Collective Energy Transfer to a Spectator Atom via Multi-Center Intermolecular Coulombic Decay

Molecular mechanisms that enable collective and upconverted energy transfer from multiple photoacceptors to a non-absorbing spectator reaction center are highly desirable for efficient light-energy utilization. Here, we show that intermolecular Coulombic decay (ICD), a nonlocal energy relaxation channel in photoexcited molecules, offers an avenue for such a novel energy transfer mechanism. On irradiation of pyridine-argon gas mixture at 266 nm and at low laser intensities, we observed a surprisingly dominant formation of argon cations. Measurements of the laser power dependence, together with systematic studies of Ar${}^{+}$ yield versus laser intensity and molecular density, reveal that ICD mediates the collective funneling of excitation energy from multiple photoexcited pyridine molecules to a non-photoabsorbing argon atom, leading to its ionization. The density of the reaction center offers an efficient handle to optimize this collective energy transfer. This mechanism opens new avenues in light harvesting design and may help explain the remarkable resistance of biomolecules to photodamage.