Interparticle correlations and chemical bonding from physical side: Covalency $\textit{versus}$ atomicity and ionicity

TL;DR

This paper reexamines covalency and ionicity in molecules, introduces the concept of atomicity to correct covalency behavior at large distances, and connects these ideas to Mott-Hubbard localization, using $H_2$ as a case study.

Contribution

It introduces the concept of atomicity to refine covalency definitions and links molecular-to-atomic state transitions to localization phenomena.

Findings

Corrected covalency behavior at large interatomic distances

Defined true covalency and ionicity using atomicity

Connected molecular state evolution to Mott-Hubbard localization

Abstract

In this Chapter we reexamine the concept of $\textit{covalency}$ and $\textit{ionicity}$ on example of the simplest molecules. First, starting from the exact expression for the two-particle wave function in the case of $H_2$ 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 $\textit{atomicity}$, with the help of which, we define the $\textit{true}$ (intrinsic) $\textit{covalency}$, as well as retain the precise concept of $\textit{ionicity}$. 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 $H_2$ 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.