Formation of silicon oxide grains at low temperature

The formation of grains in the interstellar medium, i.e., at low temperature, has been proposed as a possibility to solve the lifetime problem of cosmic dust. This process lacks a firm experimental basis, which is the goal of this study. We have investigated the condensation of SiO molecules at low temperature using neon matrix and helium droplet isolation techniques. The energies of SiO polymerization reactions have been determined experimentally with a calorimetric method and theoretically with calculations based on the density functional theory. The combined experimental and theoretical values have revealed the formation of cyclic (SiO)$_k$ ($k$ = 2--3) clusters inside helium droplets at $T$ = 0.37 K. Therefore, the oligomerization of SiO molecules is found to be barrierless and is expected to be fast in the low-temperature environment of the interstellar medium on the surface of dust grains. The incorporation of numerous SiO molecules in helium droplets leads to the formation of nanoscale amorphous SiO grains. Similarly, the annealing and evaporation of SiO-doped Ne matrices lead to the formation of solid amorphous SiO on the substrate. The structure and composition of the grains were determined by infrared absorption spectroscopy, transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Our results support the hypothesis that interstellar silicates textbf{can be formed} in the low temperature regions of the interstellar medium by accretion through barrierless reactions.

On the relevance of polyynyl-substituted PAHs to astrophysics

We report on the absorption spectra of the polycyclic aromatic hydrocarbon (PAH) molecules anthracene, phenanthrene, and pyrene carrying either an ethynyl (-C2H) or a butadiynyl (-C4H) group. Measurements were carried out in the mid infrared at room temperature on grains embedded in CsI pellets and in the near ultraviolet at cryogenic temperature on molecules isolated in Ne matrices. The infrared measurements show that interstellar populations of polyynyl-substituted PAHs would give rise to collective features in the same way non-substituted PAHs give rise to the aromatic infrared bands. The main features characteristic of the substituted molecules correspond to the acetylenic CH stretching mode near 3.05 mum and to the almost isoenergetic acetylenic CCH in- and out-of-plane bending modes near 15.9 mum. Sub-populations defined by the length of the polyynyl side group cause collective features which correspond to the various acetylenic CC stretching modes. The ultraviolet spectra reveal that the addition of an ethynyl group to a non-substituted PAH molecule results in all its electronic transitions being redshifted. Due to fast internal energy conversion, the bands at shorter wavelengths are significantly broadened. Those at longer wavelengths are only barely affected in this respect. As a consequence, their relative peak absorption increases. The substitution with the longer butadiynyl chain causes the same effects with a larger magnitude, resulting in the spectra to show a prominent if not dominating pi-pi* transition at long wavelength. After discussing the relevance of polyynyl-substituted PAHs to astrophysics, we conclude that this class of highly conjugated, unsaturated molecules are valid candidates for the carriers of the diffuse interstellar bands.

Abundances of PAHs in the ISM: Confronting Observations with Experimental Results

We present recent UV laboratory spectra of various polycyclic aromatic hydrocarbons (PAHs) and explore the potential of these molecules as carriers of the DIBs. From a detailed comparison of gas-phase and Ne-matrix absorption spectra of anthracene, phenanthrene, pyrene, 2,3-benzofluorene, benzo[ghi]perylene, and hexabenzocoronene with new interstellar spectra, we infer upper limits in the abundance of these PAHs in the interstellar medium. Upper limits in the column densities of anthracene of $0.8 - 2.8 times 10^{12}$ cm$^{-2}$ and of pyrene and 2,3-benzofluorene ranging from $2 - 8 times 10^{12}$ cm$^{-2}$ are inferred. Upper limits in the column densities of benzo[ghi]perylene are $0.9 - 2.4 times 10^{13}$ and $10^{14}$ cm$^{-2}$ for phenanthrene. The measurements indicate fractional abundances of anthracene, pyrene, and 2,3-benzofluorene of a few times $10^{-10}$. Upper limits in the fractional abundance of benzo[ghi]perylene of a few times $10^{-9}$ and of phenanthrene of few times $10^{-8}$ are inferred. {Toward CPD $-32^circ 1734$, we found near 3584 {AA} an absorption line of OH$^+$, which was discovered in the interstellar medium only very recently. The fractional abundances of PAHs inferred here are up to two orders of magnitude lower than estimated total PAH abundances in the interstellar medium. This indicates that either neutral PAHs are not abundant in translucent molecular clouds, or that a PAH population with a large variety of molecules is present.

Electronic spectroscopy of medium-sized polycyclic aromatic hydrocarbons: Implications for the carriers of the 2175 {AA} UV bump

Mixtures of polycylic aromatic hydrocarbons (PAHs) have been produced by means of laser pyrolysis. The main fraction of the extracted PAHs were primarily medium-sized, up to a maximum size of 38 carbon atoms per molecule. The use of different extraction solvents and subsequent chromatographic fractionation provided mixtures of different size distributions. UV-VIS absorption spectra have been measured at low temperature by matrix isolation spectroscopy and at room temperature with PAHs as film-like deposits on transparent substrates. In accordance with semi-empirical calculations, our findings suggest that large PAHs with sizes around 50 to 60 carbon atoms per molecule could be responsible for the interstellar UV bump at 217.5 nm.