Global and local approaches to population analysis: bonding patterns in superheavy element compounds

TL;DR

This paper investigates the bonding patterns in superheavy element compounds using local and global density matrix analyses, revealing the importance of atomic spinor populations for understanding their unique chemical bonding.

Contribution

It introduces a novel approach analyzing local properties of molecular density matrices to understand superheavy element bonding, complementing existing global analysis methods.

Findings

Atomic spinor population differences are crucial for superheavy element bonding.

Local density matrix analysis aligns with global projection methods.

Relativistic effects significantly influence bonding patterns.

Abstract

Relativistic effective atomic configurations of superheavy elements Cn, Nh and Fl and their lighter homologues (Hg, Tl and Pb) in their simple compounds with fluorine and oxygen are determined using the analysis of local properties of molecular Kohn-Sham density matrices in the vicinity of heavy nuclei. The difference in populations of atomic spinors with the same orbital angular momentum and different total angular momenta is demonstrated to be essential for understanding the peculiarities of chemical bonding in superheavy element compounds. The results are fully compatible with those obtained by the relativistic iterative version of conventional projection analysis of global density matrices.