We investigate the influence of modifications of the surface charge-density
profile on photon-excited collective excitations of valence electrons, thr
ough a comparison of the angle- and energy-resolved photoyield of clean Al
and the Al/Na "surface alloy." Although the charge-density profile is consi
derably different for the clean and surface alloy systems, the Al multipole
plasmon energy is essentially similar, in contrast to what one might expec
t from simple charge-density arguments. A Na multipole plasmon is observed
only when excess Na is deposited over the surface alloy. We base a qualitat
ive explanation for these observations on results of surface electronic str
ucture calculations using total-energy density-functional theory.