Molecular d-orbital exponents for phosphonitriles and sulphonitriles determined by an exchange overlap variation. Part 2.—Bond structure of the phosphonitriles and sulphonitriles

Abstract

The molecular exponent sets derived for phosphonitriles and sulphonitriles in part 1, ¹ are used to calculate the bonded overlap values from the exchange overlap approximation. The relation of these bonded overlap values to covalent bond energies and molecular energies is discussed. The exchange overlap variation (EOV)¹ optimization method is evaluated by correlating the calculated results with experimental properties, and is shown to be an acceptable approximation for the molecules considered. The EOV method predicts a chain nitrogen angle of 150–155° in the ionic linear phosphonitrile [Cl₃PNPCl₃]⁺ for a C_2v configuration.