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. (C) 2014 AIP Publishing LLC.