Towards Complementary Characterization of the Chemical Bond

TL;DR

This paper rigorously characterizes chemical bonds by analyzing two-particle wave functions, introducing measures of covalency, atomicity, and ionicity, and tracing their evolution from molecular to atomic states.

Contribution

It provides a new rigorous framework for analyzing chemical bonds using two-particle wave functions, linking covalency, atomicity, and Mott-Hubbard atomicity.

Findings

Defined and determined intrinsic covalency and atomicity in  molecule.

Established a systematic evolution of molecular states with interatomic distance.

Connected covalency and ionicity to Mott-Hubbard atomicity.

Abstract

A precise discussion of a single bond requires consideration of two-particle wave function for the particles involved. Here we define and determine rigorously the intrinsic covalency and connected characteristics on the canonical example of \ch{H2} molecule. This is achieved by starting from analytic form for the two--particle wave function for electrons forming the bond, in which we single out the atomic contribution (\textit{atomicity}) in an unequivocal manner. The presence the of atomicity and ionicity factors complements the existing attributes of the bond. In this way, a gradual evolution of the molecular state to its two-atomic correspondant is traced systematically with increasing interatomic distance. In effect, a direct relation to the onset of incipient Mott-Hubbard atomicity (\textit{Mottness}) to the intrinsic covalency and ionicity is established. This goal is achieved by combining the single--particle wave function readjustment with a simultaneous determination of two--particle states in the particle (second--quantization) representation.