We present experimental and modeling studies of UV nanosecond pulsed laser desorption and ablation of (111) bulk silicon. The results involve a new approach to the analysis of plume formation dynamics under high-energy photon irradiation of the semiconductor surface. Non-thermal, photo-induced desorption has been observed at low laser fluence, well below the melting threshold. Under ablation conditions, the non-thermal ions also have a high concentration. The origin of these ions is discussed on the basis of electronic excitation of Si surface states associated with the Coulomb explosion mechanism. We present a model describing dynamics of silicon target excitation, heating and charge-carrier transport.