4.8 Article

Angstrom Scale Chemical Analysis of Metal Supported Trans- and Cis-Regioisomers by Ultrahigh Vacuum Tip-Enhanced Raman Mapping

期刊

NANO LETTERS
卷 19, 期 5, 页码 3267-3272

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.nanolett.9b00826

关键词

Angstrom scale; regioisomer; ultrahigh vacuum scanning tunneling microscopy (UHV-STM); single molecule spectroscopy; tip-enhanced Raman spectroscopy (TERS); time-dependent density functional theory (TDDFT)

资金

  1. University of Illinois at Chicago
  2. National Science Foundation [CHE-1807465]
  3. ACS Petroleum Research Fund
  4. National Scientific Foundation of China [21778002, 21621061, 21861162008]

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Real space chemical analysis of two structurally very similar components, that is, regioisomers lies at the heart of heterogeneous catalysis reactions, modern-age electronic devices, and various other surface related problems in surface science and nanotechnology. One of the big challenges in surface chemistry is to identify different surface adsorbed molecules and analyze their chemical properties individually. Herein, we report a topological and chemical analysis of two regioisomers, trans- and cis-tetrakispentafluorophenylporphodi-lactone (trans- and cis-H2F20TPPDL) molecules by high resolution scanning tunneling microscopy, and ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS). Both isomeric structures are investigated individually on Ag(100) at liquid nitrogen temperature. Following that, we have successfully distinguished these two regioisomeric molecules simultaneously through TERS with an angstrom scale (8 A) spatial resolution. Also, the two-component organic heterojunction has been characterized at large scale using high-resolution two-dimensional mapping. Combined with time-dependent density functional theory simulations, we explain the TERS spectral discrepancies for both isomers in the fingerprint region.

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