A density functional study of Fe(SINGLE BOND)N2, Fe(SINGLE BOND)N+2, and Fe(SINGLE BOND)N?2

The interaction of an iron atom with molecular nitrogen was studied using density functional theory. Calculations were of the all-electron type and both conventional local and gradient-dependent models were used. A ground state of linear structure was found for Fe(SINGLE BOND)N2, with 2S + 1 = 3, whereas the triangular Fe(SINGLE BOND)N2 geometry, of C2v symmetry, was located 2.1 kcal/mol higher in energy, at least for the gradient-dependent model. The reversed order was found using the conventional local approximation. In Fe(SINGLE BOND)N2, the N(SINGLE BOND)N bond is strongly perturbed by the iron atom: It has a bond order of 2.4, a vibrational frequency of 1886 cm−1, and an equilibrium bond length of 1.16 Å: These values are 3.0, 2359 cm−1, and 1.095 Å, respectively, for the free N2 molecule. With the gradient-dependent model and corrections for nonsphericity of the Fe atom, a very small binding energy, 8.8 kcal/mol, was calculated for Fe(SINGLE BOND)N2. Quartet ground states were found for both Fe(SINGLE BOND)N+2 and Fe(SINGLE BOND)N−2. The adiabatic ionization potential, electron affinity, and electronegativity were also computed; the predicted values are 7.2, 1.22, and 4.2 eV, respectively. © 1997 John Wiley & Sons, Inc.