Mechanism of plasmon-induced chemical reactions

Plasmon-induced chemical reactions offer a unique opportunity to control molecular transformations through the interplay of light and matter at the nanoscale. This thesis investigates the fundamental mechanisms driving these reactions, focusing on the formation and characteristics of hybrid electronic states. Using a combined quantum chemical–quantum/classical hybrid approach, the effects of molecular binding modes, molecule–molecule interactions on the nanoparticle surface, near-field electromagnetic enhancement, and charge-transfer phenomena were systematically explored. It is shown that the characteristics of hybrid charge-transfer excitations are central to understanding the mechanisms that govern both reactivity and selectivity in plasmon-catalyzed processes. These excited states—and their ability to mediate chemical transformations—are highly sensitive to molecular orientation, dispersive interactions, and environmental factors. Theoretical insights are validated through close collaboration with SERS and TERS experiments, enabling a molecular-level understanding of excitation-driven catalysis. Altogether, this research provides a comprehensive framework for understanding and controlling plasmon-induced chemical reactions and offers guiding principles for the rational design of plasmonic catalysts.