Adsorption of Ag on Pt(100) surfaces including the multilayer regime h
as been studied using the low energy electron diffraction, X-ray photo
electron spectroscopy, ultraviolet electron spectroscopy, and thermal
desorption spectroscopy methods. Deposition of Ag sub-monolayers on Pt
(100) below 300 K leads to the formation of three-dimensional crystall
ites, which decompose into a pseudomorphic layer upon annealing above
approximate to 350 K. Deposition of Ag multilayers proceeds along the
same growth mode. Adsorbed Ag lifts the hex reconstruction of the Pt(1
00) surface. Up to an Ag coverage of approximate to 0.8, Ag desorbs ac
cording to a zero-order desorption rate law, E(des) = 322 kJ mol(-1).
This desorption order is interpreted by the presence of a mixed Pt/Ag
layer on top of the square Pt(100) substrate into which all excess Pt
atoms from the hex surface are expelled upon lifting of the reconstruc
tion. Therefore, Ag desorption reflects the decomposition of a monolay
er-confined Ag-Pt alloy. Between Ag coverages of Theta approximate to
0.7 and Theta = 1, first-order desorption is observed, while above The
ta = 1 zero-order desorption is again observed (E(des) = 288 kJ mol(-1
)). A 760 K annealed Ag monolayer suffices to suppress CO adsorption.
XP spectra reveal a binding energy shift of the Ag 3d(5/2) level from
367.5 eV (monolayer) to 368.1 eV (thick multilayer). In UP spectra an
Ag/Pt(100) interface state at 1.5 eV below the Fermi level is observed
, which is interpreted to stem from Pt 5d electrons. Low-temperature d
eposited Ag sub-monolayers exhibit in IP spectra a broad 4d band struc
ture, which collapses upon annealing into two extremely narrow AE 4d e
mission peaks, Delta E approximate to 0.2 eV, at 4.6 eV and 4.8 eV. Th
ey are interpreted as emission from chain-like structures of Ag atoms
in the mixed Pt/Ag layer structures which are formed in the annealing
process.