A new mechanism is introduced to describe desorption from surfaces under conditions of strong electronic excitation. When repetitive excitations occur within the relaxation time for the adsorbate-surface vibration, the process of desorption induced by multiple electronic transitions may provide an enhancement of orders of magnitude over a single-excitation mechanism. This generalization of the classic Menzel-Gomer-Redhead picture encompasses within one formalism both single-excitation processes and a thermal limit. The mechanism may be operative in desorption by femtosecond laser pulses. © 1992 The American Physical Society.