The relative level populations in beam-foil excited sodium-like argon (Ar VIII) and copper-like krypton (Kr VIII) have been studied at 2 MeV projectile energy. In Ar VIII, the 3p and the 3d terms are strongly excited. The level population decreases rapidly with increasing value of the principal quantum number n, reaches a minimum for levels with n=5 or 6, but increases then and reaches a strong maximum for levels with n≅11. Also the Kr VIII data show a population maximum for levels with n=11. The strong 3p and 3rd level excitations in Ar VIII are explained as selective inner-shell processes which can be understood in the molecular-orbital electron-promotion picture. The preferential population of high-lying Rydberg states is explained as resulting from a near-resonance electron transfer from the valence band of the carbon foil to the projectile. This process takes place when the projectile leaves the back of the foil.