Structure sensitivity in adsorption: CO interaction with stepped and reconstructed Pt surfaces

The structure sensitivity of CO adsorption on different flat, stepped, kinked and reconstructed Pt surfaces is studied using large-scale density-functional calculations. We find an extremely strong structure sensitivity in the adsorption energy with variations up to 1 eV (or 100%) from one structure to the next. We propose a model to explain this behavior, and use it to discuss more generally the origin of structure sensitivity in heterogeneous catalysis.