Recombination of D atoms resurfacing from the octahedral subsurface site on Ni(1 11) has been investigated as a model for the reaction of sub-surface D. The desorbing flux is made up of two components: translationally hot D-2 formed in the reaction of energetic D atoms from the subsurface with chernisorbed D and a low energy component attributed to recombination of thermalised D. The D-2 product shows no preferred scattering direction, consistent with a 'hot precusor' mechanism for reaction. Resurfacing D atoms scatter across the D/Ni(1 1 1) surface, losing any stereochemical memory of the resurfacing site before they react with chemisorbed D. (C) 2002 Published by Elsevier Science B.V.