Subgap Two-Photon States in Polycyclic Aromatic Hydrocarbons: Evidence for Strong Electron Correlations

Strong electron correlation effects in the photophysics of quasi-one-dimensional \(\pi\)-conjugated organic systems such as polyenes, polyacetylenes, polydiacetylenes, etc., have been extensively studied. Far less is known on correlation effects in two-dimensional \(\pi\)-conjugated systems. Here we present theoretical and experimental evidence for moderate repulsive electron-electron interactions in a number of finite polycyclic aromatic hydrocarbon molecules with \(D_{6h}\) symmetry. We show that the excited state orderings in these molecules are reversed relative to that expected within one-electron and mean-field theories. Our results reflect similarities as well as differences in the role and magnitude of electron correlation effects in these two-dimensional molecules compared to those in polyenes.