The dynamics of short pulsed laser-induced desorption of alkali atoms from poly-dimethylsiloxane (PDMS) coated glass prism surfaces is investigated. Kinetic energies of desorbing sodium atoms of several hundred meV are found, increasing with increasing laser fluence. Evanescent wave measurements suggest that the desorbed atoms stein from a subsurface layer of the PDMS film, resulting in diffusional characteristics for the total yield of the desorption process. (C) 2004 Elsevier B.V. All rights reserved.