Farid Salama

Jet-discharge cavity ring-down spectroscopy of ionized polycyclic aromatic hydrocarbons: progress in testing the PAH hypothesis for the diffuse interstellar band problem

Naphthalene cations (C10H+8) were produced in a slit jet coupled with an electronic discharge, and cavity ring down was used to obtain its absorption spectrum in the region 645-680 nm. Two of the strongest C10H+8 bands previously characterized by matrix isolation spectroscopy were found, both with a fractional blue shift of about 0.5%. This is the first gas-phase electronic absorption spectrum of an ionized polycyclic aromatic hydrocarbon (PAH). This work opens the way for a direct comparison of laboratory PAH spectra with the diffuse interstellar bands (DIB), the origin of which still constitutes an open problem in astrophysics.

Matrix-isolated Nano-sized Carbon Grains as an Analog for the 217.5 Nanometer Feature Carrier

The effect of particle shape or particle clustering on the extinction behavior of nano-sized hydrogenated carbon grains is investigated experimentally. The particles were extracted by a molecular beam technique at different condensation and clustering states and isolated in an argon matrix for UV spectroscopy. The state of clustering in the samples was controlled by transmission electron microscopy analysis. The simple spherical morphology of the matrix-isolated nonagglomerated particles permitted the derivation of reliable optical constants. A clear correlation was found between the measured UV feature width and the degree of particle clustering, in agreement with theoretical investigations based on the derived optical data. Therefore, the results prove unambiguously the expectation that the optical properties of carbonaceous grain material are strongly influenced by the particle shape and the clustering degree. For particles produced in hydrogen-containing atmospheres, the UV extinction peak was shifted blueward to a position close to the 217.5 nm hump. This shift was found to be nearly independent of the amount of hydrogen in the condensation zone. We also discuss the infrared spectra of the hydrogenated carbon materials. The astrophysical implications of the results are discussed with regard to the observational as well as the elemental abundance constraints.

Pulsed discharge nozzle cavity ringdown spectroscopy of cold polycyclic aromatic hydrocarbon ions

The gas-phase electronic absorption spectra of the naphthalene (C10H8+) and acenaphthene (C12H10+) cations have been measured in the visible range in a free jet planar expansion in an attempt to collect data in an astrophysically relevant environment. The direct absorption spectra of two out of four bands measured of the gas-phase cold naphthalene cation along with the gas-phase vibronic absorption spectrum of the cold acenaphthene cation are reported for the first time. Direct absorption spectra of their van der Waals complexes with argon are also reported for the first time. The study has been carried out using the ultrasensitive and versatile technique of cavity ringdown spectroscopy (CRDS) coupled to a pulsed discharge slit nozzle (PDN). The new PDN-CRDS set up is described and its characteristics are evaluated. The direct-absorption spectra of the polycyclic aromatic hydrocarbon (PAH) ions are discussed and compared to the gas-phase and solid-phase data available in the literature. The analysis of th...

The Role of Polycyclic Aromatic Hydrocarbons in Ultraviolet Extinction. I. Probing Small Molecular Polycyclic Aromatic Hydrocarbons

We have obtained new Hubble Space Telescope/Space Telescope Imaging Spectrograph spectra to search for structure in the ultraviolet interstellar extinction curve, with particular emphasis on a search for absorption features produced by polycyclic aromatic hydrocarbons (PAHs). The presence of these molecules in the interstellar medium has been postulated to explain the infrared emission features seen in the 3-13 μm spectra of numerous sources. Ultraviolet (UV) spectra are uniquely capable of identifying specific PAH molecules. We obtained high signal-to-noise ratio UV spectra of stars that are significantly more reddened than those observed in previous studies. These data put limits on the role of small (30-50 carbon atoms) PAHs in UV extinction and call for further observations to probe the role of larger PAHs. PAHs are of importance because of their ubiquity and high abundance inferred from the infrared data, and also because they may link the molecular and dust phases of the interstellar medium. A presence or absence of UV absorption bands due to PAHs could be a definitive test of this hypothesis. We should be able to detect a 20 A wide feature down to a 3 σ limit of ~0.02 AV. No such absorption features are seen other than the well-known 2175 A bump.

Electronic absorption spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. II. The phenanthrene cation (C14H10+) and its 1-methyl derivative

The ultraviolet, visible, and near infrared absorption spectra of phenanthrene (C14H10), 1-methylphenanthrene [(CH3)C14H9], and their radical ions [C14H10+; (CH3)C14H9+], formed by vacuum-ultraviolet irradiation, were measured in neon matrices at 4.2 K. The associated vibronic band systems and their spectroscopic assignments are discussed. The oscillator strengths were calculated for the phenanthrene ion and found lower than the theoretical predictions. This study presents the first spectroscopic data for phenanthrene and its methyl derivative trapped in a neon matrix where the perturbation of the isolated species by its environment is minimum; a condition crucial to astrophysical applications.

Spectroscopy of large PAHs Laboratory studies and comparison to the Diffuse Interstellar Bands

Polycyclic Aromatic Hydrocarbons (PAHs) are thought to be the carriers of the ubiquitous infrared emission bands (UIBs). Data from the Infrared Space Observatory (ISO) have provided new insights into the size distribution and the structure of interstellar PAH molecules pointing to a trend towards larger-size PAHs. The mid-infrared spectra of galactic and extragalactic sources have also indicated the presence of 5-ring structures and PAH structures with attached side groups. This paper reports for the first time the laboratory measurement of the UV-Vis-NIR absorption spectra of a representative set of large PAHs that have also been selected for a long duration exposure experiment on the International Space Station ISS. PAHs with sizes up to 600 amu, including 5-ring species and PAHs containing heteroatoms, have been synthesized and their spectra measured using matrix isolation spectroscopy. The spectra of the neutral species and the associated cations and anions measured in this work are also compared to astronomical spectra of Diuse Interstellar Bands (DIBs).

Interstellar gas, dust and diffuse bands in the SMC

Aims. In order to gain new insight into the unidentified identity of the diffuse interstellar band (DIB) carriers, this paper describes research into possible links between the shape of the interstellar extinction curve (including the 2175 A bump and far-UV rise), the presence or absence of DIBs, and physical and chemical conditions of the diffuse interstellar medium (gas and dust) in the Small Magellanic Cloud (SMC). Methods. We searched for DIB absorption features in VLT/UVES spectra of early-type stars in the SMC whose reddened lines-ofsight probe the diffuse interstellar medium of the SMC. Apparent column density profiles of interstellar atomic species (Na i ,K i ,C aii and Ti ii) are constructed to provide information on the distribution and conditions of the interstellar gas. Results. The characteristics of eight DIBs detected toward the SMC wing target AzV 456 are studied and upper limits are derived for the DIB equivalent widths toward the SMC stars AzV 398, AzV 214, AzV 18, AzV 65 and Sk 191. The amount of reddening is derived for these SMC sightlines, and, using RV and the H i column density, converted into a gas-to-dust ratio. From the atomic column density ratios we infer an indication of the strength of the interstellar radiation field, the titanium depletion level and a relative measure of turbulence/quiescence. The presence or absence of DIBs appears to be related to the shape of the extinction curve, in particular with respect to the presence or absence of the 2175 A feature. Our measurements indicate that the DIB characteristics depend on the local physical conditions and chemical composition of the interstellar medium of the SMC, which apparently determine the rate of formation (and/or) destruction of the DIB carriers. The UV radiation field (via photoionisation and photo-destruction) and the metallicity (i.e. carbon abundance) are important factors in determining diffuse band strengths which can differ greatly both between and within galaxies.

Time-dependent Density Functional Theory Calculations of Large Compact Polycyclic Aromatic Hydrocarbon Cations: Implications for the Diffuse Interstellar Bands

We investigate the electronic absorption spectra of several maximally pericondensed polycyclic aromatic hydrocarbon radical cations with time-dependent density functional theory calculations. We find interesting trends in the vertical excitation energies and oscillator strengths for this series containing pyrene through circumcircumcoronene, the largest species containing close to 100 carbon atoms. We discuss the implications of these new results for the size and structure distribution of the diffuse interstellar band carriers.

PAH charge state distribution and DIB carriers: Implications from the line of sight toward HD 147889

We have computed physical parameters such as density, degree of ionization and temperature, constrained by a large observational data set on atomic and molecular species, for the line of sight toward the single cloud HD147889. Diffuse interstellar bands ( DIBs) produced along this line of sight are well documented and can be used to test the PAH hypothesis. To this effect, the charge state fractions of different polycyclic aromatic hydrocarbons (PAHs) are calculated in HD147889 as a function of depth for the derived density, electron abundance and temperature profile. As input for the construction of these charge state distributions, the microscopic properties of the PAHs, e. g., ionization potential and electron affinity, are determined for a series of symmetry groups. The combination of a physical model for the chemical and thermal balance of the gas toward HD147889 with a detailed treatment of the PAH charge state distribution, and laboratory and theoretical data on specific PAHs, allow us to compute electronic spectra of gas phase PAH molecules and to draw conclusions about the required properties of PAHs as DIB carriers. We find the following. 1) The variation of the total charge state distribution of each specific class ( series) of PAH in the translucent cloud toward HD147889 ( and also of course for any other diffuse/ translucent cloud) depends strongly on the molecular symmetry and size ( number of p electrons). This is due to the strong effects of these parameters on the ionization potential of a PAH. 2) Different wavelength regions in the DIB spectrum are populated preferentially by different PAH charge states depending on the underlying PAH size distribution. 3) The PAH size distribution for HD147889 is constrained by the observed DIB spectrum to be Gaussian with a mean of 50 carbon atoms. 4) For the given PAH size distribution it is possible to constrain the total small catacondensed PAH column density along the line of sight to HD147889 to 2.4 x 10(14) cm(-2) by comparing the total observed UV extinction to the strong UV absorptions of neutral PAHs in the 2000-3000 Angstrom region. 5) Catacondensed PAHs with sizes above some 40 C-atoms are expected to show strong DIBS longward of 10 000 Angstrom. Large condensed PAHs in the series, pyrene, coronene, ovalene,...., on the other hand, mainly absorb between 4000 and 10 000 Angstrom but extrapolation to even larger pericondensed PAHs in this series also shows strong absorptions longward of 10 000 Angstrom. 6) Only the weak DIBs in HD147889 could be reproduced by a mix of small catacondensed PAHs (<50 C atoms) while for large pericondensed PAHs ( 50 <C atoms <100) the intermediate DIBs are well reproduced. Small catacondensed PAHs cannot contribute more than 50% of the total observed equivalent width toward HD147889. Strong DIBs can only be reproduced by addition of very specific PAH molecules or homologue series to the sample set (i.e., a small number of PAHs with high oscillator strength or a large number of PAHs with a low oscillator strength). An outline is provided for a more general application of this method to other lines of sight, which can be used as a pipeline to compute the spectroscopic response of a PAH or group of PAHs in a physical environment constrained by independent (non-DIB) observations.

Cavity ring-down spectroscopy and theoretical calculations of the S1(B3u1)←S0(Ag1) transition of jet-cooled perylene

As part of our long-term program to test the diffuse interstellar band-polycyclic aromatic hydrocarbon hypothesis, we have investigated the S(1)<--S(0) electronic transition of neutral perylene (C(20)H(12)) in a combined experimental and theoretical study. Jet-cooled perylene was prepared with a pulsed discharge slit nozzle and detected by cavity ring-down spectroscopy. A number of vibronic features were observed in the 24 000-24 900 cm(-1) spectral range. Density functional and ab initio calculations were performed to determine the geometries, harmonic vibrational frequencies, and normal coordinates of both the S(0) and S(1) electronic states. A rotational temperature of 52+/-5 K was derived from a rotational contour analysis of the vibronic band associated with the 0-0 transition. A Franck-Condon treatment was carried out to calculate the vibronic spectrum of the S(1)<--S(0) transition. A good agreement was found between the calculated and the experimental spectra. A vibrational assignment is proposed and six normal modes are identified. The contribution of neutral compact polycyclic aromatic hydrocarbons to the diffuse interstellar bands is briefly discussed.