The mechanism of laser-induced removal of Xe overlayers from a Si substrate has been investigated employing MD simulations and evaluated by buffer layer assisted laser patterning experiments. Two distinct regimes of overlayer removal are identified in the simulations of a uniform heating of the Si substrate by a 5 ns laser pulse: The intensive evaporation from the surface of the Xe overlayer and the detachment of the entire Xe overlayer driven by explosive boiling in the vicinity of the hot substrate. Simulations of selective heating of only a fraction of the silicon substrate suggest that the lateral heat transfer and bonding to the unheated, colder regions of the Xe overlayer is very efficient and suppresses the separation of a fraction of the overlayer from the substrate. Interaction with surrounding cold Xe is responsible for significant increase in the substrate temperature required for achieving the spatially selective ablation of the overlayer. The predictions of the MD simulations are found to be in a qualitative agreement with the results of experimental measurements of the threshold laser power required for the removal of Xe overlayers of different thickness and the shapes of metallic stripes generated by buffer-assisted laser patterning. SI