Beyond Exciton Theory:  A Time-Dependent DFT and Franck−Condon Study of Perylene Diimide and Its Chromophoric Dimer

The diimide perylene motif exhibits a dramatic intensity reversal between the 0 → 0 and 0 → 1 vibronic bands upon π−π stacking; this distinct spectral property has previously been used to measure folding dynamics in covalently bound oligomers and synthetic biological hybrid foldamers. It is also used as a tool to assess organization of the π-stacking, indicating the presence of H- or J-aggregation. The zeroth-order exciton model, often used to describe the optical properties of chromophoric aggregates, is solely a transition dipole coupling scheme, which ignores the explicit electronic structure of the system as well as vibrational coupling to the electronic transition. We have therefore examined the optical properties of gas-phase perylene tetracarboxylic diimide (PTCDI) and its chromophoric dimer as a function of conformation to relate the excited-state distributions predicted by exciton theory with that of time-dependent density functional theory (TDDFT). Using ground- and excited-state geometries, the Franck−Condon (FC) factors for the lowest energy molecular nature electronic transition have been calculated and the origin of the intensity reversal of 0 → 0 and 0 → 1 vibronic bands has been proposed.