IR photodesorption is a type of desorption that occurs when an infrared light hits a surface and activates processes involving the excitation of an internal vibrational mode of the previously absorbed molecules followed by the desorption of the species into the gas phase. One can selectively excite electrons or vibrations of the adsorbate or of the adsorbate-substrate coupled system. This relaxation of the bonds together with a sufficient energy exchange from the incident light to the system will eventually lead to desorption. 
Generally, the phenomenon is more effective for weaker-bound physisorbed species, which have a smaller adsorption potential depth compared to that of the chemisorbed ones. In fact, a shallower potential requires lower laser intensities to set a molecule free from the surface and make IR-photodesorption experiments feasible, because the measured desorption times are usually longer than the inverse of the other relaxation rates in the problem.