Molecular orbital study of molecular nitrogen fixation

The model systems of molecular nitrogen fixation [N2 + H]⋅, [N2 + H]+, [N2 + H]−, [N2 + H2], [N2 + H2]+, and [N2 + H2]− were studied by the semiempirical INDO method. The study was based on the formal analogy between the catalytic reactions and the photochemical, radical, and ionic reactions on the other side. Symmetrical and donor‐acceptor properties of necessary catalytic systems were proposed using the dependence of energy characteristics and electron structure on reaction coordinate. On the basis of this MO study we have proposed the appropriate symmetry types of catalysts for each of acceptable models of nitrogen fixation. For one of the proposed systems there was realised a model MO computation with explicit inclusion of atoms of transition metals (Fe, V).