Exceptional Spatial Variation of Charge Injection Energies on Plasmonic Surfaces.

Autor: Lei X; Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106, United States., Canestraight A; Department of Chemical Engineering, University of California Santa Barbara, Santa Barbara, California 93106, United States., Vlcek V; Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, California 93106, United States.; Department of Materials, University of California Santa Barbara, Santa Barbara, California 93106, United States.
Jazyk: angličtina
Zdroj: The journal of physical chemistry letters [J Phys Chem Lett] 2023 Sep 28; Vol. 14 (38), pp. 8470-8476. Date of Electronic Publication: 2023 Sep 18.
DOI: 10.1021/acs.jpclett.3c02223
Abstrakt: Charge injection into a molecule on a metallic interface is a key step in many photoactivated reactions. We employ the many-body perturbation theory and compute the hole and electron injection energies for CO 2 molecule on an Au nanoparticle with ∼3,000 electrons and compare it to results for idealized infinite surfaces. We demonstrate a surprisingly large variation of the injection energy barrier depending on the precise molecular position on the surface. Multiple "hot spots," characterized by low energy barriers, arise due to the competition between the plasmonic coupling and the degree of hybridization between the molecule and the substrate. The charge injection barrier to the adsorbate on the nanoparticle surface decreases from the facet edge to the facet center. This finding contrasts with the typical picture in which the electric field enhancement on the nanoparticle edges is considered the most critical factor.
Databáze: MEDLINE
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