Silver selectively catalyzes the hydrogenation of the C=O group of alpha, beta-unsaturated aldehydes, indicating preferential adsorption-induced activation of this bond compared to the adjacent C=C bond. Using a density functional method and periodic slab models, we studied the propensity of the flat Ag(110) and the stepped Ag(221) surfaces to activate the C=O bond of adsorbed acrolein. Our calculations show acrolein to interact only weakly with all adsorption sites under study (by at most 35 kJ mol(-1)), resulting in very limited bond activation. Therefore, we conclude that other active sites on silver catalysts participate in the experimentally observed selective hydrogenation. (c) 2005 Elsevier B.V. All rights reserved.