Origins of blinking in single-molecule Raman spectroscopy

We observe spectral and intensity fluctuations in Raman scattering from single molecules of 4-mercaptopyridine (4-Mpy) adsorbed on textured silver surfaces. We present evidence that the root cause of these fluctuations is thermal. Analysis of the spectra shows that in some cases the spectral changes are associated with molecular reorientation and in others with chemical reactions of the 4-Mpy. Analogous surfaces fully covered with 4-Mpy exhibit similar behavior, indicating that monolayer Raman spectra are dominated by a few molecules at most.