Experimental and theoretical studies of plasmon–molecule interactions

Plasmon–molecule interactions are widely believed to involve photo-induced interferences between the localized excitation of individual electrons in molecules and the large collective excitation of conduction electrons in metal particles. The intrinsic multi-scale characteristics of plasmon–molecule interactions not only offer great opportunities for realizing precise top-down control of the optical properties of individual molecules, but also allow for accurate bottom-up manipulation of light polarization and propagation as a result of molecular excitation. However, the temporal and spatial complexity of plasmon–molecule experiments severely limits our interpretation and understanding of interactions that have important applications in dye-sensitized solar cells, single-molecule detectors, photoconductive molecular electronics, all-optical switching and photo-catalytic water splitting. This review aims to outline recent progress in experimental practice and theory for probing and exploiting the subtle coupling between discrete molecular orbitals and continuous metallic bands. For each experimental technique or theoretical model, the fundamental mechanisms and relevant applications are discussed in detail with specific examples. In addition, the experimental validation of theoretical models and the computational design of functional devices are both highlighted. Finally, a brief summary is presented together with an outlook for potential future directions of this emerging interdisciplinary research field. (review article)