Statistical analysis of intensity fluctuations in single molecule SERS spectra

We have investigated the fluctuations of the intensity and the line intermittency in the surface enhanced Raman spectra of a single iron-protoporphyrin IX molecule. A statistical analysis has revealed a high correlation between the intensity of each frequency couple in the spectrum. Removal of the continuum background has led to a suppression of the correlation at those frequencies where no Raman lines are present. Conversely, we have observed the persistence of a strong correlation at the intensities corresponding to the vibrational modes of the molecule. Further evidence of correlation between the intensities and the background signal indicates that the background is involved in the enhancement mechanism. Moreover, analysis of the Raman line intermittency reveals a random activation of the different molecular vibrational modes. These results can be generally put into relationship to the presence of two different contributions to the intensity fluctuations: one, strictly related to the continuum background, and affecting the whole spectrum, and another one which selectively acts on the various vibrational modes of the molecule.