Electron tunneling through the tip-surface junction at hydrogen-passivated silicon surfaces is well-known to cause hydrogen desorption via inelastic electron-phonon interactions. We develop a model that allows multiple-quantum transitions in the Si-H stretching mode. This model agrees quantitatively with available desorption data. We apply this model to desorption processes where the Si-H stretching vibration is pre-excited by near-infrared radiation. Although overtone excitation is inefficient, it is more efficient than inelastic electron scattering. Hence the combination of electron tunneling from the tip with pre-pumping of the long-lived Si-H stretching vibrations could lead to orders of magnitude enhanced patterning rates, while maintaining spatial resolution. (C) 2002 Elsevier Science B.V. All rights reserved.