Molecular bending as a vital step toward transforming planar PAHs to fullerenes and tubular structures

Context. Polycyclic aromatic hydrocarbons (PAHs) and fullerenes are the largest molecules found in the interstellar medium (ISM). They are abundant and widespread in various astronomical environments. However, the detailed connection between these two species is unknown; in particular, no quantum chemical studies have been performed. Aims. In this work, we investigate a vital step in transforming planar PAHs to fullerenes, that is, the tubulation processes of PAHs. Methods. We used density functional theory for this study. The molecular structures and vibrational frequencies were calculated using the hybrid density functional B3LYP method. To better describe intermolecular forces, we considered Grimme’s dispersion correction in the calculations for this work. Intrinsic reaction coordinate calculations were also performed to confirm that the transition state structures are connected to their corresponding local potential energy surface minima. Results. As expected, we find that it is easier to bend a molecule as it gets longer, whereas it is harder to bend the molecule if it gets “wider” (i.e., with more rows of benzene rings). The change of multiplicity slightly alters the bending energies, while (a complete) dehydrogenation alleviates the bending barrier significantly and facilitates the formation of pentagons, which may act as an indispensable step in the formation of fullerenes in the ISM.