Surface-induced C-O bond anharmonicity of methoxy adsorbed on Cu(100): experiments and density-functional theory calculations.

The anharmonic properties of a surface intermediate, methoxy, adsorbed on Cu(100) are investigated by surface infrared overtone spectroscopy and density-functional-theory electronic structure calculations. The anharmonicity is measured in the zero-coverage limit, and it is observed that the anharmonicity is increased upon adsorption as compared with the free methanol. By combining experiments with calculations we demonstrate that modifications of the anharmonicity of the methoxy species is indeed induced by adsorption onto the copper surface and not by the formation of the methoxy species.