Vibrational fine structure in the C 1s core level photoemission of chemisorbed molecules: ethylene and ethylidyne on Rh(111)

The origin of fine structure in the core-level photoemission spectra of the C2H4, C2D4, C2H3 and C2D3 molecules chemisorbed on Rh(111) is probed in a careful high-resolution study showing that this structure arises from internal molecular vibrations rather than from other chemically-shifted carbon atoms. It is shown by comparison of the adsorbate and gas-phase spectra that the underlying features are the same despite differences arising from adsorption. This new approach to the investigation of adsorbed molecules may prove to be useful in further studies of other systems and the possibility that such effects may exist could lead to the reinterpretation of other adsorbate systems.