Interparticle correlations and chemical bonding from physical side: Covalency versus atomicity and ionicity
Abstract
In this Chapter we reexamine the concept of covalency and ionicity on example of the simplest molecules. First, starting from the exact expression for the two-particle wave function in the case of H2 molecule within the Heitler-London model, we demonstrate an unphysical behavior of the covalency at large interatomic distance which, within standard definition, reaches the maximal value in the limit of separated atoms. Second, we correct this deficiency by introducing the concept of atomicity, with the help of which, we define the true (intrinsic) covalency, as well as retain the precise concept of ionicity. We connect the introduced atomicity to the onset of Mott-Hubbard localization, adopted here from the well established notion in the condensed matter. The evolution from the molecular to atomic states develops rapidly with interatomic distance beyond the localization threshold. This brief overview is intented as pedagogical in nature, nonetheless is analyzed quantitatively for the case of H2 molecule. At the end, we outline a similar-type of model for the related case of the hydrogen bond on example of adenine-tymine pair. Methodologically, the approach is based on combining the first- (wave mechanics) and second-quantization into a single scheme of formal description.