Intermolecular Covalent Interactions: Nature and Directionality

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F62690094%3A18450%2F23%3A50020112" target="_blank" >RIV/62690094:18450/23:50020112 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202203791" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202203791</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202203791" target="_blank" >10.1002/chem.202203791</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Intermolecular Covalent Interactions: Nature and Directionality

Popis výsledku v původním jazyce

Quantum chemical methods were employed to analyze the nature and the origin of the directionality of pnictogen (PnB), chalcogen (ChB), and halogen bonds (XB) in archetypal FmZ⋅⋅⋅F− complexes (Z=Pn, Ch, X), using relativistic density functional theory (DFT) at ZORA-M06/QZ4P. Quantitative Kohn-Sham MO and energy decomposition analyses (EDA) show that all these intermolecular interactions have in common that covalence, that is, HOMO−LUMO interactions, provide a crucial contribution to the bond energy, besides electrostatic attraction. Strikingly, all these bonds are directional (i.e., F−Z⋅⋅⋅F− is approximately linear) despite, and not because of, the electrostatic interactions which, in fact, favor bending. This constitutes a breakdown of the σ-hole model. It was shown how the σ-hole model fails by neglecting both, the essential physics behind the electrostatic interaction and that behind the directionality of electron-rich intermolecular interactions. Our findings are general and extend to the neutral, weaker ClI⋅⋅⋅NH3, HClTe⋅⋅⋅NH3, and H2ClSb⋅⋅⋅NH3 complexes. © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Název v anglickém jazyce

Intermolecular Covalent Interactions: Nature and Directionality

Popis výsledku anglicky

Quantum chemical methods were employed to analyze the nature and the origin of the directionality of pnictogen (PnB), chalcogen (ChB), and halogen bonds (XB) in archetypal FmZ⋅⋅⋅F− complexes (Z=Pn, Ch, X), using relativistic density functional theory (DFT) at ZORA-M06/QZ4P. Quantitative Kohn-Sham MO and energy decomposition analyses (EDA) show that all these intermolecular interactions have in common that covalence, that is, HOMO−LUMO interactions, provide a crucial contribution to the bond energy, besides electrostatic attraction. Strikingly, all these bonds are directional (i.e., F−Z⋅⋅⋅F− is approximately linear) despite, and not because of, the electrostatic interactions which, in fact, favor bending. This constitutes a breakdown of the σ-hole model. It was shown how the σ-hole model fails by neglecting both, the essential physics behind the electrostatic interaction and that behind the directionality of electron-rich intermolecular interactions. Our findings are general and extend to the neutral, weaker ClI⋅⋅⋅NH3, HClTe⋅⋅⋅NH3, and H2ClSb⋅⋅⋅NH3 complexes. © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

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

29

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

9

Strana od-do

"Article Numbere: e202203791"

Kód UT WoS článku

000921666000001

EID výsledku v databázi Scopus

2-s2.0-85147035317