Energy partitioning for generalized product functions: The interferencecontribution to the energy of generalized valence bond and spin coupled wave functions

摘要

The main driving force for the formation of the covalent bond is the quantum-mechanicalinterference effect among one-electron states, as has been suggested in several works by the use ofpartition schemes to calculate the interference contributions to the energy. However, due to somedifficulties associated with the original approaches, calculations were only carried out for a few,mostly diatomic molecules. In this work, we propose a general approach of partitioning based ongeneralized product functions with generalized valence bond at the perfect pairing approximationand spin-coupled groups, which should allow the investigation of a broader array of molecules, andhopefully, shed light on the nature of the chemical bond in molecules with unusual chemicalfeatures. Among other things, this approach lends itself naturally to the investigation of interferencein individual bonds or groups of bonds in a molecule.