Submicron aerosol particles of carbon, different metals and exhaust particles from a diesel engine are characterized via the charge p they obtain by photoelectron emission when irradiated by specially designed excimer lamps. The high intensity of these monochromatic lamps makes it possible to charge all particles to the limit defined by Coulomb recapture of the electron. This maximum charge p(max)(R, Phi) depends only on the particle radius R and photothreshold Phi(infinity) and can therefore be used for identification and separation of different materials as well as detection of small changes in the state of the surface in terms of the outermost atomic layer. The latter effect is demonstrated on C, Cu and diesel particle coated with Zn or surface oxidized with O-3. The function p(max)(R, Phi) for spherical particles holds well for agglomerated structures, if particle size is defined by the electric mobility of the particles. As long as less than 10% of p(max) are reached at short radiation time or small intensity, the photoemission probability mu linearly depends on a photoemission parameter c related to the absorption behaviour of the particles. The charge distribution under these conditions is explained by Poisson statistics. The parameters Phi(infinity), c and R can all be determined using excimer lamp photoelectric sensors containing lamps of different wavelengths. Excimer lamps represent an interesting alternative to conventional charging principles in electrostatic precipitators for gas cleaning.