F-2(.+) ions have been generated in the external ion source of a FT-IC
R mass spectrometer, and their reactivity with a choice of neutrals, r
anging from noble gases to polyatomic molecules, has been investigated
. With the exception of He and Ne, all neutrals react with F-2(.+) at
the collision controlled limit, yielding predominantly electron transf
er and fragmentation products. Noteworthy, a formal F+ transfer proces
s takes place from the reaction of F-2(.+) With Ar, among the noble ga
ses, and with CO and N-2, among diatomic molecules. The unimolecular a
nd bimolecular reactivity of F2H+, obtained from the F-2(.+) reaction
with H-2, allowed the proton affinity of elemental fluorine (PA = 79 /- 5 kcal mol(-1)) ro be experimentally derived.