Single-molecule Tip-enhanced Raman Spectroscopy
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. © 2011 American Chemical Society.
Journal of Physical Chemistry C
Chemistry and Biochemistry
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.; and Van Duyne, Richard P., "Single-molecule Tip-enhanced Raman Spectroscopy" (2012). Faculty Publications. 1719.