ELECTRONIC AND GEOMETRIC STRUCTURE OF CLEAN PT3TI(111)

Photoemission spectra and scanning tunneling microscopy (STM) images of the clean Pt3Ti(111) surface are presented. Grazing-emission core-level spectra show that the topmost layer is pure platinum, modified compared with the Pt(111) surface. The Pt 4f levels at the surface are shifted 0.4 eV toward the Fermi level relative to bulk Pt3Ti while the Pt 4f and Ti 2p levels in the bulk are shifted 0.4 and 1.3 eV to higher binding energy relative to pure bulk platinum and titanium, respectively, Tunneling measurements show a surface with only metallic atoms and a small p(2 x 2) buckling. Our observations of molecularly adsorbed CO are not compatible with metallic titanium atoms at the surface and the STM data thus indirectly confirm that only platinum atoms are present in the topmost layer. Linear muffintin-orbital calculations of the bulk band structure and valence-band photoemission spectra reveal highly hybridized electron states between the Pt d and Ti d levels. The calculations give a minor charge transfer from Ti to Pt, 0.37 electrons per Ti atom, but the large core-level shifts reflect the stability of the alloy and the response to the excitation rather than the amount of charge transfer. The observed segregation of platinum to the surface and the altered electronic structure of the topmost layer, due to interaction with the underlying alloy, are in full agreement with earlier conclusions based on low-energy electron-diffraction measurements and on the chemical properties of the surface.