In more recent years, the characteristic and well-identifiable visible light emission of excimers, particularly those based on pyrene, has been exploited in various technological applications. These applications range from organic light-emitting diodes to fluorescent probes used for studying the conformation and internal dynamics of large macromolecules, including nucleic acids, proteins, and polymers. From a computational and theoretical point of view, many studies targeted the characteristic binding region of the prototypical pyrene excimer through static single-point calculations-that is, by obtaining the potential energy profiles associated with the scan of some relevant coordinate. Several electronic structure methods have been applied, including time-dependent density functional theory (TD-DFT)