Ultrafast charge transfer processes from adsorbates to substrates are belie
ved to occur on the timescale of (sub)-femtoseconds. In this paper we prese
nt experimental evidence for resonant tunneling of electrons at surfaces in
the time regime ranging from <1 to similar to 50 fs. The technique used to
measure these ultrafast processes is based on high-resolution spectroscopy
of the decay of core-excited states. We use the natural lifetime of the co
re-excited states, which is on the order of a few femtoseconds for the syst
ems investigated, as an internal clock of the adsorbate systems, (C) 2000 E
lsevier Science B.V. All rights reserved.