Abstract

The dynamics of an adsorbed atom irradiated by an infrared laser in resonance with the vibrational levels of the adbond can be described by the reduced density matrix of the adbond. A nonperturbative approach for the laser-adbond interaction is presented. Relaxation against the substrate degrees of freedom is described by second-order perturbation theory. Both pulsed lasers and cw lasers are considered. Expressions for the transition probabilities are derived in the low-intensity and in the high-intensity limits. It appears that the time evolution of the occupation probabilities is coupled to those of the coherences, i.e., a master equation cannot be obtained. The time evolution of all the elements of the reduced density matrix has to be taken into account. These expressions act as a basis for the study of physical processes as resonant de sorption, resonant heating, and laser-induced thermal desorption. Resonant desorption is described by the addition of loss terms into the equations of motion of the occupation probabilities. Expressions for the rate of desorption as well as the rate of energy transfer to the substrate are given. In particular, a comparison is made for the effect of a cw laser vs a pulsed laser on the desorption and resonant heating.

© 1986 Optical Society of America