High-resolution tip-enhanced Raman scattering probes sub-molecular density changes

Xing Chen, Pengchong Liu, Zhongwei Hu, Lasse Jensen

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Tip-enhanced Raman spectroscopy (TERS) exhibits new selection rule and sub-nanometer spatial resolution, which is attributed to the plasmonic near-field confinement. Despite recent advances in simulations of TERS spectra under highly confined fields, a simply physical mechanism has remained elusive. In this work we show that single-molecule TERS images can be explained by local sub-molecular density changes induced by the confined near-field during the Raman process. The local sub-molecular density changes determine the spatial resolution in TERS and the gradient-based selection rule. Using this approach we find that the four-fold symmetry of meso-tetrakis(3,5-di-tert-butylphenyl)porphyrin (H2TBPP) TERS images observed in experiments arises from the combination of degenerate normal modes localized in the functional side groups rather than the porphyrin ring as previously considered. As an illustration of the potential of the method, we demonstrate how this new theory can be applied to microscopic structure characterization.

Original languageEnglish (US)
Article number2567
JournalNature communications
Volume10
Issue number1
DOIs
StatePublished - Dec 1 2019

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Molecular Probes
Raman Spectrum Analysis
Raman spectroscopy
Raman scattering
Raman spectra
probes
high resolution
Porphyrins
porphyrins
near fields
spatial resolution
gradients
Molecules
rings
symmetry
molecules
simulation
Experiments

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

Cite this

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title = "High-resolution tip-enhanced Raman scattering probes sub-molecular density changes",
abstract = "Tip-enhanced Raman spectroscopy (TERS) exhibits new selection rule and sub-nanometer spatial resolution, which is attributed to the plasmonic near-field confinement. Despite recent advances in simulations of TERS spectra under highly confined fields, a simply physical mechanism has remained elusive. In this work we show that single-molecule TERS images can be explained by local sub-molecular density changes induced by the confined near-field during the Raman process. The local sub-molecular density changes determine the spatial resolution in TERS and the gradient-based selection rule. Using this approach we find that the four-fold symmetry of meso-tetrakis(3,5-di-tert-butylphenyl)porphyrin (H2TBPP) TERS images observed in experiments arises from the combination of degenerate normal modes localized in the functional side groups rather than the porphyrin ring as previously considered. As an illustration of the potential of the method, we demonstrate how this new theory can be applied to microscopic structure characterization.",
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High-resolution tip-enhanced Raman scattering probes sub-molecular density changes. / Chen, Xing; Liu, Pengchong; Hu, Zhongwei; Jensen, Lasse.

In: Nature communications, Vol. 10, No. 1, 2567, 01.12.2019.

Research output: Contribution to journalArticle

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AU - Liu, Pengchong

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