The energy-loss spectrum associated with scattering of 100-keV H+ ions from K, Rb, and Cs atoms adsorbed on Al(111) has been investigated both experimentally and theoretically. Theoretical simulations were conducted based on calculations of the energy loss experienced in specific ion trajectories at the surface, using coupled-channel calculations to describe inner-shell ionization and excitation as a function of impact parameter. The energy losses can be attributed entirely to single atomic collisions from the alkali atoms, and the experiments reproduce the markedly increased asymmetry in scattering from Rb and Cs relative to K, attributable largely to the role of 3d and 4d excitations, respectively, and particularly the role of multiple excitations of these states. For Rb and Cs scattering, the data show excellent quantitative agreement between theory and experiment; for the K scattering, a discrepancy of a low-energy shoulder is attributed to a problem associated with the sample preparation.