T-shaped dimer of coronene

Abstract

An evidence of importance of the T-shaped configuration of coronene dimer is presented. That is, the dimer's lowest energy configuration is not necessarily a stack, as it might had been expected a priori. This is a surprising result for dimer of such a large polycyclic aromatic hydrocarbon (PAH) as coronene. The energy of the T-shaped configuration at all considered levels of density functional theory (B3LYP,PBE/6-31+G(d),D95,cc-pVDZ,cc-pVTZ) was systematically lower than the energies of three plausible stack configurations. In order to get a better description of the van der Waals interaction,the density functional theory (DFT) results were adjusted by adding a phenomenological Lennard-Jones-type term into the total energy of the system. However, the van der Waals correction is somewhat arbitrary and its magnitude can not be rigorously justified. Depending on the choice of the parameters in the phenomenological term both the T-shaped and the parallel-displaced (PD) stack configurations can be the global energy minimum of the system. A simple model is proposed which is useful for qualitative understanding of possible geometries of the coronene dimer and larger coronene clusters. The model represents coronene dimer as two sets of charged rings interacting via Coulomb and Lennard-Jones potentials. The model provides an intuitively clear explanation why the T-shaped dimers can be of importance even for some of moderately large PAHs such as coronene and, may be, for circumcoronene.