One-electron bonds are not “half-bonds”

Abstract

Despite the success of the molecular orbital (MO) and valence-bond (VB) models to describe the electronic structure and properties of molecules, neither MO nor VB provides an explanation for the nature of the chemical bond. The first to address this problem was Ruedenberg, who showed that chemical bonds result from quantum interference. He developed a method to calculate the interference contribution to the total electronic energy and density and applied it to molecules containing typical two-centre two-electron (2c-2e) covalent bonds. To test the generality of Ruedenberg's hypothesis, we developed a powerful Interference Energy Analysis (IEA) method to calculate the interference contributions of individual chemical bonds to the total energy of diatomic and polyatomic molecules, and showed that any two-electron bond, despite its polarity, results from quantum interference. Nevertheless, many stable molecules are experimentally known whose chemical structures clearly indicate the existence of two-centre one-electron bonds (2c-1e). Therefore, the question remains if quantum interference will be the dominant effect for these systems. This work describes the extension of the IEA for treating two-centre one-electron bonds, making use of a Generalised Product Function (GPF) built from spin coupled wave functions of N electrons in M orbitals, SC(N,M). Several diatomic and polyatomic molecules were analysed and whenever possible the results were compared with the analogous case of a two-electron bond. The results indicate that interference is the dominant effect for the one-electron bonds, which reinforces the role of quantum interference as the central element in chemical bonding theory.