Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4'-Bipyridine Gold Nanosphere Oligomers.
We clarify mechanistic questions regarding plasmon-driven chemistry and nanoscale photocatalysis within optically confined near-field plasmonic systems. Using surfaceenhanced Raman scattering (SERS), we directly monitor the photoinduced reaction dynamics of 4,4'-bipyridine molecules, localized in pl...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 42; pp. 15212 - 15222 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
10/25/2017
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=125899034&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 125899034 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 10/25/2017 vid: 139 iid: 42 pid: 997 pub: American Chemical Society artinfo: ui: 125899034 10.1021/jacs.7b08868 ppf: 15212 ppct: 10 formats: tig: atl: Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4'-Bipyridine Gold Nanosphere Oligomers. aug: au: Sprague-Klein, Emily A. McAnally, Michael O. Zhdanov, Dmitry V. Zrimsek, Alyssa B. Apkarian, Vartkess A. Seideman, Tamar Schatz, George C. Van Duyne, Richard P. affil: Applied Physics Graduate Program, Northwestern University, Evanston, Illinois 60208, United States Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States Department of Chemistry, University of California, Irvine, California 92697, United States su: Charge exchange Plasmons (Physics) Photocatalysis SERS spectroscopy Oligomers Density functional theory Oxidation-reduction reaction sug: subj: Charge exchange Plasmons (Physics) Photocatalysis SERS spectroscopy Oligomers Density functional theory Oxidation-reduction reaction ab: We clarify mechanistic questions regarding plasmon-driven chemistry and nanoscale photocatalysis within optically confined near-field plasmonic systems. Using surfaceenhanced Raman scattering (SERS), we directly monitor the photoinduced reaction dynamics of 4,4'-bipyridine molecules, localized in plasmonic hot spots within individual gold nanosphere oligomers. Our experiment generates surface electrons from the gold nanoparticle using an intense offmolecular resonance continuous wave pump field and detects radical anion products via SERS. This is done by adopting a dualwavelength spectroscopic approach. Empirical evidence of plasmon-driven electron transfer is provided for the first time by direct detection of the 4,4'-bipyridine radical anion species localized in the plasmonic hot spots of individual gold nanosphere oligomers, corroborated by open-shell density functional theory calculations. An isotopologue approach using both protonated and deuterated 4,4'-bipyridine molecules demonstrates the single molecule response of plasmon-driven electron transfer occurring in single nanosphere oligomer systems with a 3% yield, a phenomenon unobserved in ensemble measurements under analogous experimental conditions. This mechanism has broad applicability to using nanoscale chemical reactors for surface redox reactions on the subnanometer scale. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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