Hot-Carrier Transfer across a Nanoparticle-Molecule Junction: The Importance of Orbital Hybridization and Level Alignment
Artikel i vetenskaplig tidskrift, 2022
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.
TDDFT
Hot-carrier
Plasmonic catalysis
Nanoparticles
Adsorption
Författare
Jakub Fojt
Chalmers, Fysik, Kondenserad materie- och materialteori
T. P. Rossi
Aalto-Yliopisto
Mikael Juhani Kuisma
Danmarks Tekniske Universitet (DTU)
Paul Erhart
Chalmers, Fysik, Kondenserad materie- och materialteori
Nano Letters
1530-6984 (ISSN) 1530-6992 (eISSN)
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Styrkeområden
Nanovetenskap och nanoteknik
Infrastruktur
C3SE (Chalmers Centre for Computational Science and Engineering)
Ämneskategorier
Atom- och molekylfysik och optik
Teoretisk kemi
Den kondenserade materiens fysik
DOI
10.1021/acs.nanolett.2c02327
PubMed
36200744
Relaterade dataset
Data for "Hot-carrier transfer across a nanoparticle-molecule junction: The importance of orbital hybridization and level alignment" [dataset]
DOI: 10.5281/zenodo.6524101