Hot-Carrier Transfer across a Nanoparticle-Molecule Junction: The Importance of Orbital Hybridization and Level Alignment

While direct hot-carrier transfer can increase photocatalytic activity, it is difficult to discern experimentally and competes with several other mechanisms. To shed light on these aspects, here, we model from first-principles hot-carrier generation across the interface between plasmonic nanoparticles and a CO molecule. The hot-electron transfer probability depends non-monotonically on the nanoparticle-molecule distance and can be effective at long distances, even before a strong chemical bond can form; hot-hole transfer on the other hand is limited to shorter distances. These observations can be explained by the energetic alignment between molecular and nanoparticle states as well as the excitation frequency. The hybridization of the molecular orbitals is the key predictor for hot-carrier transfer in these systems, emphasizing the necessity of ground state hybridization for accurate predictions. Finally, we show a nontrivial dependence of the hot-carrier distribution on the excitation energy, which could be exploited when optimizing photocatalytic systems.

Automated summary

This study models the generation of hot carriers across the interface between plasmonic nanoparticles and a CO molecule, finding that the hot electron transfer probability depends on the distance, energetic alignment, and excitation frequency, while hot hole transfer is limited to shorter distances. The hybridization of molecular orbitals is the key predictor for hot carrier transfer.