[en] We present full scale ab initio relativistic calculations for the L-K vacancy transfer in collisions of 208 MeV Ni²³⁺ on Ge-solid target. Our time dependent Dirac-Fock-Slater method allows to achieve a very accurate quantitative explanation for the experimental impact parameter-dependent Ni-K and Ge-K vacancy probabilities recently measured at GSI. Darmstadt in terms of dynamic creation and annihilation of Ni n=2 shell vacancies in the collision. Our calculations reveal that both the radial and rotational coupling between the molecular levels contribute to the L-K vacancy transfer. (orig.)