Effect of electronic degeneracy on interatomic interaction parameters

Abstract

The contribution into interatomic interactions for electrons forming ordinary and multiple covalent bonds is shown to depend on the degeneracy of their state. The additive characteristics of atoms or molecules involved in the description of interatomic interactions using the generalized charge theory (the so-called “electronic volumes”) differ for π and σ electrons by a factor of √2. An expression for the product of electronic volumes of atoms through their bond lengths is derived by matching the quantum-chemical description of the covalent bond and the generalized charge theory. A simple relationship between the length and multiplicity of a covalent bond and the atomic numbers of interacting atoms is deduced.