Radiolytic studies of naphthalene in the presence of water.

Naphthalene is an interesting candidate to study in the framework of organic delivery to planetary surfaces as well as in the origin of life. Additionally, naphthalene is of environmental interest, because of its chronic and acute effects on living systems, such as humans and animals (e.g. moths). Naphthalene has been well studied in both fields. In this paper we give an overview of radiolytic studies of naphthalene in the presence of both liquid water and water ice. From our review it appears that OH radicals are formed both in liquid water and in interstellar ices and that these radicals play a considerable role in the degradation of naphthalene. However, it also appears that upon irradiation of naphthalene in liquid water, hydrogen peroxide, a species that accelerates naphthalene degradation, is formed. Based on this review we suggest that the role of hydrogen peroxide in interstellar ices should be further investigated.

The valence electronic structure and conformational flexibility of epichlorohydrin.

The electronic structure of epichlorohydrin is investigated in the whole valence region by a combined experimental and theoretical study. The issue of controversial assignments of the molecular electronic structure is here addressed. Photoelectron spectra (PES) and Threshold Photoelectron spectra (TPES) of room temperature molecules in the gas phase are recorded. Geometries and energies of the stable conformers due to internal rotation of the C-C-C-Cl dihedral angle, gauche-II (g-II), gauche-I (g-I), and cis, are calculated, and the effect of the conformational flexibility on the photoionization energetics is studied by DFT and 2h-1p Configuration Interaction (CI) methods. Strong breakdown of the Koopmans Theorem (KT) is obtained for the four outermost ionizations, which are further investigated by higher level ab initio calculations. The full assignment of the spectrum is put on a firm basis by the combination of experimental and theoretical results. The orbital composition from correlated calculations is found closer to the DFT orbitals, which are then used to analyze the electronic structure of the molecule. The Highest Occupied Molecular Orbital (HOMO) and HOMO--2 are n(O)/n(Cl) mixed orbitals. The nature of each valence MO is generally preserved in all the conformers, although the magnitude of the n(O)/n(Cl) mixing in HOMO and HOMO--2 varies to some extent with the C-C-C-Cl dihedral angle. The low energy part of the HOMO PE band is predicted to be substantially affected by the conformational flexibility, as experimentally observed in the spectra. The rest of the spectrum is described in terms of the dominant conformer g-II, and a good agreement between experiment and theory is found. The inner-valence PE spectrum is characterized by satellite structures, due to electron correlation effects, which are interpreted by means of 2h-1p CI calculations.

The interstellar chemistry of PAH cations.

Diffuse interstellar bands (DIBs) are mysterious absorption lines in the optical spectra of stars, and have been known for 75 years. Although it is widely believed that they arise from gas-phase organic molecules (rather than from dust grains) in the interstellar medium, no consensus has been reached regarding their precise cause. The realization that many emission features in astronomical infrared spectra probably arise from polycyclic aromatic hydrocarbons (PAHs), which may themselves be very abundant in the interstellar medium, has led to the suggestion that ionized PAHs might be the source of the DIBs. Laboratory investigations have revealed that small, positively charged PAHs in matrices have absorption features that bear some resemblance to DIBs, but no clear identification of any DIB with any specific PAH cation has yet been made. Here we report a laboratory study of the chemical reactivity of PAH cations (C6H6+, C10H8+ and C16H10+) in the gas phase. We find that these PAH cations are very reactive, and are therefore unlikely to survive in high abundances in the interstellar medium. Rather, such molecules will react rapidly with hydrogen, and we therefore suggest that the resulting protonated PAH cations (and species derived from them) should become the focus of future searches for a correspondence between molecular absorption features and the DIBs.