Gas-Phase Fluorescence of Proflavine Reveals Two Close-Lying, Brightly Emitting States

Surprising excitation-dependent, dual emission from a small organic model fluorophore is reported. Gas-phase fluorescence spectra of proflavine (a diaminoacridine) ions reveal two long-lived emitting states, with distinct bands separated by just 1700 cm^-1. The relative intensities of these two bands depend on the excitation wavelength. Time-dependent density functional theory (TD-DFT) calculations support the existence of two close-lying singlet electronic states, with excitation into S₂ predicted to be >1000-fold more likely than into S₁. These data strongly suggest that internal conversion (IC) rates are suppressed relative to solvated proflavine, and that IC is competitive with intramolecular vibrational relaxation (IVR). This work offers an in-depth assessment of the gas-phase photophysics of a simple fluorophore that could open a new pathway to understanding dual emission in fluorophores.