Hot-Carrier Transfer across a Nanoparticle-Molecule Junction: The Importance of Orbital Hybridization and Level Alignment
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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
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Date
2022-11-09
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Language
en
Pages
7
8786-8792
8786-8792
Series
Nano Letters, Volume 22, issue 21
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.Description
Funding Information: We gratefully acknowledge helpful discussions with Patrick Rinke. This research has been funded by the Knut and Alice Wallenberg Foundation (Grants 2015.0055 and 2019.0140; J.F. and P.E.), the Swedish Foundation for Strategic Research Materials framework (Grant RMA15-0052; J.F. and P.E.), the Swedish Research Council (Grants 2015-04153 and 2020-04935; J.F. and P.E.), the European Union’s Horizon 2020 Research and Innovation Programme under the Marie Skłodowska-Curie Grant Agreement 838996 (T.P.R.), and the Academy of Finland under Grant 332429 (T.P.R.). The computations were enabled by resources provided by the Swedish National Infrastructure for Computing (SNIC) at NSC, C3SE, and PDC partially funded by the Swedish Research Council through Grant Agreement 2018-05973 as well as by the CSC─IT Center for Science, Finland, and by the Aalto Science-IT project, Aalto University School of Science. | openaire: EC/H2020/838996/EU//RealNanoPlasmon
Keywords
Adsorption, Hot-carrier, Nanoparticles, Plasmonic catalysis, TDDFT
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Citation
Fojt, J, Rossi, T P, Kuisma, M & Erhart, P 2022, ' Hot-Carrier Transfer across a Nanoparticle-Molecule Junction: The Importance of Orbital Hybridization and Level Alignment ', Nano Letters, vol. 22, no. 21, pp. 8786-8792 . https://doi.org/10.1021/acs.nanolett.2c02327
