Bond Orbitals and Bond Energy in Elementary Phosphorus

Abstract

A discussion of the relative stability of the P4 molecule and black phosphorus is carried out, with use of hybrid spd bond orbitals. The amount of strain in the P4 molecule, in which the bond angles are 60°, is calculated to be 22.8 kcal mole^–1. This value is shown to be compatible with thermochemical data; it corresponds to the value 51.3 kcal mole^–1 for the bond energy of the normal P-P bond. A structure is proposed for red phosphorus and other allotropic forms of the element, and some of their properties are discussed in relation to their structure.

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