Relativistic Spin-Orbit Electronegativity and the Chemical Bond Between a Heavy Atom and a Light Atom
Status PubMed-not-MEDLINE Jazyk angličtina Země Německo Médium print-electronic
Typ dokumentu časopisecké články
Grantová podpora
21-06991S
Grantová Agentura České Republiky
LM2018140
Ministerstvo Školství, Mládeže a Tělovýchovy
2/0135/21
Agentúra Ministerstva Školstva, Vedy, Výskumu a Športu SR
APVV-19-0516
Agentúra na Podporu Výskumu a Vývoja
PubMed
35229922
DOI
10.1002/chem.202200277
Knihovny.cz E-zdroje
- Klíčová slova
- bond distances, bond theory, electron charge density, quantum chemistry, spin-orbit coupling,
- Publikační typ
- časopisecké články MeSH
Relativistic effects are known to alter the chemical bonds and spectroscopic properties of heavy-element compounds. In this work, we introduce the concept of spin-orbit (SO) electronegativity of a heavy atom, as reflected by an SO-induced change in the interatomic distance between the heavy atom (HA) and a neighboring light atom (LA). We provide a transparent interpretation of these SO effects by using the concept of spin-orbit electron deformation density (SO-EDD). Spin-orbit coupling at the HA induces rearrangement of the electron density for the scalar-relativistically optimized geometry that, in turn, exerts a new force on the LA. The resulting expansion or contraction of the HA-LA bond depends on the nature and electron configuration of the HA. In addition, we quantify the change in atomic electronegativity induced by SO coupling for a series of hydrides, thereby complementing the SO-EDD picture. The trends in the SO-induced electronegativity and the HA-LA bond length across the periodic table of elements are demonstrated and interpreted, and also linked, intuitively, with the SO-induced NMR shielding at the LA.
CEITEC Central European Institute of Technology Masaryk University Kamenice 5 62500 Brno Czechia
Department of Chemistry Faculty of Science Masaryk University Kamenice 5 62500 Brno Czechia
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Quadratic Spin-Orbit Mechanism of the Electronic g-Tensor
