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

Jakub Fojt, Tuomas P. Rossi, Mikael Kuisma, Paul Erhart*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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Abstract

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 nonmonotonically 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.

Original languageEnglish
JournalNano Letters
Volume22
Issue number21
Pages (from-to)8786–8792
ISSN1530-6984
DOIs
Publication statusPublished - 2022

Keywords

  • Adsorption
  • Hot-carrier
  • Nanoparticles
  • Plasmonic catalysis
  • TDDFT

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