Molecular orbital studies of dinitrogen tetroxide and related molecules |
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Authors: | RL Griffiths RGAR Maclagan LF Phillips |
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Institution: | Department of Chemistry. University of Canterbury, Christchurch, New Zealand |
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Abstract: | Hartree-Fock LCAO MO calculations for N2O4 have been performed in a basis of symmetry orbitals formed from a minimal Slater basis set. Effects of rounding and truncation errors were minimized by the use of the symmetry basis, which also allowed the order or tilling of molecular orbitals to be specified independently of orbital energies. Convergence difficulties were overcome by combined use of the conjugate gradients method and Roothaan's iterative procedure; the method of steepest descents was less effective than either of these. Multicentre ‘non-NDDO’ two-electron integrals were evaluated by the gaussian expansion technique. The wavefunction obtained for the lowest state is NN antibonding, largely as a result of the filling of the 6b1u antibonding sigma orbital in preference to the 6ag bonding sigma orbital. There is only a small amount of NN pi-bonding. A bond energy analysis shows that the lowest state is markedly stabilized by NNO three-centre interactions. |
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