Theoretica chimica acta

, Volume 82, Issue 3–4, pp 299–308 | Cite as

Electronic structure and the unimolecular reactions of imine peroixde HNOO

  • Takayuki Fueno
  • Keiichi Yokoyama
  • Shin-ya Takane
Article

Summary

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(3Σg) are investigated by the SCF and MRD-CI calculations employing the 6–31G** basis functions. HNOO in its ground state (1A′) 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(1A′) 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(1A′) 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.

Key words

Imine peroxide (HNOO) Diradicaloid Diradicals 1,3-Hydrogen migration Hydroperoxynitrene (NOOH) 

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Copyright information

© Springer-Verlag 1992

Authors and Affiliations

  • Takayuki Fueno
    • 1
  • Keiichi Yokoyama
    • 1
  • Shin-ya Takane
    • 1
  1. 1.Department of Chemistry, Faculty of Engineering ScienceOsaka UniversityToyonaka, OsakaJapan

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