The formation of the hydrogenic sub-surface layer during the early stages of silane dosing on Cu(111) has been shown to be due to the interaction between the 1t(2) state of the silane molecule and the Cu 3d surface band. The concurrently formed delocalised Cu 4s/4p surface band has been seen to interact with the 2a(1) state of the silane molecule. The electronic structure of the hydrogenated Cu(111) surface shows that the hydrogen ion cores induce a rotation of the surface Cu 3d states and a repolarisation of the more diffuse Cu 4s and 4p surface states. (C) 2011 Elsevier B.V. All rights reserved.