Activation of Dinitrogen with a Superalkali Species, Li3 F2.

The capability of the superalkali Li3 F2 to activate dinitrogen (N2 ) is presented. The (Li3 F2 )nN2 clusters (n=1-6) were investigated first at the MP2/6-311+G(3d2f,2df,2p)//B3LYP/6-311G(2d,d,p) level of theory. Clusters up to n=4 were also optimized through the CBS-QB3 composite model. The complete dissociation of N2 was confirmed through visualized molecular orbitals and bond order calculation. The N-N bond is weakened by the addition of Li3 F2 superalkali units. The enthalpy of atomization ΔatH0∘ and formation (ΔfH0∘ ), charge flows (Δq), binding energies, and the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital are calculated to help explain the N2 activation.