(542b) First-Principles Modeling of Hot-Carrier-Assisted Hydrogenation Reactions

Generation of highly energetic carriers (electrons and holes) in plasmonic nanostructures opens new pathways to trigger and enhance chemical transformations toward a certain desired product by harvesting solar energy. Here we intend to reveal, at the atomic level, the fundamental mechanism in the plasmonic hot-carrier-driven hydrogenation reactions. We employed density functional theory (DFT) calculations to explore the potential energy surfaces of hydrogenation of 4-nitrophenol and phenylacetylene. The reaction profiles with and without hot electrons at the different unoccupied molecular orbitals were calculated and compared to address the reaction mechanism. This work shed lights on the bond association process, which is a key elementary step in many practical industrial processes.