This research article published Springer Nature Switzerland AG.,2008The geometric parameters, normal vibration frequencies, and thermochemical characteristics of the ions present in vapor over sodium fluoride, Na2F+, Na3F 2+, NaF 2−, and Na2F 3−, were calculated ab initio by the Hartree-Fock method and taking into account electron correlation. The main equilibrium configuration of all ions was found to be the linear configuration of D ∞h symmetry. Pentaatomic ions could also exist as two isomers, planar cyclic of C 2v symmetry and bipyramidal of D 3h symmetry. Their energies were higher than that of the D ∞h isomers, and their contents in vapor were negligibly low. The energies and enthalpies of dissociation of the ions with the elimination of the NaF molecule were calculated. The enthalpies of formation of the ions were obtained.