Intermolecular Covalent Interactions: Nature and Directionality
The result's identifiers
Result code in 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>
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Intermolecular Covalent Interactions: Nature and Directionality
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10406 - Analytical chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Chemistry - a European Journal
ISSN
0947-6539
e-ISSN
1521-3765
Volume of the periodical
29
Issue of the periodical within the volume
14
Country of publishing house
DE - GERMANY
Number of pages
9
Pages from-to
"Article Numbere: e202203791"
UT code for WoS article
000921666000001
EID of the result in the Scopus database
2-s2.0-85147035317