, Volume 82, Issue 3-4, pp 299-308

Electronic structure and the unimolecular reactions of imine peroixde HNOO

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Electronic structure and possible unimolecular reaction paths of a linear four-atom molecule HNOO to be formed by the addition of NH(3Σ) toward O2(3Σ g ) are investigated by the SCF and MRD-CI calculations employing the 6–31G** basis functions. HNOO in its ground state (1 A′) is an ozone-like diradicaloid, whose N–O binding energy is only 27 kJ/mol. Geometries and excitation energies of various diradical (excited) states, both singlet and triplet, are examined. The isomerization paths of the ground-state HNOO(1 A′) are traced by a multi-configuration (MC) SCF procedure and the activation barrier heights evaluated by the CI treatment. It has proved that energetically the most favorable is the 1,3-hydrogen migration to give hydroperoxynitrene NOOH(1 A′) with the barrier height of 62 kJ/mol. The nitrene should be extremely unstable; it is liable to be decomposed to NO + OH with virtually no activation barrier.