Single-molecule tip-enhanced Raman spectroscopy

Matthew D. Sonntag, Jordan M. Klingsporn, Luis K. Garibay, John M. Roberts, Jon A. Dieringer, Tamar Seideman, Karl A. Scheidt, Lasse Jensen, George C Schatz, Richard P. Van Duyne

Research output: Contribution to journalArticle

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Abstract

An existence proof for single-molecule tip-enhanced Raman spectroscopy (SMTERS) is given using the frequency domain approach involving the two isotopologues of Rhodamine 6G (R6G) that were previously employed for single-molecule surface-enhanced Raman spectroscopy (SMSERS). A combination of experimental and theoretical studies provides a detailed view of the isotopic response of R6G-d 0 and R6G-d 4 in the 600 - 800 cm -1 region. The single-molecule nature of the TERS experiment is confirmed through two lines of evidence. First, the vibrational signature of only one isotopologue at a time was observed from multiple TER spectra. Second, the spectral wandering of the 610 cm -1 mode of R6G-d 0 was less than ±4 cm -1, which in turn is less than the 10 cm -1 isotopic shift so that no confusion in assignment resulted. As a consequence, the total TERS enhancement factor can now be accurately established as EF TERS = 1.0 × 10 13 because only one molecule at a time is measured. Furthermore, EF TERS can be partitioned into an electromagnetic contribution of 10 6 and a molecule-localized resonance Raman contribution of 10 7.

Original languageEnglish
Pages (from-to)478-483
Number of pages6
JournalJournal of Physical Chemistry C
Volume116
Issue number1
DOIs
Publication statusPublished - Jan 12 2012

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Raman spectroscopy
rhodamine
Molecules
molecules
confusion
signatures
electromagnetism
rhodamine 6G
augmentation
shift
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Sonntag, M. D., Klingsporn, J. M., Garibay, L. K., Roberts, J. M., Dieringer, J. A., Seideman, T., ... Van Duyne, R. P. (2012). Single-molecule tip-enhanced Raman spectroscopy. Journal of Physical Chemistry C, 116(1), 478-483. https://doi.org/10.1021/jp209982h

Single-molecule tip-enhanced Raman spectroscopy. / Sonntag, Matthew D.; Klingsporn, Jordan M.; Garibay, Luis K.; Roberts, John M.; Dieringer, Jon A.; Seideman, Tamar; Scheidt, Karl A.; Jensen, Lasse; Schatz, George C; Van Duyne, Richard P.

In: Journal of Physical Chemistry C, Vol. 116, No. 1, 12.01.2012, p. 478-483.

Research output: Contribution to journalArticle

Sonntag, MD, Klingsporn, JM, Garibay, LK, Roberts, JM, Dieringer, JA, Seideman, T, Scheidt, KA, Jensen, L, Schatz, GC & Van Duyne, RP 2012, 'Single-molecule tip-enhanced Raman spectroscopy', Journal of Physical Chemistry C, vol. 116, no. 1, pp. 478-483. https://doi.org/10.1021/jp209982h
Sonntag MD, Klingsporn JM, Garibay LK, Roberts JM, Dieringer JA, Seideman T et al. Single-molecule tip-enhanced Raman spectroscopy. Journal of Physical Chemistry C. 2012 Jan 12;116(1):478-483. https://doi.org/10.1021/jp209982h
Sonntag, Matthew D. ; Klingsporn, Jordan M. ; Garibay, Luis K. ; Roberts, John M. ; Dieringer, Jon A. ; Seideman, Tamar ; Scheidt, Karl A. ; Jensen, Lasse ; Schatz, George C ; Van Duyne, Richard P. / Single-molecule tip-enhanced Raman spectroscopy. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 1. pp. 478-483.
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