Total L-shell ionisation cross sections have been investigated for the collision systems Ge-Ge, Kr-Kr, In-In, MO-MO and Xe-Xe by measuring the x-ray yield in the impact energy range 50 keV< E,,,<3 MeV. Energy steps between 2.5 and 40 keV were selected in order to get detailed information about the ionisation threshold behaviour. The influence of multiple collisions on the ionisation process was studied by comparing the x-ray yield obtained from gaseous and solid targets. The experimental data were compared with theoretical results deduced from coupled-state as well as simplified two-state calculations. We found that in addition to the well known 4fp-4f8-4fr-4fu rotational coupling with the initially unoccupied 4fp MO further couplings with orbitals originating from the M shell have to be included in order to explain satisfactorily the observed structure in the threshold cross sections.