Cargando…
Optical Images of Molecular Vibronic Couplings from Tip-Enhanced Fluorescence Excitation Spectroscopy
[Image: see text] 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 nu...
Autores principales: | , , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2021
|
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8790811/ https://www.ncbi.nlm.nih.gov/pubmed/35098231 http://dx.doi.org/10.1021/jacsau.1c00442 |
_version_ | 1784640098018525184 |
---|---|
author | Qiu, Feifei Gong, Zu-Yong Cao, Dongwei Song, Ce Tian, Guangjun Duan, Sai Luo, Yi |
author_facet | Qiu, Feifei Gong, Zu-Yong Cao, Dongwei Song, Ce Tian, Guangjun Duan, Sai Luo, Yi |
author_sort | Qiu, Feifei |
collection | PubMed |
description | [Image: see text] 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. |
format | Online Article Text |
id | pubmed-8790811 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-87908112022-01-27 Optical Images of Molecular Vibronic Couplings from Tip-Enhanced Fluorescence Excitation Spectroscopy Qiu, Feifei Gong, Zu-Yong Cao, Dongwei Song, Ce Tian, Guangjun Duan, Sai Luo, Yi JACS Au [Image: see text] 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. American Chemical Society 2021-12-23 /pmc/articles/PMC8790811/ /pubmed/35098231 http://dx.doi.org/10.1021/jacsau.1c00442 Text en © 2021 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Qiu, Feifei Gong, Zu-Yong Cao, Dongwei Song, Ce Tian, Guangjun Duan, Sai Luo, Yi Optical Images of Molecular Vibronic Couplings from Tip-Enhanced Fluorescence Excitation Spectroscopy |
title | Optical Images of Molecular Vibronic Couplings from
Tip-Enhanced Fluorescence Excitation Spectroscopy |
title_full | Optical Images of Molecular Vibronic Couplings from
Tip-Enhanced Fluorescence Excitation Spectroscopy |
title_fullStr | Optical Images of Molecular Vibronic Couplings from
Tip-Enhanced Fluorescence Excitation Spectroscopy |
title_full_unstemmed | Optical Images of Molecular Vibronic Couplings from
Tip-Enhanced Fluorescence Excitation Spectroscopy |
title_short | Optical Images of Molecular Vibronic Couplings from
Tip-Enhanced Fluorescence Excitation Spectroscopy |
title_sort | optical images of molecular vibronic couplings from
tip-enhanced fluorescence excitation spectroscopy |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8790811/ https://www.ncbi.nlm.nih.gov/pubmed/35098231 http://dx.doi.org/10.1021/jacsau.1c00442 |
work_keys_str_mv | AT qiufeifei opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy AT gongzuyong opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy AT caodongwei opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy AT songce opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy AT tianguangjun opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy AT duansai opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy AT luoyi opticalimagesofmolecularvibroniccouplingsfromtipenhancedfluorescenceexcitationspectroscopy |