The origin of relative intensity fluctuations in single-molecule tip-enhanced Raman spectroscopy

Matthew D. Sonntag, Dhabih Chulhai, Tamar Seideman, Lasse Jensen, Richard P. Van Duyne

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Abstract

An explanation of the relative intensity fluctuations observed in single-molecule Raman experiments is described utilizing both single-molecule tip-enhanced Raman spectroscopy and time-dependent density functional theory calculations. No correlation is observed in mode to mode intensity fluctuations indicating that the changes in mode intensities are completely independent. Theoretical calculations provide convincing evidence that the fluctuations are not the result of diffusion, orientation, or local electromagnetic field gradients but rather are the result of subtle variations of the excited-state lifetime, energy, and geometry of the molecule. These variations in the excited-state properties will provide information on adsorbate-adsorbate and adsorbate-substrate interactions and may allow for inversion of experimental results to obtain these excited-state properties.

Original languageEnglish (US)
Pages (from-to)17187-17192
Number of pages6
JournalJournal of the American Chemical Society
Volume135
Issue number45
DOIs
StatePublished - Nov 13 2013

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All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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