Plasmon‐driven molecular scission

Abstract Plasmon‐driven photocatalysis offers a unique means of leveraging nanoscale light–matter interactions to convert photon energy into chemical energy in a chemoselective and regioselective manner under mild reaction conditions. Plasmon‐driven bond cleavage in molecular adsorbates represents a critical step in virtually all plasmon‐mediated photocatalytic reactions and has been identified as the rate‐determining step in many cases. This review article summarizes critical insights concerning plasmon‐triggered bond‐cleaving mechanisms gained through combined experimental and computational efforts over the past decade or so, elaborating on how the plasmon‐derived physiochemical effects, metal–adsorbate interactions, and local chemical environments profoundly influence chemoselective bond‐cleaving processes in a diverse set of molecular adsorbates ranging from small diatomic molecules to aliphatic and aromatic organic compounds. As demonstrated by several noteworthy examples, insights gained from fundamental mechanistic studies lay a critical knowledge foundation guiding rational design of nanoparticle–adsorbate systems with desired plasmonic molecule‐scissoring functions for targeted applications, such as controlled release of molecular cargos, surface coating of solid‐state materials, and selective bond activation for polymerization reactions.