The adsorption of Xe adatoms on the Fe(0 0 1) surface is investigated by first-principles calculations. The van der Waals interactions are considered in the optimization of the geometric structure. An equilibrium distance of 3.345 angstrom between Xe and the substrate is obtained for the on-top site adsorption. The induced states are predicted by the local density of states. The electron redistribution and donation at the 5p states are revealed by the differential electron densities. The sublevel splitting of the 5p(3/2) states is observed at very low coverage. Negative/positive spin polarization of the 5p(3/2)/induced states is well described by the calculated spin density. (C) 2011 Elsevier B. V. All rights reserved.