Relativistic Spin–Orbit Electronegativity and the Chemical Bond Between a Heavy Atom and a Light Atom

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F22%3A00119735" target="_blank" >RIV/00216224:14740/22:00119735 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1002/chem.202200277" target="_blank" >https://doi.org/10.1002/chem.202200277</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202200277" target="_blank" >10.1002/chem.202200277</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Relativistic Spin–Orbit Electronegativity and the Chemical Bond Between a Heavy Atom and a Light Atom

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Relativistic Spin–Orbit Electronegativity and the Chemical Bond Between a Heavy Atom and a Light Atom

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10400 - Chemical sciences

Projekt

<a href="/cs/project/GA21-06991S" target="_blank" >GA21-06991S: Relativistické efekty v paramagnetické NMR spektroskopii</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

28

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

„e202200277“

Kód UT WoS článku

000772517400001

EID výsledku v databázi Scopus

2-s2.0-85126901757