High-resolution electron spectroscopy of different adsorption states of ethylene on Pd(111)

The adsorption of ethylene at 100 K on clean and oxygen precovered Pd(1 1 1) surfaces and the thermal evolution of the ethylene adsorbate layers have been investigated experimentally by high-resolution electron energy loss spectroscopy (HREELS), high-resolution X-ray photoelectron spectroscopy with synchrotron radiation, thermal desorption spectroscopy and theoretically by ab initio density functional theory (DFT) calculations. On the clean Pd(1 1 1) surface at 100 K ethylene is adsorbed in a di-sigma bonding state, whereas on the oxygen precovered Pd(1 1 1)2 x 2-O surface the pi-bonded configuration is more stable; this has been established both experimentally and theoretically. Upon adsorption at room temperature ethylidyne adspecies are formed on both surfaces, but neither di-sigma nor pi-bonded ethylene transform into ethylidyne on heating from low temperature up to 450 K. Complete molecular desorption of ethylene is observed in both cases, with no signs of dehydrogenation. The spectroscopic data recorded during the thermal evolution of the low temperature adsorbate phase have been analysed with the help of DFT and indicate that pi-bonded ethylene adsorption states may become populated upon heating the low temperature adlayer to 350 K. (C) 2003 Elsevier B.V. All rights reserved.