The adsorption of ethyl pyruvate on Pt(111) at low temperature was investig
ated by XP and UP spectroscopy. The assignment of the photoelectron spectra
was assisted by calculation of correlated ionization potentials. Compariso
n of the XP and UP spectra of the condensed and chemisorbed layer indicates
a strong ethyl pyruvate adsorption bond in the latter. Upon chemisorption,
the HOMO of ethyl pyruvate, which is a lone-pair orbital delocalized over
both C=O groups, is stabilized by about 0.7 eV with respect to the other or
bitals, which is characteristic for a lone-pair bonding mechanism. The same
bonding mechanism was found for coverages far below saturation. The XP spe
ctra further indicate that the ketone C=O is more strongly involved in the
chemisorption bond than the carboxyl C=O of ethyl pyruvate. The packing den
sity of the saturated chemisorbed ethyl pyruvate layer, as determined by XP
S, is high. This points toward an upright or tilted orientation of ethyl py
ruvate in this layer, in line with the observed bonding mechanism.