biostudies-literatureFojt JAcademy of FinlandH2020 Marie Sklodowska-Curie ActionsKnut och Alice Wallenbergs StiftelseStiftelsen f?r Strategisk ForskningVetenskapsr?det8786-8792https://www.ebi.ac.uk/biostudies/studies/S-EPMC9650767biostudies-literatureUnknown22(21)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 Nano lettersHot-Carrier Transfer across a Nanoparticle-Molecule Junction: The Importance of Orbital Hybridization and Level Alignment.PMC96507678389963324292015-04153RMA15-00522015.00552019.01402020-04935Kuisma MErhart PRossi TPFojt JfalseHot-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 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 2022-01-01T00:00:00Z2022 Nov2025-04-04T09:02:38.079Z2025-04-04T09:02:38.079ZS-EPMC96507673620074410.1021/acs.nanolett.2c02327