A CALCULATION OF THE H2O2 MOLECULE BY THE LCAO–MO–SCF METHOD

Abstract

The electronic structure of the hydrogen peroxide molecule in three different configurations, namely the cis, the trans, and the non-planar or skew forms, were calculated according to the LCAO–MO–SCF approximation. All the electrons were considered except those of the K-shell of the oxygen atoms. The orbitals of these atoms are essentially of the sp3 hybrid type. It was shown that the skew form of the molecule with an azimuthal angle Φ of about 120° is the most stable, due mainly to conjugation of the σ5 and σ6 orbitals of the oxygen atoms with the other molecular orbitals. On the contrary, in the cis and trans forms these two orbitals are non-bonding. Because of the approximate nature of the treatment, especially as regards the screening effect of the K-electrons, the calculated orbital energies are definitely too large. However, the heights found for the cis and the trans barriers are in a reasonable mutual ratio. Numerical values were also obtained for the ionization potentials and the dipole moment of the skew model; the latter result, 2.05 D, agrees well with the experimental data.