The X-ray emissions in the interaction of 3–6 MeV Xe23+ ions into thick solid In target are measured. The projectile-to-target and target Lα/Lβ X-ray production intensity ratios are observed to strongly depend on the projectile energy. The dependence deviates from Coulomb ionization predictions, which implies the important roles of coupling between subshells and the activation of 4fσ rotational couplings for projectile energy larger than 5 MeV.