Theoretical investigations of the perylene electronic structure: Monomer,dimers, and excimers

The structural and electronic properties of perylene molecule, dimers, and excimers have been computationally studied. The present work represents the first systematic study of perylene molecule and dimer forms by means of long‐range corrected time‐dependent density functional theory (TDDFT) approaches. Initially, the study explores the photophysical properties of the molecular species. Vertical transitions to many excited singlet states have been computed and rationalized with different exchange‐correlation functionals. Differences between excitation energies are discussed and compared to the absorption spectrum of perylene in gas phase and diluted solution. De‐excitation energy from the relaxed geometry of the lowest excited singlet is in good agreement with the experimental fluorescence emission. Optimization of several coplanar forms of the perylene pair prove that, contrary to generalized gradient approximation (GGA) and hybrid exchange‐correlation functionals, corrected TDDFT is able to bind the perylene dimer in the ground state. Excitation energies from different dimer conformers point to dimer formation prior to photoexcitation. The fully relaxed excimer geometry belongs to the perfectly eclipsed conformation with D_2h symmetry. The excimer equilibrium intermolecular distance is shorter than the separation found for the ground state, which is an indication of stronger interchromophore interaction in the excimer state. Excimer de‐excitation energy is in rather good agreement with the excimer band of perylene in concentrated solution. The study also scans the energy profiles of the ground and lowest excited states along several geometrical distortions. The nature of the interactions responsible for the excimer stabilization is explored in terms of excitonic and charge resonance contributions. © 2015 Wiley Periodicals, Inc.