Coupling between Plasmonic and Molecular Excitations: TDDFT Investigation of an Ag-Nanorod/BODIPY-Dye Interaction

A time-dependent density functional theory (TDDFT) computational approach is employed to study the optical coupling between a plasmonic system (a Ag₅₀ nanorod) and a fluorescent dye (BODIPY). It is found that the BODIPY dye can interact with a plasmonic system in a rather different and selective way according to the mutual orientation of the fragments. Indeed, (i) the plasmon excitation turns out to be sensitive to the presence of the BODIPY transition and (ii) this can lead to amplify or suppress the resonance accordingly to the relative orientation of the corresponding transition dipoles. To understand the coupling mechanism, we analyze the shape of the induced density in real space and the Individual Component Map of the Oscillator Strength (ICM-OS) plots and achieve a simple rationalization and insight on the origin and features of the coupling. The resulting possibility of understanding plasmon/fluorophore interactions by simple qualitative arguments opens the way to a rational design of hybrid (plasmon + dye) systems with the desired optical behavior.