Plasmon induced hot carrier generation in a pyridine@Au20 composite.

Using time-dependent density functional theory calculations, we have investigated the generation of hot carriers (HCs) in a system comprising a pyridine molecule and a tetrahedral Au 20 plasmonic cluster. Our findings indicate that the decay of the localized surface plasmon resonance (LSPR) induced in the pyridine@Au 20 system by a laser pulse facilitates the direct transfer of hot electrons from the occupied states of the Au 20 cluster to the unoccupied molecular orbitals of pyridine. Notably, we have identified that the interparticle gap distance between the Au 20 cluster and the pyridine molecule plays a critical role in controlling the generation of HCs. By precisely controlling the interaction between the plasmonic cluster and the molecule, we can effectively manipulate the energy distribution of the generated HCs. These insights have the potential to drive advancements in the development of more efficient systems for plasmonic catalysis.