Cryogenic Ion Fluorescence Spectroscopy: FRET in Rhodamine Homodimers and Heterodimers.

The internal electronic communication between two or more light-absorbers is fundamental for energy-transport processes, a field of large current interest. Here the intrinsic photophysics of homo- and heterodimers of rhodamine cations were studied where just two methylene units bridge the dyes. Gas-phase experiments were done on frozen molecular ions at cryogenic temperatures using the newly built LUNA2 mass spectroscopy setup in Aarhus. Both absorption (from fluorescence excitation) and dispersed-fluorescence spectra were measured. In the gas phase, there is no dielectric screening from solvent molecules, and the effect of charges on transition energies is maximum. Indeed, bands are redshifted compared to those of monomer dyes due to the electric field that each dye senses from the other in a dimer. Importantly, also, as two chemically identical dyes in a homodimer do not experience the same field along the long axis, each dye has separate absorption. At low temperatures, it is therefore possible to selectively excite one dye. Fluorescence is dominantly from the dye with the lowest transition energy no matter which dye is photoexcited. Hence this work unequivocally demonstrates Förster Resonance Energy Transfer even in homodimers where one dye acts as donor and the other as acceptor.