Adsorption, mobility, and dimerization of benzaldehyde on Pt(111)

Building on results for the adsorption of benzene on Pt(111), the adsorption of benzaldehyde is investigated using density functional theory. Benzaldehyde is found to chemisorb preferentially with its aromatic ring in the flat-lying bridge geometry that is also preferred for benzene. Across the investigated geometries, adsorption is homogeneously weakened compared to corresponding benzene geometries. This is found to be true for very different adsorption modes, namely, η(6) and η(8) modes, the latter having metal atoms inserted in the carbonyl bond. Reorientation and diffusion of benzaldehyde is found to have low energy barriers. Aggregation of molecules in dimers bound by aryl C-H···O hydrogen bonds is investigated, and specific configurations are found to be up to 0.15 eV more favorable than optimally configured, separated adsorbates. The binding is significantly stronger than what is found for gas phase dimers, suggesting an enhancing effect of the metal interaction.