At fluences well below the threshold for plasma formation, we have characterized the direct desorption of atomic ions from fused silica surfaces during 157-nm irradiation by time-resolved mass spectroscopy. The principal ions are Si + and O + . The emission intensities are dramatically increased by treatments that increase the density of surface defects. Molecular dynamics simulations of the silica surface suggest that silicon ions bound at surface oxygen vacancies (analogous to E' centers) provide suitable configurations for the emission of Si + . We propose that emission is best understood in terms of a hybrid mechanism involving both antibonding chemical forces (MenzelGomer-Redhead model) and repulsive electrostatic forces on the adsorbed ion after laser excitation of the underlying defect.