Surface-enhanced Raman excitation spectroscopy of a single rhodamine 6G molecule

Jon A. Dieringer, Kristin L. Wustholz, David J. Masiello, Jon P. Camden, Samuel L. Kleinman, George C. Schatz, Richard P. Van Duyne

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248 Citations (Scopus)


The surface-enhanced Raman excitation profiles (REPs) of rhodamine 6G (R6G) on Ag surfaces are studied using a tunable optical parametric oscillator excitation source and versatile detection scheme. These experiments afford the ability to finely tune the excitation wavelength near the molecular resonance of R6G (i.e., ~500-575 nm) and perform wavelength-scanned surface-enhanced Raman excitation measurements of a single molecule. The ensemble-averaged surface-enhanced REPs are measured for collections of molecules on Ag island films. The relative contributions of the 0-0 and 0-1 vibronic transitions to the surface-enhanced REPs vary with vibrational frequency. These results highlight the role of excitation energy in determining the resonance Raman intensities for R6G on surface-enhancing nanostructures. Single-molecule measurements are obtained from individual molecules of R6G on Ag colloidal aggregates, where single-molecule junctions are located using the isotope-edited approach. Overall, single-molecule surface-enhanced REPs are narrow in comparison to the ensemble-averaged excitation profiles due to a reduction in inhomogeneous broadening. This work describes the first Raman excitation spectroscopy studies of a single molecule, revealing new information previously obscured by the ensemble.

Original languageEnglish
Pages (from-to)849-854
Number of pages6
JournalJournal of the American Chemical Society
Issue number2
Publication statusPublished - Jan 21 2009

ASJC Scopus subject areas

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

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    Dieringer, J. A., Wustholz, K. L., Masiello, D. J., Camden, J. P., Kleinman, S. L., Schatz, G. C., & Van Duyne, R. P. (2009). Surface-enhanced Raman excitation spectroscopy of a single rhodamine 6G molecule. Journal of the American Chemical Society, 131(2), 849-854.