Electronic energy transfer ionization in naphthalene-CO₂ clusters reveals excited states of dry ice

Electronic energy relaxation and transfer shapes the photochemistry in molecules and materials that are exposed to UV radiation in areas ranging from astrochemistry to biology. The interaction between CO₂ and polycyclic aromatic hydrocarbons (PAHs) specifically, is of paramount interest in astrochemically relevant ices, the transition to renewable energy and the development of green chemistry. We investigate the vacuum UV excitation of the naphthalene-CO₂ complex and observe excited states of CO₂ through a newly identified molecular electronic energy transfer ionization mechanism. We evaluate the spectral development upon cluster growth with time-dependent density functional theory and show that the photoionization spectrum of naphthalene-CO₂ closely resembles the photon-stimulated desorption spectrum of CO₂ ice. The molecular electronic energy transfer ionization mechanism may affect the energy redistribution and charge balance in the interstellar medium significantly and therefore we discuss its implications for astrochemical models.