Lighting up long-range charge-transfer states by a localized plasmonic field

Abstract

The long-range charge-transfer states in a donor–acceptor system exhibit well separated electron–hole pairs, but are often difficult to achieve by optical means owing to a very small overlap between the wave functions of the donor and acceptor. We have found that the introduction of a spatially confined plasmon can enhance the transition probability to the long-range charge-transfer states as it can effectively break the intrinsic symmetry selection rule imposed on the system. Meanwhile, the intensity borrowed from local excitations could also be selectively promoted, allowing the manipulation of the excited quantum states. In addition, our calculations reveal that the donor and acceptor moieties can be unambiguously visualized in real space by tip-enhanced resonance Raman images. These findings can benefit light-harvesting and also be readily extended to diverse optical processes.