Carbon is a major player in the evolutionary scheme of the universe because of its abundance and its ability to form complex species. It is also a key element in the evolution of prebiotic molecules. The different forms of cosmic carbon are reviewed ranging from carbon atoms and carbon-bearing molecules to complex, solid-state, carbonaceous structures. The current state of knowledge is assessed on the observational and laboratory fronts. Fundamental astrophysical implications are examined as well as the impact of these studies on the hitherto poorly understood physical and chemical properties of carbon materials in space.

The potential link between neutral and/or ionized polycyclic aromatic hydrocarbons (PAHs) and the diffuse interstellar band (DIB) carriers is examined. Based on the study of the general physical and chemical properties of PAHs, an assessment is made of their possible contribution to the DIB carriers. It is found that, under the conditions reigning in the diffuse interstellar medium, PAHs can be present in the form of neutral molecules as well as positive and/or negative ions. The charge distribution of small PAHs is dominated, however, by two charge states at one time with compact PAHs present only in the neutral and cationic forms. Each PAH has a distinct spectral signature depending on its charge state. Moreover, the spectra of ionized PAHs are always clearly dominated by a single band in the DIB spectral range. In the case of compact PAH ions, the strongest absorption band is of type A (i.e., the band is broad, falls in the high-energy range of the spectrum, and possesses a large oscillator strength), and seems to correlate with strong and broad DIBs. For noncompact PAH ions, the strongest absorption band is of type I (i.e., the band is narrow, falls in the low-energy range of the spectrum, and possesses a small oscillator strength), and seems to correlate with weak and narrow DIBs. Potential molecular size and structure constraints for interstellar PAHs are derived by comparing known DIB characteristics to the spectroscopic properties of PAHs. It is found that (i) only neutral PAHs larger than about 30 carbon atoms could, if present, contribute to the DIBs. (ii) For compact PAHs, only ions with less than about 250 carbon atoms could, if present, contribute to the DIBs. (iii) The observed distribution of the DIBs between strong/moderate and broad bands on the one hand and weak and narow bands on the other can easily be interpreted in the context of the PAH proposal by a distribution of compact and noncompact PAH ions, respectively. A plausible correlation between PAH charge states and DIB "families" is thus provided by the PAH-DIB proposal. Following this proposal, DIB families would reflect conditions within a cloud which locally determine the relative importance of cations, anions, and neutral species, rather than tracers of a specific species. Observational predictions are given to establish the viability of the PAH hypothesis. It is concluded that small PAH ions are very promising candidates as DIB carriers provided their population is dominated by a finite number (100-200) of species. A key test for the PAH proposal, consisting of laboratory and astronomical investigations in the ultraviolet range, is called for.

The absorption spectra of neutral pentacene (C 22 H 14 ) and its radical cation (C 22 H 14 + ) and anion (C 22 H 14 -) isolated in solid Ne, Ar, and Kr have been measured from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing molecular anion production in matrices doped with alkali metal (Na or K). TD-DFT calculations were carried out to assist in the assignments for the measured spectral features of the pentacene ions.

We discussthe proposalrelating the origin of someof the diffuse interstellar bands (DIBs) to neutral and ionized polycyclic aromatic hydrocarbons(PAHs) presentin interstellar clouds. Laboratory spectra of severalPAHs, isolated at low temperature in inert gas matrices, are comparedwith an extensiveset of astronomical spectra of reddened,early type stars. From this comparison,it is concludedthat PAH ions are good candidatesto explain someof the DIBs.Unambiguousassignmentsare difficult, however,dueto the shift in wavelengths and the band broadeninginducedin the laboratory spectra by the solid matrix." Definitive band assignmentsand, ultimately, the test of the of the proposal that PAH ions carry someof the DIB must await the availability of gas-phase measurementsin the laboratory. The presentassessment offers a guideline for future laboratory experimentsby allowing the preselectionof PromisingPAH moleculesto be studied in jet expansions.

The absorption spectra of neutral pentacene (C 22 H 14 ) and its radical cation (C 22 H 14 + ) and anion (C 22 H 14 -) isolated in solid Ne, Ar, and Kr have been measured from the ultraviolet to the near-infrared. The associated vibronic band systems and their spectroscopic assignments are discussed together with the physical and chemical conditions governing molecular anion production in matrices doped with alkali metal (Na or K). TD-DFT calculations were carried out to assist in the assignments for the measured spectral features of the pentacene ions.

We discuss the proposal relating the origin of some of the diffuse interstellar bands (DIBs) to neutral and ionized polycyclic aromatic hydrocarbons (PAHs) present in interstellar clouds. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices, are compared with the spectra of five reddened early-type stars selected from an extensive set of astronomical spectra. From this comparison, it is concluded that PAH ions are good candidates to explain some of the DIBS. Unambiguous assignments are difficult, however, because of the shift in wavelengths and the band broadening induced in the laboratory spectra by the solid matrix. This situation is illustrated by a comparison with the gas-phase spectra made available recently for two PAH ions. Definitive band assignments and, ultimately, the test of the proposal that PAH ions carry some of the DIBs must await the availability of a larger set of gas-phase measurements in the laboratory. The present assessment offers a guideline for future laboratory experiments by allowing the preselection of promising PAH molecules to be studied in jet expansions.

Abstract.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 HD 147889. 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 HD 147889 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 HD 147889 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 HD 147889 (and also of course for any other diffuse/translucent cloud) depends strongly on the molecular symmetry and size (number of π 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 HD 147889 is constrained by the observed DIB spectrum to be Gaussian with a mean of 50 carbon atoms.

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 Å 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, Ca ii 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 R V 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 Å 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.