Electronic Transitions of Protonated PAHs in 6 K Neon Matrices

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Protonated polycyclic aromatic hydrocarbons (H-PAH+s) are fundamental intermediates in organic chemistry and have been studied several decades ago in strong acidic solutions by NMR, IR and optical methods. Recently, they have been considered as possible carriers of certain diffuse interstellar bands (DIBs). According to TD-DFT calculations, such cations despite their closed-shell electronic structure could have strong transitions in the visible, where DIBs are detected. Diffuse interstellar absorption bands provide an unambiguous identification of interstellar molecules if their laboratory electronic spectra match astronomical observations. Therefore, the gas-phase spectroscopic measurements on H-PAH+s are necessary; they are limited currently to electronic spectra of protonated naphthalene and some larger protonated linear acenes. In the present contribution electronic absorption spectra of small H-PAH+s, anthracene, phenanthrene, pyrene and others, isolated in 6 K neon matrices are reported. The experimental setup is described. The cations of interest were produced in a hot-cathode discharge source, mass selected and codeposited with neon. The corresponding neutral species were produced in the same matrices by photobleaching the sample. The observed electronic transitions of the investigated species are compared to ab initio calculations, providing starting point for gas-phase measurements.

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