Electron Correlations and Two-Photon States in Polycyclic Aromatic Hydrocarbon Molecules: A Peculiar Role of Geometry

We present numerical studies of one- and two-photon excited states ordering in a number of polycyclic aromatic hydrocarbon molecules: coronene, hexa-peri-hexabenzocoronene and circumcoronene, all possessing \(D_{6h}\) point group symmetry versus ovalene with \(D_{2h}\) symmetry, within the Pariser-Parr-Pople model of interacting \(\pi\)-electrons. The calculated energies of the two-photon states as well as their relative two-photon absorption cross-sections within the interacting model are qualitatively different from single-particle descriptions. More remarkably, a peculiar role of molecular geometry is found. The consequence of electron correlations is far stronger for ovalene, where the lowest spin-singlet two-photon state is a quantum superposition of pairs of lowest spin triplet states, as in the linear polyenes. The same is not true for \(D_{6h}\) group hydrocarbons. Our work indicates significant covalent character, in valence bond language, of the ground state, the lowest spin triplet state and a few of the lowest two-photon states in \(D_{2h}\) ovalene but not in those with \(D_{6h}\) symmetry.