Portal de Periódicos da CAPES

Molecular Orbital Treatment of Nitric Oxide Radicals. I. Electronic Structure and Spectrum of the H 2 NO Radical

1969; Oxford University Press; Volume: 42; Issue: 1 Linguagem: Inglês

10.1246/bcsj.42.47

1348-0634

Osamu Kikuchi,

Electron Spin Resonance Studies

Abstract A theoretical treatment of the H2NO radical is presented. In the calculation, the approximate SCF method of Longuet-Higgins and Pople for open-shell molecules is applied to the valence electron system, the CNDO/2 approximation is adopted, and the molecular excited states are approximated by linear combinations of some doublet Slater determinants constructed by means of the SCF MO for the ground state. The results thus obtained for the electronic structure of the H2NO radical are discussed. The calculated spectrum for the H2NO radical shows that the longest wavelength band has the n→π* character, and the π→π* transition energy is smaller than that for the n→σ* transition. The π→π* transition energy, 5.77 eV, calculated by the method in which only the π-electrons were explicitly considered, indicated that the π→π* band falls into the area near 240 mμ. From the calculated results for the H2NO radical and the solvent effect on the absorption bands of aliphatic nitric oxide radicals, two bands, at 450 mμ, and 240 mμ, characteristic of the latter radicals have been assigned to the n→π* and π→π* transitions respectively.