  We propose an explanation for the recently measured slow fluctuations and
``blinking'' in the surface enhanced Raman scattering (SERS) spectrum of single
molecules adsorbed on a silver colloidal particle. We suggest that these
fluctuations may be related to the dynamic relaxation of the surface roughness
on the nanometer scale and show that there are two classes of roughness with
qualitatively different dynamics. The predictions agree with measurements of
surface roughness relaxation. Using a theoretical model for the kinetics of
surface roughness relaxation in the presence of charges and optical electrical
fields, we predict that the high-frequency electromagnetic field increases both
the effective surface tension and the surface diffusion constant and thus
accelerates the surface smoothing kinetics and time scale of the Raman
fluctuations in manner that is linear with the laser power intensity, while the
addition of salt retards the surface relaxation kinetics and increases the time
scale of the fluctuations. These predictions are in qualitative agreement with
the Raman experiments.

Soft Condensed Matter;Statistical Mechanics