The electronic structure and localized molecular orbitals in S₄N₄ by the CNDO/BW theory

Abstract

The energies calculated for tetranitrogen tetrasulfide, S₄N₄, by the CNDO/BW theory favor a structure with coplanar nitrogen atoms and not a structure with coplanar sulfur atoms. Both structures have been proposed from experimental studies. Localized molecular orbitals are calculated for S₄N₄ and used to choose the appropriate Lewis structure for the molecule. The hybridization at the nitrogen and sulfur atoms is discussed. There is electron delocalization in the molecule, the S-N bond is a bent bond involving pure p-orbitals on the sulfur and nitrogen atoms and there is a pure p-bent bond between the sulfur atoms on the same side of the coplanar nitrogen atoms. There is no N-N bond in S₄N₄.