Density Functional Tight-Binding Captures Plasmon-Driven H₂ Dissociation on Al Nanocrystals

Aluminum nanocrystals offer a promising platform for plasmonic photocatalysis, yet a detailed understanding of their electron dynamics and consequent photocatalytic performance has been challenging due to computational limitations. Here, we employ density functional tight-binding methods (DFTB) to investigate the optical properties and H2 dissociation dynamics of Al nanocrystals with varying sizes and geometries. Our real-time simulations reveal that Al’s free electron nature enables efficient light-matter interactions and rapid electronic thermalization. Cubic and octahedral nanocrystals ranging from 0.5 to 4.5 nm exhibit size-dependent plasmon resonances in the ultraviolet, with distinct spectral features arising from the particle geometry and electronic structure. By simulating H2 dissociation near Al nanocrystals, we demonstrate that hot electrons generated through plasmon excitation can overcome the molecule’s strong chemical bond within tens of femtoseconds. The laser intensity threshold is comparable to previous reports for Ag nanocrystals, although significantly lower than that of Au. Notably, the dipolar plasmon mode demonstrates a higher efficiency for this reaction than the localized interband transition for particles at these sizes. Taken together, this work provides mechanistic insights into plasmon-driven catalysis and showcases DFTB’s capability to study quantum plasmonics at unprecedented length and time scales.