Measurements ofK&agr; andK&bgr; x rays induced by proton and &agr;‐particle beams from an electrostatic accelerator show a divergence from the normal x‐ray spectra as the nuclear charge increases. These measurements are consistent with the explanation that the ion excitation produces multiple inner‐shell electron vacancies, which in turn cause electronic‐shell energy shifts. The intensity of these shifted lines is a measure of the amount of multiple inner‐shell ionization.