Ab Initio Simulations Predict Highly Efficient Transfer of Hot Electrons from Noble-Metal Nanoclusters To Degrade Per- and Polyfluoroalkyl Substances

Plasmons, collective oscillations of conduction electrons in metallic nanoclusters (NCs), enable plasmon-mediated photochemistry by generating energetic hot carriers (HCs) through a nonradiative decay mechanism. Maximizing both HC generation within NCs and their efficient transfer to adjacent molecules remains a central challenge for advancing plasmon-driven photocatalysis. Here, we establish how NC composition, geometry, and PFAS–NC configuration can be tuned to achieve >25% efficiency in direct hot electron transfer from NCs to nearby per- and polyfluoroalkyl substances (PFAS). We find that silver (Ag) NCs exhibit substantially higher efficiencies in HC generation and interfacial HC transfer than their gold (Au) counterparts. Among the geometries considered (icosahedral, cuboctahedral, and tetrahedral), tetrahedral Ag NC shows the greatest enhancement in both HC production and direct hot-electron injection to PFAS. Furthermore, we reveal that the hot-electron transfer probability from a tetrahedral Ag NC increases substantially when PFAS is positioned at the plasmonic hot spot associated with maximal field enhancement. Together, these findings yield fundamental structure–property rules and strategic pathways for designing NC platforms that achieve superior plasmon-mediated HC generation and transfer, which are essential for high-performance photocatalysis.