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The electrophoretic motion in monodisperse and polydisperse systems of silica microspheres was studied by evanescent wave dynamic light scattering technique with homodyne detection. Instead of the attempts to calculate average autocorrelation function, the intensity temporal profile was assessed by short-time Fourier transform was followed by multivariate curve resolution. The profile contained random alternate smooth regions and oscillating regions with definite frequencies. The effect was attributed to the few number of moving particles in the narrow zone, illuminated by evanescent wave. The changes in the short-time spectrum corresponded to entry or exit of individual particles. Feasibility to evaluate the mobility of individual particles in polydisperse systems is discussed.

Analysis of intensity/time series obtained in homodyne evanescent wave DLS electrophoretic experiments