- Plasmon-driven dehalogenation of brominated purines has been recently explored as a model system to understand fundamental aspects of plasmon-assisted chemical reactions. Here, it is shown that divalent Ca2+ ions strongly bridge the adsorption of bromoadenine (Br-Ade) to Ag surfaces.
Such ion-mediated binding increases the molecule's adsorption energy leading to an overlap of the metal energy states and the molecular states, enabling the chemical interface damping (CID) of the plasmon modes of the Ag nanostructures (i.e., direct electron transfer from the metal to Br-Ade).
Consequently, the conversion of Br-Ade to adenine almost doubles following the addition of Ca2+.
These experimental results, supported by theoretical calculations of the local density of states of the Ag/Br-Ade complex, indicate a change of the charge transfer pathway driving the dehalogenation reaction, from Landau damping (in the lack of Ca2+ ions) to CID (after the addition of Ca2+).
The results show that the surface dynamics of chemical speciesPlasmon-driven dehalogenation of brominated purines has been recently explored as a model system to understand fundamental aspects of plasmon-assisted chemical reactions. Here, it is shown that divalent Ca2+ ions strongly bridge the adsorption of bromoadenine (Br-Ade) to Ag surfaces.
Such ion-mediated binding increases the molecule's adsorption energy leading to an overlap of the metal energy states and the molecular states, enabling the chemical interface damping (CID) of the plasmon modes of the Ag nanostructures (i.e., direct electron transfer from the metal to Br-Ade).
Consequently, the conversion of Br-Ade to adenine almost doubles following the addition of Ca2+.
These experimental results, supported by theoretical calculations of the local density of states of the Ag/Br-Ade complex, indicate a change of the charge transfer pathway driving the dehalogenation reaction, from Landau damping (in the lack of Ca2+ ions) to CID (after the addition of Ca2+).
The results show that the surface dynamics of chemical species (including water molecules) play an essential role in charge transfer at plasmonic interfaces and cannot be ignored. It is envisioned that these results will help in designing more efficient nanoreactors, harnessing the full potential of plasmon-assisted chemistry.…
MetadatenAuthor details: | Andrei Stefancu, Lin Nan, Li Zhu, Vasile Chis, Ilko BaldORCiDGND, Min Liu, Nicolae Leopold, Stefan A. MaierORCiDGND, Emiliano CortesORCiD |
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DOI: | https://doi.org/10.1002/adom.202200397 |
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ISSN: | 2195-1071 |
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Title of parent work (English): | Advanced optical materials |
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Publisher: | Wiley-VCH |
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Place of publishing: | Weinheim |
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Publication type: | Article |
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Language: | English |
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Date of first publication: | 2022/05/11 |
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Publication year: | 2022 |
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Release date: | 2024/06/07 |
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Tag: | Hofmeister effect; chemical interface damping; hydration layer; plasmonic chemistry; specific ion effects; surface-enhanced Raman scattering |
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Volume: | 10 |
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Issue: | 14 |
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Article number: | 2200397 |
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Number of pages: | 10 |
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Funding institution: | Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under; Germany's Excellence Strategy [EXC 2089/1 - 390776260]; Bavarian program; Solar Technologies Go Hybrid (SolTech); Center for NanoScience (CeNS);; European Commission through the ERC [802989]; Romanian Ministry of; Research and Innovation, CCCDI-UEFISCDI [PN-III-P4-ID-PCCF-2016-0112,; PN-III-P2-2.1-PED-2019-3268, PN-III-P4-ID-PCE-2020-1292]; Natural; Science Foundation of China [21872174, 22002189, U1932148];; International Science and Technology Cooperation Program; [2017YFE0127800]; Hunan Province Key Field RD Program [2020WK2002];; Hunan Provincial Natural Science Foundation of China [2020JJ2041,; 2020JJ5691]; Projekt DEAL |
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Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
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DDC classification: | 5 Naturwissenschaften und Mathematik / 53 Physik / 530 Physik |
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| 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
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Peer review: | Referiert |
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Publishing method: | Open Access / Hybrid Open-Access |
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License (German): | CC-BY - Namensnennung 4.0 International |
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