Valence Bond Studies of N2F+

Abstract

The results of STO-6G valence bond (VB) calculations for the linear cation N₂F⁺ show that (a) the dominant Lewis-type VB structures involve a single positive charge which is located on either of the nitrogen atoms, and (b) a small amount of N–F π-bonding arises primarily from the formation of one-electron N–F π-bonds. It is suggested that N–F π-bonding is one of several factors which are responsible for the shortening of the N–F bond of N₂F⁺ relative to that of NF₄⁺. Valence bond and bond length considerations imply that the extent of N–O π-bonding in N₂O and NO₄^3- exceeds the degree of N–F π-bonding in N₂F⁺ and NF₄⁺.