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Optical Images of Molecular Vibronic Couplings from Tip-Enhanced Fluorescence Excitation SpectroscopyY
Yanshan Univ, Sch Sci, State Key Lab Metastable Mat Sci & Technol, Qinhuangdao 066004, Hebei, Peoples R China.;Yanshan Univ, Sch Sci, Key Lab Microstruct Mat Phys Hebei Prov, Qinhuangdao 066004, Hebei, Peoples R China..
Fudan Univ, Collaborat Innovat Ctr Chem Energy Mat, Shanghai Key Lab Mol Catalysis & Innovat Mat, MOE Key Lab Computat Phys Sci,Dept Chem, Shanghai 200433, Peoples R China..
Yanshan Univ, Sch Sci, State Key Lab Metastable Mat Sci & Technol, Qinhuangdao 066004, Hebei, Peoples R China.;Yanshan Univ, Sch Sci, Key Lab Microstruct Mat Phys Hebei Prov, Qinhuangdao 066004, Hebei, Peoples R China..
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, Hefei 230026, Anhui, Peoples R China.;Univ Sci & Technol China, Synerget Innovat Ctr Quantum Informat & Quantum P, Hefei 230026, Anhui, Peoples R China.
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2022 (English)In: JACS Au, E-ISSN 2691-3704, Vol. 2, no 1, p. 150-158Article in journal (Refereed) Published
Abstract [en]

Tip-based photoemission spectroscopic techniques have now achieved subnanometer resolution that allows visualization of the chemical structure and even the ground-state vibrational modes of a single molecule. However, the ability to visualize the interplay between electronic and nuclear motions of excited states, i.e., vibronic couplings, is yet to be explored. Herein, we theoretically propose a new technique, namely, tip-enhanced fluorescence excitation (TEFE). TEFE takes advantage of the highly confined plasmonic field and thus can offer a possibility to directly visualize the vibronic effect of a single molecule in real space for arbitrary excited states in a given energy window. Numerical simulations for a single porphine molecule confirm that vibronic couplings originating from Herzberg-Teller (HT) active modes can be visually identified. TEFE further enables high-order vibrational transitions that are normally suppressed in the other plasmon-based processes. Images of the combination vibrational transitions have the same pattern as that of their parental HT active mode's fundamental transition, providing a direct protocol for measurements of the activity of Franck-Condon modes of selected excited states. These findings strongly suggest that TEFE is a powerful strategy to identify the involvement of molecular moieties in the complicated electron-nuclear interactions of the excited states at the single-molecule level.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2022. Vol. 2, no 1, p. 150-158
Keywords [en]
vibronic coupling, tip-enhanced fluorescence excitation, single-molecule imaging, plasmonic field, Franck-Condon activity
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-310791DOI: 10.1021/jacsau.1c00442ISI: 000772069200015PubMedID: 35098231Scopus ID: 2-s2.0-85134593877OAI: oai:DiVA.org:kth-310791DiVA, id: diva2:1650479
Note

QC 20220407

Available from: 2022-04-07 Created: 2022-04-07 Last updated: 2024-03-15Bibliographically approved

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Song, CeTian, GuangjunDuan, Sai

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