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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
