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Abstract

The dissociative adsorption reaction of hydrogen on noble metals is believed to be well-described within the Born–Oppenheimer approximation. In this work, we have experimentally derived translational energy distributions for selected quantum states of H2 and D2 formed in associative desorption reactions at a Au(111) surface. Using the principle of detailed balance, we compare our results to theory carried out at the same level of sophistication as was done for the reaction on copper. The theory predicts translational excitation that is much higher than is seen in experiment and fails to reproduce the experimentally observed isotope effect. The large deviations between experiment and theory are surprising because, for the same reactions occurring on Cu(111), a similar theoretical strategy agreed with experiment, yielding “chemical accuracy”. We argue that electron–hole pair excitation is more important for the reaction on gold, an effect that may be related to the reaction’s later transition state.