Hot-Carrier Transfer across a Nanoparticle-Molecule Junction: The Importance of Orbital Hybridization and Level Alignment
Journal article, 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
Author
Jakub Fojt
Chalmers, Physics, Condensed Matter and Materials Theory
T. P. Rossi
Aalto University
Mikael Juhani Kuisma
Technical University of Denmark (DTU)
Paul Erhart
Chalmers, Physics, Condensed Matter and Materials Theory
Nano Letters
1530-6984 (ISSN) 1530-6992 (eISSN)
Vol. 22 21 8786-8792Plasmon-exciton coupling at the attosecond-subnanometer scale: Tailoring strong light-matter interactions at room temperature
Knut and Alice Wallenberg Foundation (2019.0140), 2020-07-01 -- 2025-06-30.
Plastic Plasmonics
Swedish Foundation for Strategic Research (SSF) (RMA15-0052), 2016-05-01 -- 2022-06-30.
Towards nanoscale reality in plasmonic hot-carrier generation (RealNanoPlasmon)
European Commission (EC) (EC/H2020/838996), 2019-04-01 -- 2021-03-31.
Nanolegeringar för plasmoniska tillämpningar
Swedish Research Council (VR) (2015-04153), 2016-01-01 -- 2019-12-31.
Single Particle Catalysis in Nanoreactors (SPCN)
Knut and Alice Wallenberg Foundation (KAW2015.0057), 2016-01-01 -- 2020-12-31.
Phase behavior and electronic properties of mixed halide perovskites from atomic scale simulations
Swedish Research Council (VR) (2020-04935), 2020-12-01 -- 2024-11-30.
Areas of Advance
Nanoscience and Nanotechnology
Infrastructure
C3SE (Chalmers Centre for Computational Science and Engineering)
Subject Categories
Atom and Molecular Physics and Optics
Theoretical Chemistry
Condensed Matter Physics
DOI
10.1021/acs.nanolett.2c02327
PubMed
36200744
Related datasets
Data for "Hot-carrier transfer across a nanoparticle-molecule junction: The importance of orbital hybridization and level alignment" [dataset]
DOI: 10.5281/zenodo.6524101