Usefulness of one electron properties in the study of the nitromethane-to-methyl nitrite rearrangement

Large-scale multiple reference configuration interaction calculations for a unimolecular rearrangement reaction of nitromethane to methyl nitrite are presented. The complicated structure of potential energy curves is explained in terms of interactions between ground and excited states. An explanation for an extremely long C--N and C--O bond distances in the transition state is also given. The study of corresponding dipole moments and electrostatic molecular potentials enhances the overall understanding of the reaction.