviolet extinction

Aims: We explore the relation between charge state of polycyclic aromatic hydrocarbons (PAHs) and extinction curve morphology. Methods: We fit extinction curves with a dust model including core-mantle spherical particles of mixed chemical composition (silicate core, $sp^2$ and $sp^3$ carbonaceous layers), and an additional molecular component. We use exact methods to calculate the extinction due to classical particles and accurate computed absorption spectra of PAHs in different charge states, for the contribution due to the molecular component, along a sample of five rather different lines of sight. Results: A combination of classical dust particles and mixtures of real PAHs satisfactorily matches the observed interstellar extinction curves. Variations of the spectral properties of PAHs in different charge states produce changes consistent with the varying relative strengths of the bump and non-linear far-UV rise.Comment: 5 pages, 3 figures, Astronomy & Astrophysics Letters, in pres

Photo-desorption of H2O:CO:NH3 circumstellar ice analogs: Gas-phase enrichment

We study the photo-desorption occurring in H$_2$O:CO:NH$_3$ ice mixtures irradiated with monochromatic (550 and 900 eV) and broad band (250--1250 eV) soft X-rays generated at the National Synchrotron Radiation Research Center (Hsinchu, Taiwan). We detect many masses photo-desorbing, from atomic hydrogen (m/z = 1) to complex species with m/z = 69 (e.g., C$_3$H$_3$NO, C$_4$H$_5$O, C$_4$H$_7$N), supporting the enrichment of the gas phase. At low number of absorbed photons, substrate-mediated exciton-promoted desorption dominates the photo-desorption yield inducing the release of weakly bound (to the surface of the ice) species; as the number of weakly bound species declines, the photo-desorption yield decrease about one order of magnitude, until porosity effects, reducing the surface/volume ratio, produce a further drop of the yield. We derive an upper limit to the CO photo-desorption yield, that in our experiments varies from 1.4 to 0.007 molecule photon$^{-1}$ in the range $\sim 10^{15} - 10^{20}$~absorbed photons cm$^{-2}$. We apply these findings to a protoplanetary disk model irradiated by a central T~Tauri star

Chemistry in Evaporating Ices: Unexplored Territory

We suggest that three-body chemistry may occur in warm high density gas evaporating in transient co\textendash desorption events on interstellar ices. Using a highly idealised computational model we explore the chemical conversion from simple species of the ice to more complex species containing several heavy atoms, as a function of density and of adopted three body rate coefficients. We predict that there is a wide range of densities and rate coefficients in which a significant chemical conversion may occur. We discuss the implications of this idea for the astrochemistry of hot cores.Comment: Accepted in Ap

Dehydrogenated polycyclic aromatic hydrocarbons and UV bump

Recent calculations have shown that the UV bump at about 217.5 nm in the extinction curve can be explained by a complex mixture of PAHs in several charge states. Other studies proposed that the carriers are a restricted population made of neutral and singly-ionised dehydrogenated coronene molecules (C24Hn, n less than 3), in line with models of the hydrogenation state of interstellar PAHs predicting that medium-sized species are highly dehydrogenated. To assess the observational consequences of the latter hypothesis we have undertaken a systematic study of the electronic spectra of dehydrogenated PAHs. We use our first results to see whether such spectra show strong general trends upon dehydrogenation. We used state-of-the-art techniques in the framework of the density functional theory (DFT) to obtain the electronic ground-state geometries, and of the time- dependent DFT to evaluate the electronic excited-state properties. We computed the absorption cross-section of the species C24Hn (n=12,10,8,6,4,2,0) in their neutral and cationic charge-states. Similar calculations were performed for other PAHs and their fullydehydrogenated counterparts. pi electron energies are always found to be strongly affected by dehydrogenation. In all cases we examined, progressive dehydrogenation translates into a correspondingly progressive blue shift of the main electronic transitions. In particular, the pi-pi* collective resonance becomes broader and bluer with dehydrogenation. Its calculated energy position is therefore predicted to fall in the gap between the UV bump and the far-UV rise of the extinction curve. Since this effect appears to be systematic, it poses a tight observational limit on the column density of strongly dehydrogenated medium-sized PAHs.Comment: 5 pages, 7 figures, Astronomy & Astrophysics, in pres