High resolution NEXAFS studies of aromatic molecules adsorbed and condensed on Ni(111)

High resolution near-edge X-ray absorption fine structure measurements have been performed on benzene, pyridine and pyrazine adsorbed and condensed on Ni(111). The carbon K-edge multilayer data show the splitting of the e_2u level of benzene into b₁ and a₂ levels for pyridine and into b_3u and a_u levels for pyrazine; the corresponding π resonances are asymmetric due to the vibrational fine structure. At the nitrogen K-edge the transitions into the a₂ and a_u levels are not observed. The benzene data suggest that the Rydberg orbitais are quenched in the condensed phase and that the broad structure above a photon energy of ~ 300 eV is made up of (at least) two σ resonances. On adsorption the π resonances are considerably broadened at the adsorption edges of atoms which interact strongly with the substrate.