Catalytic surface controls hot-carriers in hybrid plasmonic nanostructures

Understanding and controlling hot carrier (HC) dynamics at metal-molecule interfaces is central to advancing plasmon-driven photocatalysis and optoelectronics. In this work, we use real-time time-dependent density functional theory (RT-TDDFT) to uncover how catalytic surface engineering with Pd and Pt layers modulates hot carrier generation, localization, and energy transfer in hybrid aluminum nanostructures coupled to a pyrazine molecule. We demonstrate that ultrathin Pd/Pt coatings not only drastically reshape the energetic and spatial distribution of hot carriers but also enable precise tuning of HC transfer to the molecular adsorbate. This surface-controlled modulation of HC behavior introduces a powerful design strategy for achieving site-selective energy conversion at functionalized plasmonic interfaces. Our results provide atomistic insight into plasmon decay pathways in complex nanoarchitectures and open new avenues for engineering responsive plasmonic materials for nanoscale photocatalysis, energy harvesting, and molecular electronics.