Abstract: Surf. Sci. 345 (1996) 331-346

U. Gutdeutsch, E. Bertel, E. Cramer, J. C. Boettger, U. Birkenheuer, and N. Rösch
On the Adsorption Site of Ethylene on Ni(110). An Experimental and Theoretical Study Involving the Unoccupied Band Structure
Surf. Sci. 345 (1996) 331-346.
[Jan. 20, 1996]


The adsorption of ethylene on Ni(110) was investigated by angle resolved inverse photoemission (ARIPE) spectroscopy as well as by detailed density functional model cluster and slab model band structure calculations to clarify the preferred adsorption site. Cluster model calculations both at the local density as well as at the gradient corrected level of theory gave a slight preference for the di-sigma over the pi coordinated geometry on top of the ridges, but no or, at best, a very weak binding over the troughs. A dispersionless band in the ARIPE spectra about 1.8 eV above E(F) is assigned to the band derived from the lowest unoccupied ethylene orbital, 1b(3g)(pi*). The surface state feature of the clean Ni(110) surface connecting the image state at <(Gamma)over bar> and the d(yz), state S-2 at (Y) over bar is lowered almost uniformly by 0.8 eV through the interaction with the adsorbate. For adsorption on top of the ridges in the so-called ''half-bridge'' position intermediate between the short bridge (di-sigma) and the top site (pi), the symmetry requirements imposed by the surface state band are ideally met by the second lowest unoccupied band of the adsorbate monolayer which changes its character from ethylene 4a(g) at Gamma' to 2b(3u) at Y'. A similarly strong and uniform interaction is not possible when ethylene adsorbs above the troughs. Taking all experimental and theoretical evidence together, the adsorption site in the densely packed c(2 x 4) C2H4/Ni(110) adsorption system is identified as the half-bridge position on top of the ridges.