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Absolute transition probability measurement of nondipole valenceshell (7-70 eV) electronic transitions of SF6 by angleresolved electron energy loss spectroscopy (e ,2e) spectroscopy has been used to obtain information on the electronic properties of the SF 6 molecule, in particular on the valence states. The ordering of the orbitals given by ESCA spectroscopy has been confirmed. The measured electron momentum distributions are compared with the ones calculated from literature wave functions and show a poor agreement. Namely, it is shown that the minimum energy criterion that is successful in calculating the energy eigenvalues is not always sufficient to determine a good wave function basis set suitable to reproduce other chemical-physics properties. Bonding character of the three outermost orbitals is evidenced well by their momentum distributions; two configuration interaction peaks following the valence orbitals are characterized as well.3182