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.