For the bond-length relaxed PES, at the six "fusion" configurations, the system dissociates as "F2 + Xe + F2" in an analogous manner to SiF4. All direct approaches to the "fusion" configurations display a more complex behaviour than is the case for SiF4 with symmetrical rings of maximal energies present at approximately 20° distant from the symmetric linear SL-4 configurations. This behaviour reflects the redox nature of the Xe -F2 system.