Photochemistry of the PAH pyrene in water ice: the case for ion-mediated solid-state astrochemistry

Context. Icy dust grains play an important role in the formation of complex inter- and circumstellar molecules. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are abundantly present in the ISM in the gas phase. It is likely that these non-volatile species freeze out onto dust grains as well and participate in the astrochemical solid-state network, but experimental PAH ice studies are largely lacking. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, \water and CO. Pyrene ionisation is found to be most efficient in \water ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py^+ and PyH are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionised in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are put in an astrophysical context by determining the importance of PAH ionisation in a molecular cloud. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.Comment: 11 pages, 8 figures, accepted for publication in A&

Modeling the interstellar aromatic infrared bands with co-added spectra of PAHs

The observed variations in profiles of the interstellar aromatic infrared bands correlate with the object type and are indicative of PAH populations existing i n different sources. Spectroscopic studies on PAHs can provide tools for the int erpretation of variations accompanying the AIBs. As the observed spectra results from a mix of possible species in the region attempt is made to model this comp osite spectra by co-adding emissions from PAHs in different size groups. Theoretical IR data of PAHs having 10 to 96 carbon atoms is used to obtain emis sion spectra. The models are taken in size groups making up of small, medium and large PAHs. The models show good profile match with observations for the 7.7 $\mu m$ complex having sub-features at 7.6 and 7.8 $\mu m$. The 7.6 $\mu m$ sub-feature dominates in the spectra of medium sized PAH cations matching observations from UV rich interstellar environments. The 7.8 $\mu m$ component is more intense in the spectra of large PAH cations (model III) correlating with observations from benign astrophysical regions. A possible interpretation for the observations of $C-H$ out-of-plane bend modes and the weak outliers on the blue side of the intense 11.2 $\mu m$ band is proposed. The models provide pointers to possible PAH populations in different regions.Comment: accepted for publication in A&

Time-dependent density functional study of the electronic spectra of oligoacenes in the charge states -1, 0, +1, and +2

We present a systematic theoretical study of the five smallest oligoacenes (naphthalene, anthracene, tetracene, pentacene, and hexacene) in their anionic,neutral, cationic, and dicationic charge states. We used density functional theory (DFT) to obtain the ground-state optimised geometries, and time-dependent DFT (TD-DFT) to evaluate the electronic absorption spectra. Total-energy differences enabled us to evaluate the electron affinities and first and second ionisation energies, the quasiparticle correction to the HOMO-LUMO energy gap and an estimate of the excitonic effects in the neutral molecules. Electronic absorption spectra have been computed by combining two different implementations of TD-DFT: the frequency-space method to study general trends as a function of charge-state and molecular size for the lowest-lying in-plane long-polarised and short-polarised $\pi\to\pi^\star$ electronic transitions, and the real-time propagation scheme to obtain the whole photo-absorption cross-section up to the far-UV. Doubly-ionised PAHs are found to display strong electronic transitions of $\pi\to\pi^\star$ character in the near-IR, visible, and near-UV spectral ranges, like their singly-charged counterparts. While, as expected, the broad plasmon-like structure with its maximum at about 17-18 eV is relatively insensitive to the charge-state of the molecule, a systematic decrease with increasing positive charge of the absorption cross-section between about 6 and about 12 eV is observed for each member of the class.Comment: 38 pages, 11 figures, 7 tables, accepted for publication in Chemical Physic

Theoretical evaluation of PAH dications properties

Aims. We present a systematic theoretical study on 40 polycyclic aromatic hydrocarbons dications (PAHs++) containing up to 66 carbon atoms. Methods. We performed our calculations using well established quantum-chemical techniques in the framework of the density functional theory (DFT) to obtain the electronic ground-state properties, and of the time-dependent DFT (TD-DFT) to evaluate the excited\textendash state properties. Results. For each PAH++ considered we computed the absolute visible-UV photo-absorption cross-section up to about 30 eV. We also evaluated their vibrational properties and compared them to those of the corresponding neutral and singly-ionised species. We estimated the adiabatic and vertical second ionisation energy DeltaI through total energy differences. Conclusions. The DeltaI values obtained fall in the energy range 8-13 eV, confirming that PAHs could reach the doubly-ionised state in HI regions. The total integrated IR absorption cross-sections show a marked increase upon ionization, being on the average about two and five times larger for PAHs++ than for PAHs+ and PAHs, respectively. The visible-UV photo-absorption cross-sections for the 0, +1 and +2 charge-states show comparable features but PAHs++ are found to absorb slightly less than their parent neutrals and singly ionized species between ~7 and ~12 eV. Combining these pieces of information we found that PAHs++ should actually be more stable against photodissociation than PAHs and PAHs+,_if_ dissociation tresholds are nearly unchanged by ionization.Comment: 13 pages, 7 figures, accepted for pubblication in A&A (25/09/06

The Diffuse Interstellar Bands: A Major Problem in Astronomical Spectroscopy

A critical review of the very long-standing problem of the diffuse interstellar bands is presented with emphasis on spectroscopic aspects of observational, modelling and laboratory-based research. Some research themes and ideas that could be explored theoretically and experimentally are discussed. The article is based on the Journal of Molecular Spectroscopy Review Lecture presented at the 60th Ohio State University International Symposium on Molecular Spectroscopy, June 2005

A twisted bay-substituted quaterrylene phosphorescing in the NIR spectral region

The preparation of the first soluble quaterrylene derivative featuring peripheral tert-butyl substituents and sterically hindering, core-anchored triflate groups has been achieved. This involves a facile synthetic route based on an oxidative coupling of perylene precursors in the presence of H2O2 as oxidant. The steric hindrance between the TfO substituents at the central bay position of the quaterrylene board triggers a strong deformation of the central perylene planarity, which forces the quaterrylene platform to adopt a twisted geometry as shown by X-ray analysis. Exceptionally, photophysical investigations show that the core-twisted quaterrylene phosphoresces in the NIR spectral region at 1716 nm. Moreover, third-order nonlinear optical measurements on solutions and thin film containing the relevant molecule showed very large second hyperpolarizability values, as predicted by theoretical calculations at the CAM-B3LYP/6-31G** level of theory, making this material very appealing for photonic applications

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice ii. Near uv/vis spectroscopy and ionization rates

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